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 fibers. It can balance high elastic modulus and low linear expansion coefficient and can obtain a molten glass excellent in composition uniformity and clarity. The glass composition for glass fibers of the present invention contains, relative to the total amount, 42.00 to 70.00 mass% of SiO2, 10.00 to 30.00 mass% of Al2O3, 0.00 to 8.00 mass% of MgO, 0.00 to 5.00 mass% of CaO, 2.00 to 25.00 mass% of ZnO, 0.00 to 5.00 mass% of TiO2, 2.00 to 17.30 mass% of P2O5, and 0.01 to 2.00 mass% of MxOy (at least one or more oxides selected from the group consisting of Fe2O3, SnO2, CeO2, MnO2, Sb2O3, and As2O3), and the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the following formula (1). 0.088 ≤ (Z / P) x M 1 / 2 ≤ 3.554 … (1).

Description

TECHNICAL FIELD

[0001] The present application relates to a glass composition for glass fibers, a glass fiber, a glass fiber fabric, and a glass fiber-reinforced resin composition. BACKGROUND

[0002] Conventionally, glass fibers have been widely used in order to improve the strength of resin compositions.

[0003] In recent years, with the miniaturization and weight reduction of electronic devices, resin compositions such as printed wiring boards used in the electronic devices are required to have high rigidity and excellent dimensional stability. Therefore, glass fibers for reinforcing the above resin compositions are also required to have high elastic modulus and low linear expansion coefficient.

[0004] In order to achieve high elastic modulus and low linear expansion coefficient of glass fibers, the present applicant has filed a patent application for a glass composition for glass fibers containing ZnO and P2O5 (Japanese Patent Application No. 2023-029848, PCT / JP2023 / 014110). SUMMARY

[0005] PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] However, the glass fibers obtained by the glass composition for glass fibers described in Japanese Patent Application No. 2023-029848, PCT / JP2023 / 014110 have a problem in that the elastic modulus and the linear expansion coefficient are deviated.

[0007] The present inventors have conducted intensive studies on the cause of the above problem, and as a result, have found the following: When the glass composition for glass fibers is melted to produce a molten glass, ZnO and P2O5 are not easily dissolved in the initial stage of melting, and therefore, the composition of the molten glass is deviated due to insufficient stirring during melting, and the deviation of the composition of the molten glass is significantly generated in the glass composition for glass fibers containing both ZnO and P2O5, as a result, the elastic modulus and the linear expansion coefficient of the glass fibers obtained by using the molten glass are deviated.

[0008] Note that the aforementioned composition deviation of the molten glass in the present application is a deviation in which the composition gradually differs throughout the entirety inside the molten glass, and is different from a problem in which a heterogeneous glass region or a heterogeneous glass phase that differs in composition from the surrounding glass composition locally occurs, such as a wave, a phase separation. Note that the wave refers to a region of several mm or less in the shape of a bar having a glass composition that differs from the surrounding glass composition, and the phase separation refers to a phenomenon in which a single phase of a molten glass forms a glass phase of a different composition of several μm or less due to heating or the like. Such a heterogeneous glass region or a different glass phase differs greatly in composition from the surrounding glass, and can be observed with the naked eye or optically because it causes a difference in refractive index, but the aforementioned glass composition for glass fibers described in Japanese Patent Application No. 2023-029848, PCT / JP2023 / 014110 does not have a problem that can be found with the naked eye or the like, such as a wave or a phase separation.

[0009] That is, the aforementioned composition deviation of the molten glass in the present application is a result of in-depth research conducted by the present inventors in order to eliminate the aforementioned problem, and is a result that was first discovered by observation using a method described later.

[0010] Among them, as a method of stirring the molten glass in the melting of the molten glass, it is considered that adding Fe2O3, SnO2, CeO2, MnO2, Sb2O3, As2O3, or the like, which generates gas in the melting, to the glass composition for glass fibers. When the aforementioned component is added to the aforementioned glass composition for glass fibers, the component generates gas in the melting of the aforementioned molten glass, and the generated gas moves upward, and thus it is expected that the effect of stirring the molten glass can be obtained.

[0011] On the other hand, when the aforementioned component generates gas in the melting of the aforementioned molten glass, the clarity of the molten glass decreases, and a bubble (hollow portion) can be included in the glass filaments that constitute the aforementioned glass fibers, and when a glass fiber-reinforced resin composition using the glass fibers is made into a printed wiring board, there is a possibility that a problem that becomes a cause of a decrease in insulation reliability of the printed wiring board can occur.

[0012] Therefore, an object of the present application is to eliminate the aforementioned problem, and to provide a glass composition for glass fibers that can obtain glass fibers that have both a high elastic modulus and a low linear expansion coefficient, and can obtain a molten glass that is excellent in composition uniformity and clarity.

[0013] Means for solving the problem

[0014] As a result of repeated studies made by the present inventors in order to achieve the above object, it has been found that by adjusting the content of ZnO, P2O5, MxOy (at least one or more oxides selected from the group consisting of Fe2O3, SnO2, CeO2, MnO2, Sb2O3, As2O3) in a glass composition for glass fibers having a specific composition, a glass fiber having both a high elastic modulus and a low linear expansion coefficient can be obtained, and moreover, the composition uniformity of the molten glass can be achieved, and the amount of bubbles contained in the molten glass can be reduced, and the fining property of the molten glass is improved, thereby completing the present invention.

[0015] Therefore, the glass composition for glass fibers of the present invention is characterized by containing, in the total amount, SiO2 in the range of 42.00 to 70.00 mass%, Al2O3 in the range of 10.00 to 30.00 mass%, MgO in the range of 0.00 to 8.00 mass%, CaO in the range of 0.00 to 5.00 mass%, ZnO in the range of 2.00 to 25.00 mass%, TiO2 in the range of 0.00 to 5.00 mass%, P2O5 in the range of 2.00 to 17.30 mass%, and MxOy (at least one or more oxides selected from the group consisting of Fe2O3, SnO2, CeO2, MnO2, Sb2O3, As2O3) in the range of 0.01 to 2.00 mass% in total, the content Z of the ZnO, the content P of the P2O5, and the content M of the MxOy satisfying the following formula (1),

[0016] 0.088 ≤ (Z / P) x M 1 / 2 ≤ 3.554 … (1).

[0017] The glass composition for glass fibers of the present invention can obtain a glass fiber having both a high elastic modulus and a low linear expansion coefficient by containing, in the total amount, SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges, respectively.

[0018] wherein the glass fiber has a high elastic modulus means that the elastic modulus of the glass fiber is 70.0 GPa or more as measured by the following elastic modulus measurement method, and the glass fiber has a low linear expansion coefficient means that the linear expansion coefficient of the glass fiber is 3.0 ppm / K or less as calculated by the following linear expansion coefficient measurement method.

[0019] [Measurement method of elastic modulus]

[0020] First, a glass batch material adjusted to the composition of the above-described glass fiber glass composition is put into a platinum crucible having a diameter of 80 mm, and after being melted by heating at a temperature of 1650°C for 6 hours, the homogeneous glass block or glass chips are obtained by taking out the glass from the platinum crucible. Next, the obtained glass block or glass chips are heated at a temperature of 750°C for 8 hours to perform annealing, and the test pieces are obtained. Next, the test pieces are processed into the modulus of elasticity test pieces of 50 mm x 50 mm x 5 mm using a cutting machine such as a diamond cutter and a grinder, and the modulus of elasticity test pieces are used to measure the modulus of elasticity by the ultrasonic pulse method according to JIS R 1602: 1995.

[0021] 〔Measurement method of linear expansion coefficient〕

[0022] First, the test pieces prepared in the same manner as in the case of the measurement of the modulus of elasticity are processed into the linear expansion coefficient test pieces of 4 mm x 4 mm x 20 mm using a cutting machine such as a diamond cutter and a grinder. Next, the obtained linear expansion coefficient test pieces are heated at a temperature increasing rate of 10°C / minute, and the elongation is measured using a thermal expansion rate measuring device (manufactured by NETZSCH, product name: DIL402) in the temperature range of 50°C to 200°C, and the linear expansion coefficient is calculated from the elongation.

[0023] In addition, the glass fiber glass composition according to the present application contains SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy, each of which is contained in the above-described content range, and the content Z of the ZnO, the content P of the P2O5, and the content M of the MxOy satisfy the formula (1), whereby when the MxOy generates gas in the molten glass, the generated gas is incorporated into the fine bubbles present in the molten glass to form large bubbles, and the large bubbles easily float up to the upper portion of the molten glass and are easily separated from the molten glass. As a result, the clarity of the molten glass can be improved, and the bubbles (hollow portions) contained in the glass fiber obtained using the glass fiber glass composition can be reduced.

[0024] Here, the high clarity of the molten glass means that the number of bubbles per g of glass block measured using the following evaluation method of clarity is 150 or more and less than 1000.

[0025] 〔Evaluation method of clarity〕

[0026] First, a glass batch adjusted to the composition of the above-described glass fiber-use glass composition is put into a platinum crucible of 80 mm in diameter, and after being melted at a temperature of 1600°C for 3 hours, it is taken out of the platinum crucible to obtain a glass block. Next, after the obtained glass block is heated at a temperature of 750°C for 2 hours, it is cooled to room temperature over 8 hours to perform annealing, thereby obtaining a test piece. Next, the center portion of the obtained test piece is cut out to a size of 10 mm x 15 mm using a cutting machine such as a diamond cutter, and the surface thereof is polished with a polishing paper of #2000. Next, the number of bubbles contained in the above-described test piece whose surface is polished is measured using an optical microscope.

[0027] Further, according to the glass fiber-use glass composition of the present application, by stirring the molten glass when the large bubbles float to the upper portion of the molten glass, ZnO and P2O5 are easily dissolved, and the composition uniformity of the molten glass can be achieved.

[0028] Here, the composition uniformity of the molten glass means that the composition uniformity calculated by the following composition uniformity evaluation method is 10.0% or less.

[0029] 〔Composition uniformity evaluation method〕

[0030] First, the center portion of the test piece obtained in the same manner as in the case of the above-described clarity evaluation method is cut out to a size of 10 mm x 15 mm using a cutting machine such as a diamond cutter, and the side surface thereof is polished with a polishing paper of #2000. Next, the side surface of the above-described test piece whose surface is polished is subjected to composition analysis using EDS (Energy Dispersive Spectroscopy), and the composition difference between the upper surface region and the bottom surface region is evaluated. Specifically, a field emission type scanning electron microscope (FE-SEM, manufactured by JEOL Ltd., model number: JSM-IT800) and an energy dispersive spectroscopy device (manufactured by JEOL Ltd., model number: EDS30mm 2 detector) are used to measure the composition of an arbitrary 100 μm 2The area measurement was performed in the above view, and the content rate (%) of each element contained in the glass composition for glass fibers was measured as an oxide conversion. Note that the content rate of each element as an oxide conversion was measured for three different regions of the upper surface region and the bottom surface region, and the average of the measurement results of the three regions was used as the content rate of each element as an oxide conversion. For each element, the absolute value of the difference between the content rate as an oxide conversion of the upper surface region and the content rate as an oxide conversion of the bottom surface region was calculated, and the calculation was performed for all the detected elements. The value obtained by adding the absolute values of the difference in the above content rate of all the elements was used as the composition uniformity. Note that the smaller the numerical value of the composition uniformity, the smaller the deviation in the composition of the molten glass (the more excellent the uniformity).

[0031] In addition, it is preferable that the glass composition for glass fibers of the present application contain SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges with respect to the total amount, respectively, and the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the following formula (2).

[0032] 0.183 ≤ (Z / P) x M 1 / 2 ≤ 1.775 … (2)

[0033] The glass composition for glass fibers of the present application contains SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges with respect to the total amount, respectively, and the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy formula (2), whereby a glass fiber having a high elastic modulus and a low linear expansion coefficient can be obtained, the composition of the molten glass can be made more uniform, and the fining property of the molten glass can be further improved.

[0034] Further improvement in the fining property of the molten glass means that the number of bubbles per g of glass block measured by the above evaluation method of the fining property is less than 150. In addition, the composition of the molten glass being made more uniform means that the composition uniformity calculated by the above evaluation method of the composition uniformity is 8.0% or less.

[0035] Further, preferably, the glass composition for glass fibers of the present application contains SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges, respectively, with respect to the total amount, and when the content rate Z of the above ZnO, the content rate P of the above P2O5, and the content rate M of the above MxOy satisfy the formula (2), further contains Fe2O3 in the range of 0.01 to 2.00 mass% and SnO2 in the range of 0.01 to 2.00 mass%, and the content rate F of the above Fe2O3 and the content rate S of the above SnO2 satisfy the following formula (3).

[0036] 0.06 ≤ S / F ≤ 40.75... (3)

[0037] The glass composition for glass fibers of the present application contains SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges, respectively, with respect to the total amount, and when the content rate Z of the above ZnO, the content rate P of the above P2O5, and the content rate M of the above MxOy satisfy the formula (2), further contains Fe2O3 in the range of 0.01 to 2.00 mass% and SnO2 in the range of 0.01 to 2.00 mass%, and the content rate F of the above Fe2O3 and the content rate S of the above SnO2 satisfy the formula (3), whereby a glass fiber having a high elastic modulus and a low linear expansion coefficient can be obtained, the fining property of the molten glass can be further improved, and further uniformity of the composition of the molten glass can be achieved.

[0038] wherein the further uniformity of the composition of the molten glass means that the uniformity of the composition calculated by the aforementioned evaluation method of the uniformity of the composition is 5.0% or less.

[0039] Further, preferably, the glass composition for glass fibers of the present application contains SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges, respectively, with respect to the total amount, and when the content rate Z of the above ZnO, the content rate P of the above P2O5, and the content rate M of the above MxOy satisfy the formula (2), further contains Fe2O3 in the range of 0.01 to 2.00 mass% and SnO2 in the range of 0.01 to 2.00 mass%, and the content rate F of the above Fe2O3 and the content rate S of the above SnO2 satisfy the following formula (3).

[0040] 0.183 ≤ (Z / P) x M 1 / 2 ≤ 0.582... (4)

[0041] The glass composition for glass fibers of the present application contains SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges, respectively, with respect to the total amount, and when the content rate Z of the above ZnO, the content rate P of the above P2O5, and the content rate M of the above MxOy satisfy the formula (2), further contains Fe2O3 in the range of 0.01 to 2.00 mass% and SnO2 in the range of 0.01 to 2.00 mass%, and the content rate F of the above Fe2O3 and the content rate S of the above SnO2 satisfy the formula (3), whereby a glass fiber having a high elastic modulus and a low linear expansion coefficient can be obtained, the fining property of the molten glass can be further improved, and further uniformity of the composition of the molten glass can be achieved.

[0042] wherein the more uniform composition of the molten glass means that the composition uniformity calculated by the aforementioned evaluation method of composition uniformity is 3.0% or less.

[0043] The glass fiber of the present application is characterized by comprising a glass filament formed from any one of the aforementioned glass compositions for glass fiber. In addition, the glass fiber fabric or the glass fiber-reinforced resin composition of the present application is characterized by comprising the glass fiber of the present application. DETAILED DESCRIPTION

[0044] Next, the embodiments of the present application are further described in detail.

[0045] The glass composition for glass fiber of the first embodiment in the present embodiment contains, relative to the total amount, SiO2 in the range of 42.00 to 70.00 mass%, Al2O3 in the range of 10.00 to 30.00 mass%, MgO in the range of 0.00 to 8.00 mass%, CaO in the range of 0.00 to 5.00 mass%, ZnO in the range of 2.00 to 25.00 mass%, TiO2 in the range of 0.00 to 5.00 mass%, P2O5 in the range of 2.00 to 17.30 mass%, MxOy (at least one or more oxides selected from the group consisting of Fe2O3, SnO2, CeO2, MnO2, Sb2O3, As2O3) in the range of 0.01 to 2.00 mass% in total, the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the following formula (1), and preferably the following formula (2).

[0046] 0.088 ≤ (Z / P) x M 1 / 2 ≤ 3.554 … (1)

[0047] 0.183 ≤ (Z / P) x M 1 / 2 ≤ 1.775 … (2)

[0048] The glass composition for glass fiber according to the first embodiment of the present embodiment, by containing SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the aforementioned ranges, respectively, relative to the total amount, enables to obtain a glass fiber having a high elastic modulus and a low linear expansion coefficient.

[0049] Further, according to the glass composition for glass fibers of the first embodiment of the present embodiment, SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy are contained in the above ranges with respect to the total amount, the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the formula (1), whereby when the MxOy generates gas in the molten glass, the generated gas is incorporated into the minute bubbles present in the molten glass to form large bubbles, and the large bubbles easily float to the upper portion of the molten glass to be separated from the molten glass. As a result, the fining property of the molten glass can be improved, and the bubbles (hollows) contained in the glass fibers obtained using the glass composition for glass fibers can be reduced. Further, by stirring the molten glass when the large bubbles float to the upper portion of the molten glass, the ZnO and the P2O5 are easily dissolved, and the composition uniformity of the molten glass can be achieved.

[0050] Note that, in the above molten glass, Fe2O3 mainly generates gas at a temperature in the range of 1400 to 1500°C, SnO2 mainly generates gas at a temperature in the range of 1500 to 1630°C, CeO2 generates gas at a temperature in the range of 1100 to 1400°C, MnO2 generates gas at a temperature in the range of 1100 to 1400°C, Sb2O3 generates gas at a temperature in the range of 1000 to 1300°C, and As2O3 generates gas at a temperature in the range of 1300 to 1600°C.

[0051] Further, according to the glass composition for glass fibers of the first embodiment of the present embodiment, SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy are contained in the above ranges with respect to the total amount, the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the formula (1), whereby when the MxOy generates gas in the molten glass, the generated gas is incorporated into the minute bubbles present in the molten glass to form large bubbles, and the large bubbles easily float to the upper portion of the molten glass to be separated from the molten glass. As a result, the fining property of the molten glass can be improved, and the bubbles (hollows) contained in the glass fibers obtained using the glass composition for glass fibers can be reduced. Further, by stirring the molten glass when the large bubbles float to the upper portion of the molten glass, the ZnO and the P2O5 are easily dissolved, and the composition uniformity of the molten glass can be achieved.

[0052] Further, the glass composition for glass fibers of the second embodiment of the present embodiment contains SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges with respect to the total amount, and when the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the formula (2), contains Fe2O3 in the range of 0.01 to 2.00% by mass and SnO2 in the range of 0.01 to 2.00% by mass, and the content rate F of the Fe2O3 and the content rate S of the SnO2 satisfy the following formula (3).

[0053] 0.06 ≤ S / F ≤ 40.75 … (3)

[0054] The glass composition for glass fibers according to the second embodiment of the present embodiment contains, with respect to the total amount, SiO2, Al2O3, MgO, CaO, ZnO, TiO2, and MxOy in the above ranges, respectively, and when the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the formula (2), further contains Fe2O3 in the range of 0.01 to 2.00 mass% and SnO2 in the range of 0.01 to 2.00 mass%, the content rate F of the Fe2O3, and the content rate S of the SnO2 satisfy the formula (3), whereby it is possible to obtain glass fibers having high elastic modulus and low linear expansion coefficient, to further improve the fining property of the molten glass, and to achieve further uniformity of the composition of the molten glass.

[0055] Further, the glass composition for glass fibers according to the third embodiment of the present embodiment contains, with respect to the total amount, SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges, respectively, and the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the following formula (4).

[0056] 0.183 ≤ (Z / P) x M 1 / 2 ≤ 0.582 … (4)

[0057] The glass composition for glass fibers according to the third embodiment of the present embodiment contains, with respect to the total amount, SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5, and MxOy in the above ranges, respectively, and the content rate Z of the ZnO, the content rate P of the P2O5, and the content rate M of the MxOy satisfy the formula (4), whereby it is possible to obtain glass fibers having high elastic modulus and low linear expansion coefficient, to further improve the fining property of the molten glass, and to achieve further uniformity of the composition of the molten glass.

[0058] Note that in the glass composition for glass fibers in each of the embodiments of the present embodiment, if the value of Z / P becomes large, there is a tendency that the linear expansion coefficient of the obtained glass fibers becomes large, and if the value of Z / P becomes small, there is a tendency that the elastic modulus of the obtained glass fibers becomes small. On the other hand, if the value of M becomes large, the amount of gas generated in the molten glass becomes excessive, and there is a tendency that the fining property of the molten glass becomes poor, and if the value of M becomes small, the amount of gas generated in the molten glass is not sufficient to stir the molten glass, and there is a tendency that the uniformity and the fining property of the molten glass become poor.

[0059] Therefore, it can be considered that the value of (Z / P) x M 1 / 2 represents the balance between the linear expansion coefficient and the elastic modulus of the obtained glass fibers and the fining property and the uniformity of the composition of the molten glass.

[0060] Further, in the glass composition for glass fibers of the second embodiment of the present embodiment, if the value of S / F becomes large, the effect of stirring the molten glass in the temperature range of 1400 to 1500°C becomes insufficient, and thus there is a tendency that the uniformity of the composition of the molten glass becomes poor, and if the value of S / F becomes small, the effect of stirring the molten glass in the temperature range of 1500 to 1630°C and the effect of entraining the fine bubbles become insufficient, and thus there is a tendency that the uniformity and the fining of the composition of the molten glass become poor. Therefore, it is considered that the value of S / F represents the balance between the stirring effect of the molten glass in the temperature range of 1400 to 1500°C and the stirring effect of the molten glass in the temperature range of 1500 to 1630°C.

[0061] The value of S / F is preferably in the range of 0.20 to 14.00, more preferably in the range of 0.30 to 1.40.

[0062] In the glass composition for glass fibers of each aspect of the present embodiment, when the content ratio of SiO2 with respect to the total amount of the glass composition for glass fibers is less than 42.00 mass%, the working temperature range becomes narrow, and crystallization occurs in the spinning, which can cause clogging of the nozzle. Further, when the content ratio of SiO2 exceeds 70.00 mass%, the 1000 poise temperature becomes high, the meltability becomes poor, and SiO2 that is not completely melted flows into the nozzle as a foreign matter, causing breakage in the spinning, and thus the productivity becomes poor.

[0063] In the glass composition for glass fibers of each aspect of the present embodiment, the content ratio of SiO2 with respect to the total amount of the glass composition for glass fibers is preferably in the range of 44.00 to 65.00 mass%, more preferably in the range of 45.00 to 62.60 mass%, further preferably in the range of 46.30 to 58.50 mass%, particularly preferably in the range of 47.90 to 55.90 mass%, and especially preferably in the range of 48.90 to 54.90 mass%.

[0064] In the glass composition for glass fibers of each aspect of the present embodiment, when the content ratio of Al2O3 with respect to the total amount of the glass composition for glass fibers is less than 10.00 mass%, the 1000 poise temperature becomes high, the meltability becomes poor, and the elastic modulus decreases. Further, when the content ratio of Al2O3 exceeds 30.00 mass%, crystallization easily occurs, and thus the working temperature range becomes narrow, and the spinnability becomes poor.

[0065] In the glass composition for glass fibers of each of the above-described aspects of the present embodiment, the content ratio of Al2O3 with respect to the total amount of the glass composition for glass fibers is preferably in the range of 19.50 to 28.40% by mass, more preferably in the range of 20.50 to 27.80% by mass, further preferably in the range of 22.10 to 27.20% by mass, particularly preferably in the range of 22.60 to 26.40% by mass, and especially preferably in the range of 23.20 to 25.80% by mass.

[0066] In the glass composition for glass fibers of each of the above-described aspects of the present embodiment, when the content ratio of MgO with respect to the total amount of the glass composition for glass fibers exceeds 8.00% by mass, a glass fiber having a small linear expansion coefficient cannot be obtained.

[0067] In the glass composition for glass fibers of each of the above-described aspects of the present embodiment, the content ratio of MgO with respect to the total amount of the glass composition for glass fibers is preferably in the range of 0.00 to 5.90% by mass, more preferably in the range of 0.50 to 5.40% by mass, further preferably in the range of 1.10 to 4.90% by mass, particularly preferably in the range of 1.50 to 4.40% by mass, especially preferably in the range of 1.90 to 2.70% by mass, and most preferably in the range of 2.60 to 3.60% by mass.

[0068] In the glass composition for glass fibers of each of the above-described aspects of the present embodiment, when the content ratio of CaO with respect to the total amount of the glass composition for glass fibers exceeds 5.00% by mass, the liquidus temperature becomes high and the spinnability becomes poor.

[0069] In the glass composition for glass fibers of each of the above-described aspects of the present embodiment, the content ratio of CaO with respect to the total amount of the glass composition for glass fibers is preferably in the range of 0.00 to 5.00% by mass, more preferably in the range of 0.00 to 2.50% by mass, further preferably in the range of 0.00 to 0.90% by mass, particularly preferably in the range of 0.00 to 0.40% by mass, especially preferably in the range of 0.00% by mass or more and less than 0.10% by mass, and most preferably in the range of 0.00% by mass or more and less than 0.05% by mass.

[0070] In the glass composition for glass fibers of each of the above-described aspects of the present embodiment, when the content ratio of ZnO with respect to the total amount of the glass composition for glass fibers is 2.00% by mass or less, the 1000-poise temperature becomes high and the meltability becomes poor. In addition, when the content ratio of ZnO exceeds 25.00% by mass, a glass fiber having a small linear expansion coefficient cannot be obtained.

[0071] In the glass composition for glass fibers of each aspect described above in the present embodiment, the content of ZnO with respect to the total amount of the glass composition for glass fibers is preferably in the range of 2.50 to 22.00 mass%, more preferably in the range of 3.0 to 18.00 mass%, further preferably in the range of 4.10 to 14.10 mass%, particularly preferably in the range of 5.20 to 11.00 mass%, especially preferably in the range of 6.00 to 10.10 mass%, and most preferably in the range of 6.50 to 9.50 mass%.

[0072] In the glass composition for glass fibers of each aspect described above in the present embodiment, when the content of Ti02 with respect to the total amount of the glass composition for glass fibers exceeds 5.00 mass%, it is not possible to reduce the melt viscosity while maintaining a low linear expansion coefficient. In addition, the liquidus temperature excessively increases, and the working temperature range becomes narrow.

[0073] In the glass composition for glass fibers of each aspect described above in the present embodiment, the content of Ti02 with respect to the total amount of the glass composition for glass fibers is preferably in the range of 0.00 to 2.50 mass%, more preferably in the range of 0.00 to 1.80 mass%, further preferably in the range of 0.00 to 1.20 mass%, and particularly preferably in the range of 0.00 to 0.90 mass%.

[0074] In the glass composition for glass fibers of each aspect described above in the present embodiment, when the content of P205 with respect to the total amount of the glass composition for glass fibers is less than 2.00 mass%, the working temperature range becomes narrow, and crystallization occurs during spinning, which can cause clogging of the nozzle. In addition, when the content of P205 exceeds 17.30 mass%, the 1000-poise temperature becomes high, the meltability becomes poor, the liquidus temperature becomes high, and it becomes difficult to perform spinning.

[0075] In the glass composition for glass fibers of each aspect described above in the present embodiment, the content of P205 with respect to the total amount of the glass composition for glass fibers is preferably in the range of 3.80 to 17.00 mass%, more preferably in the range of 5.50 to 15.50 mass%, further preferably in the range of 6.50 to 14.90 mass%, particularly preferably in the range of 8.30 to 13.50 mass%, especially preferably in the range of 10.10 to 13.60 mass%, and most preferably in the range of 11.00 to 13.30 mass%.

[0076] The glass composition for glass fibers of each aspect in the present embodiment contains MxOy in the range of 0.01 to 2.00 mass% with respect to the total amount of the glass composition for glass fibers.

[0077] MxOy is one or more oxides selected from the group consisting of Fe2O3, SnO2, CeO2, MnO2, Sb2O3, As2O3. In order to avoid contamination of the equipment due to volatilization at the time of melting, which leads to inability to use for a long period of time, MxOy is preferably one or more oxides selected from the group consisting of Fe2O3, SnO2, CeO2, MnO2, which are oxides of metal elements, and more preferably one or more oxides selected from the group consisting of Fe2O3, SnO2, MnO2, which are oxides other than rare earth elements, from the viewpoint of production cost, and further preferably one or more oxides selected from the group consisting of Fe2O3 and SnO2, from the viewpoint of low toxicity of raw materials.

[0078] In the glass composition for glass fibers of each aspect of the present embodiment, from the viewpoint that the stirring effect of the molten glass can be increased for a long period of time from the temperature rise of the molten glass from low temperature to high temperature by increasing the temperature region in which gas is generated, the glass composition for glass fibers of each aspect of the present embodiment preferably contains any two or more oxides selected from the above group, and more preferably contains Fe2O3 and SnO2.

[0079] Note that, in the case where the glass composition for glass fibers contains any two or more oxides selected from the above group as MxOy, the content rate M of MxOy represents the total content rate of all oxides contained in MxOy.

[0080] In the glass composition for glass fibers of each aspect of the present embodiment, when the content rate of MxOy with respect to the total amount of the glass composition for glass fibers is less than 0.01 mass%, an amount of gas sufficient to stir the molten glass cannot be generated in the molten glass. In addition, when the content rate of MxOy exceeds 2.00 mass%, the amount of gas generated in the molten glass is excessive, and the fining property of the molten glass is deteriorated.

[0081] In the glass composition for glass fibers of each aspect of the present embodiment, the content rate of MxOy with respect to the total amount of the glass composition for glass fibers is preferably in the range of 0.10 to 1.40 mass%, more preferably in the range of 0.15 to 1.20 mass%, further preferably in the range of 0.30 to 0.90 mass%, and particularly preferably in the range of 0.40 to 0.60 mass%.

[0082] In the case where the glass composition for glass fibers of each aspect of the present embodiment contains Fe2O3, SnO2, CeO2, MnO2, Sb2O3, and As2O3, the content of each of the components is independently in the range of 0.01 to 2.00% by mass, preferably in the range of 0.01 to 1.50% by mass, more preferably in the range of 0.10 to 0.90% by mass, further preferably in the range of 0.30 to 0.70% by mass, and particularly preferably in the range of 0.40 to 0.44% by mass, with respect to the total amount of the glass composition for glass fibers.

[0083] In the case where the glass composition for glass fibers of each aspect of the present embodiment contains Fe2O3and SnO2, the ratio (S / F) of the content S of the above SnO2to the content F of the above Fe2O3is preferably in the range of 0.06 to 40.75, more preferably in the range of 0.20 to 14.00, further preferably in the range of 0.25 to 4.90, and particularly preferably in the range of 0.30 to 1.40.

[0084] In addition, the glass composition for glass fibers of the present embodiment can contain ZrO2from the viewpoint of reducing the melting viscosity of the molten glass and thus easily achieving long fiberization. In the case where ZrO2is contained, the content of ZrO2with respect to the total amount of the glass composition for glass fibers is, for example, in the range of 3.00% by mass or less, preferably in the range of 1.00% by mass or less, more preferably in the range of 0.60% by mass or less, further preferably in the range of 0.40% by mass or less, particularly preferably in the range of 0.20% by mass or less, especially preferably in the range of 0.10% by mass or less, and most preferably in the range of 0.001% by mass or less.

[0085] The glass composition for glass fibers of the present embodiment can contain B2O3from the viewpoint of improving the spinnability and thus obtaining glass fibers having a small linear expansion coefficient. In the case where B2O3is contained, the content of B2O3with respect to the total amount of the glass composition for glass fibers is, for example, in the range of 10.00% by mass or less, preferably in the range of 7.90% by mass or less, more preferably in the range of 0.50 to 5.90% by mass, further preferably in the range of 1.00 to 4.80% by mass, and particularly preferably in the range of 1.50 to 3.50% by mass.

[0086] In addition, the glass composition for glass fibers of the present embodiment can contain F2and Cl2. In the case where the glass composition for glass fibers contains F2and Cl2, the total content of F2and Cl2with respect to the total amount of the glass composition for glass fibers is, for example, in the range of 3.00% by mass or less, preferably in the range of 1.00% by mass or less, more preferably in the range of 0.40% by mass or less, further preferably in the range of 0.20% by mass or less, particularly preferably in the range of 0.10% by mass or less, and especially preferably in the range of 0.001% by mass or less.

[0087] In addition, the glass composition for glass fibers of the present embodiment can contain Li2O, Na2O, and K2O. In the case where the glass composition for glass fibers contains Li2O, Na2O, and K2O, the total content of Li2O, Na2O, and K2O with respect to the total amount of the glass composition for glass fibers is, for example, in the range of 1.00% by mass or less, preferably in the range of 0.50% by mass or less, more preferably in the range of less than 0.10% by mass, further preferably in the range of 0.05% by mass or less, particularly preferably in the range of 0.02% by mass or less, particularly preferably in the range of 0.03% by mass or less, and most preferably in the range of 0.01% by mass or less, from the viewpoint that a large amount of Li2O, Na2O, and K2O contained in the glass composition for glass fibers can cause deterioration of water resistance and coefficient of linear expansion of the glass fibers.

[0088] In addition, in the glass composition for glass fibers of the present embodiment, the ratio of the content of P2O5 to the content of ZnO (P2O5 / ZnO) is preferably in the range of 0.40 to 5.60. When the ratio of the content of P2O5 to the content of ZnO (P2O5 / ZnO) is less than 0.40, there is a tendency that the working temperature range becomes small or the coefficient of linear expansion of the glass fibers formed from the glass composition for glass fibers becomes large, and when the ratio exceeds 5.60, there is a tendency that the 1000 poise temperature becomes excessively high. The ratio of the content of P2O5 to the content of ZnO (P2O5 / ZnO) is more preferably in the range of 0.70 to 4.50, further preferably in the range of 0.80 to 3.70, particularly preferably in the range of 0.90 to 2.80, and extremely preferably in the range of 0.95 to 2.00.

[0089] In the glass composition for glass fiber of this embodiment, the total content of SiO2, Al2O3, MgO, CaO, ZnO, TiO2, P2O5 and MxOy relative to the total amount is, for example, 91.0% by mass or more, preferably 95.0% by mass or more, more preferably 98.0% by mass or more, further preferably 99.0% by mass or more, particularly preferably 99.3% by mass, especially preferably 99.5% by mass or more, extremely preferably 99.7% by mass or more, and most preferably 99.9% by mass or more.

[0090] Furthermore, the glass composition for glass fiber in this embodiment may contain oxides of Sr, Ba, Co, Ni, Cu, Cr, Mo, W, Y, La, Bi, Gd, Pr, Sc, Pb, Cd, or Yb as impurities derived from raw materials in a range of less than 3.00% by mass relative to the total amount of the glass composition for glass fiber. Preferably, the glass composition for glass fiber may contain the aforementioned oxides in a range of less than 2.00% by mass, and more preferably, in a range of less than 1.00% by mass.

[0091] In particular, when the glass composition for glass fiber in this embodiment contains SrO, BaO, Y2O3, La2O3, Bi2O3, Gd2O3, Pr2O3, Sc2O3 or Yb2O3 as impurities, their content relative to the total amount of the glass composition for glass fiber is independently 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, especially preferably less than 0.01% by mass, and most preferably less than 0.001% by mass.

[0092] Regarding the determination of the content of each component in the aforementioned glass composition for glass fibers, the content of Li, as a light element, can be determined using an ICP-based spectral analyzer. Alternatively, the content of other elements can be determined using a wavelength dispersive X-ray fluorescence analyzer.

[0093] As a method for determination, the following methods can be cited. First, the glass batch is placed in a platinum crucible and kept at a temperature of 1650°C in an electric furnace for 6 hours, while being stirred and melted, thereby obtaining homogeneous molten glass. Alternatively, glass fibers are placed in a platinum crucible and kept at a temperature of 1650°C in an electric furnace for 6 hours, while being stirred and melted, thereby obtaining homogeneous molten glass.

[0094] The glass batch material is prepared by mixing glass raw materials. In addition, in the case where the glass fiber has organic matter attached to the surface thereof or the glass fiber is contained in an organic matter (resin) mainly as a reinforcing material, the organic matter is removed by, for example, heating in a muffle furnace at 300 to 650°C for 0.5 to 24 hours or the like, and then the glass fiber is used.

[0095] Next, the obtained molten glass is poured onto a carbon plate to form glass chips, and the glass chips are crushed and powdered to obtain a glass powder.

[0096] Next, for the measurement of Li as a light element, the glass powder is subjected to heat decomposition with an acid, and then subjected to quantitative analysis using an ICP emission spectrometer. For the measurement of other elements, the glass powder is molded into a disc shape using a press, and then subjected to quantitative analysis using a wavelength dispersion type fluorescence X-ray analysis device. The quantitative analysis using the wavelength dispersion type fluorescence X-ray analysis device can be performed by preparing a standard curve sample based on the results of measurement by the fundamental parameter method, and performing analysis by the standard curve method. Note that the content of each component in the standard curve sample can be quantitatively analyzed by an ICP emission spectrometer. These quantitative analysis results can be converted into oxides to calculate the content and total amount of each component, and the content rate (mass %) of each component can be calculated from these values.

[0097] The glass fiber of the present embodiment can be formed from the glass fiber glass composition of the present embodiment in each form described above, by the following method. First, the glass raw materials are prepared based on the components contained in the ore as a glass raw material, the content rate of each component, and the volatilization amount of each component during melting, so as to become the composition of the glass fiber glass composition of the present embodiment in each form described above. Next, the prepared glass raw materials (glass batch material) are supplied to a melting furnace, and melted at a temperature region of 1000 poise or higher, specifically, a temperature range of 1450 to 1650°C. Next, the glass batch material (molten glass) melted at the temperature range described above is ejected from 100 to 8000 nozzle tips or holes of a bushing controlled to a predetermined temperature, and cooled and solidified while being stretched at high speed by high-speed take-up, thereby forming a glass single fiber (glass filament).

[0098] The glass filaments that are extruded from one nozzle head or orifice and cooled and solidified when forming the glass fibers of the present embodiment generally have a circular cross-sectional shape with a diameter in the range of 2.0 to 35.0 μm. In applications where a low coefficient of linear expansion is required, the above glass filaments preferably have a diameter in the range of 3.0 to 6.0 μm, and more preferably have a diameter in the range of 3.0 to 4.5 μm. On the other hand, in cases where the nozzle head has a non-circular shape and has a protruding portion or a notched portion for quenching the molten glass, by controlling the temperature conditions, glass filaments having a non-circular (e.g., elliptical, oblong) cross-sectional shape can be obtained. In cases where the above glass filaments have 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 circle (converted fiber diameter) is, for example, in the range of 2.0 to 35.0 μm.

[0099] The glass fibers of the present embodiment generally have the shape of a glass fiber bundle (glass strand) in which the above glass filaments are bundled in the range of 10 to 8000, and have a weight in the range of 0.3 to 10000.0 tex (g / km).

[0100] The glass fibers of the present embodiment can take various forms such as yarns, fabrics, braids, nonwoven fabrics (including chopped strand mat, multi-axial nonwoven fabric), chopped strands, roving, powder, and the like, which are obtained by further processing the above glass strands.

[0101] The glass fiber-forming glass composition according to the present embodiment has a Young's modulus of the glass fiber obtained therefrom in the range of 70.0 GPa or greater, preferably in the range of 75.0 GPa or greater, more preferably in the range of 78.0 GPa or greater, and further preferably in the range of 79.0 GPa or greater, and while the upper limit is not particularly limited, it is particularly preferred to be in the range of 80.0 to 90.0 GPa, and especially preferred to be in the range of 81.0 to 86.0 GPa.

[0102] In addition, the glass fiber-forming glass composition according to the present embodiment has a coefficient of linear expansion of the glass fiber obtained therefrom in the range of 3.0 ppm / K or less, preferably in the range of 2.9 ppm / K or less, and more preferably in the range of less than 2.5 ppm / K, and while the lower limit is not particularly limited, it is further preferred to be in the range of 1.5 to 2.3 ppm / K, and particularly preferred to be in the range of 1.8 to 2.2 ppm / K.

[0103] Further, the glass fiber obtained from the glass composition for glass fiber according to the present embodiment has a dielectric constant in the range of preferably 4.4 to 5.4 at a measurement frequency of 10 GHz, and a dielectric loss tangent in the range of preferably 0.0030 to 0.0060 at a measurement frequency of 10 GHz.

[0104] For the purpose of improving the bundling of glass filaments, improving the adhesion of glass fibers to resins, improving the uniform dispersion of glass fibers in a mixture of a resin or an inorganic material, and the like, an organic substance can be coated on the surface of the glass fiber according to the present embodiment. As such an organic substance, starch, polyurethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (particularly, carboxylic acid-modified polypropylene), copolymer of (poly)carboxylic acid (particularly, maleic acid) and an unsaturated monomer, and the like can be given.

[0105] Further, the glass fiber according to the present embodiment can be coated with a resin composition including a silane coupling agent, a lubricant, a surfactant, and the like, in addition to being coated with these resins. Further, the glass fiber according to the present embodiment can be coated with a treatment agent composition including a silane coupling agent, a surfactant, and the like, instead of containing the above-described resins.

[0106] The glass fiber according to the present embodiment in a state not coated with a resin composition or a treatment agent composition is coated with such a resin composition or a treatment agent composition in a range of 0.1 to 2.0% by mass with respect to the mass of the glass fiber.

[0107] Note that the process of coating an organic substance on a glass fiber can be performed, for example, by applying a resin solution or a resin composition solution to the glass fiber using a known method such as a roll coater in the manufacturing process of the glass fiber, and then drying the glass fiber to which the resin solution or the resin composition solution is applied. Further, the coating of the glass fiber according to the present embodiment in the form of a fabric formed of the above-described organic substance can be performed by immersing the glass fiber in a treatment agent composition solution, and then drying the glass fiber to which the treatment agent composition is applied.

[0108] As the above-described silane coupling agent, amino silane, chlorosilane, epoxy silane, mercapto silane, vinyl silane, acrylic silane, and cationic silane can be given. The above-described silane coupling agent can be used alone, or two or more of the above-described silane coupling agents can be used in combination.

[0109] As the aminosilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ- aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ- aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, and the like can be given.

[0110] As the chlorosilane, γ-chloropropyltrimethoxysilane, and the like can be given.

[0111] As the epoxy silane, γ- glycidoxypropyltrimethoxysilane, β-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, and the like can be given.

[0112] As the mercapto silane, γ-mercaptopropyltrimethoxysilane, and the like can be given.

[0113] As the vinyl silane, vinyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)- γ-aminopropyltrimethoxysilane, and the like can be given.

[0114] As the acryl silane, γ-methacryloyloxypropyltrimethoxysilane, and the like can be given.

[0115] As the cationic silane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N-phenyl-3-aminopropyltrimethoxysilane hydrochloride, and the like can be given.

[0116] As the above-mentioned lubricant, modified silicone oil, animal oil and hydrogenated additives thereof, vegetable oil and hydrogenated additives thereof, animal wax, vegetable wax, mineral wax, condensate of higher saturated fatty acid and higher saturated alcohol, polyethylene imine, polyalkyl polyamine alkyl cellobioside derivative, fatty acid amide, quaternary ammonium salt of the 4th grade can be given. The above-mentioned lubricant can be used alone, or two or more of the above-mentioned lubricants can be used in combination.

[0117] As the animal oil, beef tallow, and the like can be given.

[0118] As the vegetable oil, soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, and the like can be given.

[0119] As the animal wax, beeswax, lanolin, and the like can be given.

[0120] As the vegetable wax, candelilla wax, carnauba wax, and the like can be given.

[0121] As the mineral wax, paraffin wax, montan wax, and the like can be given.

[0122] As the condensate of higher saturated fatty acid and higher saturated alcohol, stearate such as lauryl stearate, and the like can be given.

[0123] As the fatty acid amide, for example, a polyethylene polyamine such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, and the like, and a dehydrated condensate of a fatty acid such as lauric acid, myristic acid, palmitic acid, stearic acid, and the like, can be exemplified.

[0124] As the fourth ammonium salt, an alkyl trimethyl ammonium salt such as lauryl trimethyl ammonium chloride, and the like, can be exemplified.

[0125] As the surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can be exemplified. The above surfactants can be used alone, or two or more of the above surfactants can be used in combination.

[0126] As the nonionic surfactant, an ethylene oxide propylene oxide alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene-polyoxypropylene-block copolymer ether, an alkyl polyoxyethylene-polyoxypropylene-block copolymer ether, a polyoxyethylene fatty acid ester, a polyoxyethylene fatty acid monoester, a polyoxyethylene fatty acid diester, a polyoxyethylene sorbitol fatty acid ester, a glycerin fatty acid ester ethylene oxide adduct, a polyoxyethylene stearyl ether, a hydrogenated castor oil ethylene oxide adduct, an alkyl amine ethylene oxide adduct, a fatty acid amide ethylene oxide adduct, a glycerin fatty acid ester, a polyglycerin fatty acid ester, a pentaerythritol fatty acid ester, a sorbitol fatty acid ester, a sorbitan fatty acid ester, a sucrose fatty acid ester, a polyol alkyl ether, a fatty acid alkanolamide, an acetylenic diol, an acetylenic alcohol, an ethylene oxide adduct of an acetylenic diol, an ethylene oxide adduct of an acetylenic alcohol, and the like, can be exemplified.

[0127] As the cationic surfactant, an alkyl dimethyl benzyl ammonium chloride, an alkyl trimethyl ammonium chloride, an alkyl dimethyl ethyl ammonium ethyl sulfate, an ethylene oxide adduct of a higher alkyl amine such as a higher alkyl amine acetate, a higher alkyl amine hydrochloride, a condensate of a higher fatty acid and a polyalkylene polyamine, a salt of an ester of a higher fatty acid and an alkanol amine, a salt of a higher fatty acid amide, an imidazoline type cationic surfactant, an alkyl pyridinium salt, and the like, can be exemplified.

[0128] As the anionic surfactant, a higher alcohol sulfate salt, a higher alkyl ether sulfate salt, an α-olefin sulfate salt, an alkyl benzene sulfonate salt, an α-olefin sulfonate salt, a reaction product of a higher fatty acid halide and N-methyl taurine, a sulfosuccinic acid dialkyl ester salt, a higher alcohol phosphate salt, a phosphate salt of an ethylene oxide adduct of a higher alcohol, and the like, can be exemplified. As the amphoteric surfactant, an amino acid type amphoteric surfactant such as an alkyl amino propionic acid alkali metal salt, a betaine type such as an alkyl dimethyl betaine, an imidazoline type amphoteric surfactant, and the like, can be exemplified.

[0129] The glass fiber fabric of the present embodiment contains the aforementioned glass fiber of the present embodiment. Specifically, the glass fiber fabric of the present embodiment can be produced by weaving the aforementioned glass fiber of the present embodiment as a part of at least the warp or the weft using a publicly known loom. As the loom, for example, there can be mentioned an air jet loom, a water jet loom, a projectile loom, a shuttle loom, a rapier loom, and the like. Further, as the weaving method of the loom, for example, there can be mentioned a plain weave, a satin weave, a basket weave, a twill weave, and the like, and from the viewpoint of manufacturing efficiency, the plain weave is preferred.

[0130] In the glass fiber fabric of the present embodiment, it is preferred that the aforementioned glass fiber of the present embodiment be 0.9 to 600.0 tex (g / km) in mass, in which 35 to 20,000 glass filaments each having a diameter in the range of 3.0 to 21.0 μm are bundled and 0 to 1.0 twists per 25 mm are applied.

[0131] In the glass fiber fabric of the present embodiment, in the case where the aforementioned glass fiber of the present embodiment is used as the warp or the weft, it is preferred that the warp density be in the range of 10 to 120 filaments per 25 mm and the weft density be in the range of 10 to 120 filaments per 25 mm.

[0132] The glass fiber fabric of the present embodiment can also be subjected to a deoiling treatment, a surface treatment, and a fiber opening treatment after weaving.

[0133] As the deoiling treatment, there can be mentioned a treatment in which the aforementioned glass fiber fabric is left in a heating furnace in which the atmospheric temperature is in the range of 350°C to 400°C for a period of time in the range of 40 to 80 hours, and the organic matter adhering to the glass fiber is subjected to thermal decomposition.

[0134] As the surface treatment, there can be mentioned a treatment in which the aforementioned glass fiber fabric is immersed in a solution containing the aforementioned silane coupling agent or a solution containing the aforementioned silane coupling agent and the aforementioned surfactant, and after the excess water is removed, the glass fiber fabric is heated and dried at a temperature in the range of 80 to 180°C for 1 to 30 minutes.

[0135] As the fiber opening treatment, for example, there can be mentioned a treatment in which the yarn width of the warp and the weft is expanded by applying a tension in the range of 30 to 200 N to the warp of the aforementioned glass fiber fabric while performing fiber opening using water pressure, fiber opening using high-frequency vibration with liquid as a medium, fiber opening using fluid pressure having a surface pressure, fiber opening using pressurization by a roller, and the like.

[0136] The glass fiber fabric of the present embodiment preferably has a mass per unit area in the range of 7.0 to 750.0 g / m 2 and preferably has a thickness in the range of 8.0 to 500.0 μm.

[0137] The warp yarn of the glass fiber fabric of the present embodiment preferably has a yarn width in the range of 110 to 600 μm, and the weft yarn preferably has a yarn width in the range of 110 to 600 μm.

[0138] The glass fiber fabric of the present embodiment can have a surface treatment layer containing the above-described silane coupling agent or a surface treatment layer containing the above-described silane coupling agent and the above-described surfactant. In the case where the glass fiber fabric of the present embodiment contains the above-described surface treatment layer, the surface treatment layer has a mass in the range of, for example, 0.03 to 1.50 mass% with respect to the total amount of the glass fiber fabric containing the surface treatment layer.

[0139] The glass fiber-reinforced resin composition of the present embodiment contains the aforementioned glass fiber of the present embodiment. Specifically, in a glass fiber-reinforced resin composition containing a resin (thermoplastic resin or thermosetting resin), glass fiber, and other additives, the glass fiber-reinforced resin composition of the present embodiment contains glass fiber in an amount of, for example, 10 to 90 mass% with respect to the total amount of the glass fiber-reinforced resin composition. In addition, the glass fiber-reinforced resin composition of the present embodiment contains a resin in an amount of, for example, 90 to 10 mass% with respect to the total amount of the glass fiber-reinforced resin composition, and contains other additives in an amount in the range of 0 to 40 mass%.

[0140] As the thermoplastic resin forming the glass fiber-reinforced resin composition of the present embodiment, 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), polytrimethylene terephthalate (PTT), polycarbonate, polyarylsulfide, polyether sulfone (PES), polyphenylene sulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryletherketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate (PEN), ethylene / vinyl acetate (EVA) resin, ionomer (IO) resin, polybutadiene, styrene / butadiene resin, polybutene, polymethylpentene, olefin / ethylene vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, and the like can be given.

[0141] As the polyethylene described above, high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-high-molecular-weight polyethylene, and the like can be given.

[0142] As the polypropylene described above, isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures of these polypropylenes, and the like can be given.

[0143] As the polystyrene described above, general-purpose polystyrene (GPPS) which is a random polystyrene having a random structure, impact-resistant polystyrene (HIPS) in which a rubber component is added to GPPS, atactic polystyrene having a random structure, and the like can be given.

[0144] As the methacrylic acid resin described above, a polymer in which one kind of methacrylic acid resin selected from the group consisting of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and a fatty acid vinyl ester is polymerized alone, or a polymer in which two or more kinds of the methacrylic acid resins described above are copolymerized, and the like can be given.

[0145] As the above-mentioned polyvinyl chloride, there can be mentioned a homopolymer of vinyl chloride polymerized by a method such as an emulsion polymerization method, a suspension polymerization method, a micro-suspension polymerization method, a bulk polymerization method, and the like, which are known conventionally, or a copolymer of a monomer copolymerizable with a vinyl chloride monomer, or a graft copolymer of a polymer to which a vinyl chloride monomer is grafted, and the like.

[0146] As the polyamide, there can be mentioned one or a plurality of components selected from the group consisting of polycaprolactam (polyamide 6), poly(hexamethylene adipamide) (polyamide 66), poly(hexamethylene dodecanamide) (polyamide 46), poly(decamethylene adipamide) (polyamide 410), poly(hexamethylene pentamethylene adipamide) (polyamide 56), poly(pentamethylene sebacamide) (polyamide 510), poly(hexamethylene sebacamide) (polyamide 610), poly(hexamethylene dodecanamide) (polyamide 612), poly(decamethylene adipamide) (polyamide 106), poly(decamethylene decamethylene adipamide) (polyamide 1010), poly(decamethylene dodecanamide) (polyamide 1012), polyundecanamide (polyamide 11), poly(hexamethylene hexamethylene adipamide) (polyamide 116), poly(dodecanamide) (polyamide 12), poly(xylene diamine adipamide) (polyamide XD6), poly(decamethylene decamethylene adipamide) (polyamide XD10), poly(m-xylylene adipamide) (polyamide MXD6), poly(p-xylylene adipamide) (polyamide PXD6), poly(terephthalamide) (polyamide 4T), poly(pentamethylene terephthalamide) (polyamide 5T), poly(hexamethylene terephthalamide) (polyamide 6T), poly(hexamethylene isophthalamide) (polyamide 61), poly(nona methylene terephthalamide) (polyamide 9T), poly(decamethylene terephthalamide) (polyamide 10T), poly(undecamethylene terephthalamide) (polyamide 11T), poly(dodecamethylene terephthalamide) (polyamide 12T), poly(tetramethylene polyphthalamide) (polyamide 41), poly(bis(3-methyl-4-aminohexyl)methane terephthalamide) (polyamide PACMT), poly(bis(3-methyl-4-aminohexyl)methane isophthalamide) (polyamide PACMI), poly(bis(3-methyl-4-aminohexyl)methane dodecanamide) (polyamide PACM12), poly(bis(3-methyl-4-aminohexyl)methane tetradecanamide) (polyamide PACM14), and the like, and a copolymer or a mixture thereof.

[0147] As the above-mentioned polyalkylene oxide, there can be mentioned a homopolymer of an alkylene oxide, a copolymer of two or more kinds of alkylene oxides, and the like.

[0148] As the above-mentioned polyethylene terephthalate, there can be mentioned a polymer obtained by polycondensing ethylene glycol and terephthalic acid or a derivative thereof, and the like.

[0149] As the above-mentioned polybutylene terephthalate, there can be mentioned a polymer obtained by subjecting 1,4-butanediol to polycondensation with terephthalic acid or a derivative thereof, and the like.

[0150] As the above-mentioned polypropylene terephthalate, there can be mentioned a polymer obtained by subjecting 1,3-propanediol to polycondensation with terephthalic acid or a derivative thereof, and the like.

[0151] As the above-mentioned polycarbonate, there can be mentioned a polymer obtained by using an ester exchange method of reacting a dihydroxy diaryl compound with a carbonate such as diphenyl carbonate in a molten state, or a polymer obtained by using a phosgene method of reacting a dihydroxy aryl compound with phosgene.

[0152] As the above-mentioned polyarylene sulfide, there can be mentioned a linear polyphenylene sulfide, a crosslinked polyphenylene sulfide which is high-molecular-weighted by subjecting to a curing reaction after polymerization, a polyphenylene sulfide sulfone, a polyphenylene sulfide ether, a polyphenylene sulfide ketone, and the like.

[0153] As the above-mentioned modified polyphenylene ether, there can be mentioned a polymer alloy of poly(2,6-dimethyl-l,4-phenylene) ether and polystyrene, a polymer alloy of poly(2,6-dimethyl-l,4-phenylene) ether and a styrene / butadiene copolymer, a polymer alloy of poly(2,6-dimethyl-l,4-phenylene) ether and a styrene / maleic anhydride copolymer, a polymer alloy of poly(2,6-dimethyl-l,4-phenylene) ether and a polyamide, a polymer alloy of poly(2,6-dimethyl-l,4-phenylene) ether and a styrene / butadiene / acrylonitrile copolymer, and the like.

[0154] As the above-mentioned polyaryletherketone, there can be mentioned a polyetherketone (PEK), a polyetheretherketone (PEEK), a polyetherketoneketone (PEKK), a polyetheretherketoneketone (PEEKK), and the like.

[0155] As the above-mentioned liquid crystal polymer (LCP), there can be mentioned a (co)polymer composed of one or more structural units selected from the group consisting of an aromatic hydroxycarbonyl unit, an aromatic dihydroxy unit, an aromatic dicarbonyl unit, an aliphatic dihydroxy unit, an aliphatic dicarbonyl unit, and the like as a thermotropic liquid crystalline polyester.

[0156] As the above-mentioned fluorine resin, there can be mentioned polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene resin (ECTFE), and the like.

[0157] As the above ionomer (IO) resin, a polymer in which a part of carboxyl groups of a copolymer of an olefin or styrene and an unsaturated carboxylic acid is neutralized with a metal ion, etc. can be given.

[0158] As the above olefin / vinyl alcohol resin, an ethylene / vinyl alcohol copolymer, a propylene / vinyl alcohol copolymer, a saponified product of an ethylene / vinyl acetate copolymer, a saponified product of a propylene / vinyl acetate copolymer, etc. can be given.

[0159] As the above cyclic olefin resin, a monocyclic body such as cyclohexene, a polycyclic body such as a tetra-cyclic cyclic olefin, a polymer of a cyclic olefin monomer, etc. can be given.

[0160] As the above polylactic acid, poly-L-lactic acid which is a homopolymer of L body, poly-D-lactic acid which is a homopolymer of D type, or stereocomplex polylactic acid which is a mixture thereof, etc. can be given.

[0161] As the cellulose resin, methyl cellulose, ethyl cellulose, hydroxy cellulose, methylol cellulose, hydroxyethyl cellulose, hydroxyethylmethyl cellulose, hydroxypropylmethyl cellulose, cellulose acetate, cellulose propionate, and cellulose butyrate, etc. can be given. In addition, as the above thermosetting resin which forms the glass fiber-reinforced resin composition of the present embodiment, an unsaturated polyester resin, a vinyl ester resin, an epoxy (EP) resin, a melamine (MF) resin, a phenol formaldehyde (PF) resin, a polyurethane (PU) resin, a polyisocyanate, a polyisocyanurate, a polyimide (PI), a urea formaldehyde (UF) resin, a silicone (SI) resin, a furan (FR) resin, a benzoguanamine (BR) resin, an alkyd resin, a xylene resin, a bismaleimide triazine (BT) resin, a diallyl phthalate (PDAP) resin, a thermosetting polyphenylene ether resin, etc. can be given.

[0162] Specifically, as the unsaturated polyester resin, a resin obtained by esterification reaction of an aliphatic unsaturated dicarboxylic acid and an aliphatic diol can be given.

[0163] As the vinyl ester resin, a divinyl ester resin, a novolak-based vinyl ester resin can be given.

[0164] As the epoxy resin, there can be mentioned a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol E type epoxy resin, a bisphenol S type epoxy resin, a bisphenol M type epoxy resin (4,4'-(1,3-phenylene diisopropylidene) bisphenol type epoxy resin), a bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisopropylidene) bisphenol type epoxy resin), a bisphenol Z type epoxy resin (4,4'-cyclohexene bisphenol type epoxy resin), a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a tetraphenylol ethane novolak type epoxy resin, a novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure, a biphenyl type epoxy resin, a paraxylylene type epoxy resin, or an aralkyl type epoxy resin such as a phenyl aralkyl type epoxy resin, a naphthalene ether type epoxy resin, a naphthol type epoxy resin, a naphthalenediol type epoxy resin, a 2-functional or 4-functional epoxy type naphthalene resin, a binaphthyl type epoxy resin, a naphthalene aralkyl type epoxy resin, an anthracene type epoxy resin, a phenoxy type epoxy resin, a dicyclopentadiene type epoxy resin, a norbornene type epoxy resin, an adamantane type epoxy resin, a fluorene type epoxy resin, and the like.

[0165] As the melamine resin, there can be mentioned a polymer formed by condensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0166] As the phenol resin, there can be mentioned one of a phenol novolak resin, a cresol novolak resin, a bisphenol A type phenol novolak resin, and the like, a resol type phenol resin such as a methylol type resol resin, a dimethylene ether type resol resin, or an aralkyl type phenol resin such as an aryl alkyl type phenol resin, or a resin formed by combining two or more of the resins.

[0167] As the urea resin, there can be mentioned a resin obtained by condensation of urea and formaldehyde.

[0168] The above-mentioned thermoplastic resin or the above-mentioned thermosetting resin can be used alone or in combination of two or more.

[0169] As the above-mentioned other additive, there can be mentioned a reinforcing fiber other than glass fiber (for example, a carbon fiber, a metal fiber), a filler other than glass fiber (for example, a glass powder, talc, mica), a flame retardant, an ultraviolet absorber, a heat stabilizer, an antioxidant, an antistatic agent, a flowability improver, an antiblocking agent, a lubricant, a nucleating agent, an antibacterial agent, a pigment, and the like.

[0170] The glass fiber reinforced resin composition of the present embodiment can be obtained, for example, by mixing the above-mentioned chopped strand and the above-mentioned resin in a twin-screw kneader to produce resin pellets by kneading, and injection molding using the obtained resin pellets.

[0171] In addition, the above-described glass fiber-reinforced resin composition can be obtained by the following publicly known molding methods: injection compression molding, two-color molding, hollow molding, foam molding (including supercritical fluid foam molding), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, press molding, melt method, hand lay-up molding, spray method, resin transfer molding, sheet molding, bulk film press molding, pultrusion molding, filament winding, and the like.

[0172] In addition, the glass fiber-reinforced resin composition of the present embodiment can be a prepreg obtained by impregnating the above-described resin into the above-described glass fiber fabric of the present embodiment and semi-curing it by a publicly known method.

[0173] As the use of the molded article formed from the glass fiber-reinforced resin composition of the present embodiment, for example, the following can be listed: electronic device housings, electronic parts, vehicle exterior parts, vehicle interior parts, vehicle engine peripheral parts, muffler-related parts, high-pressure tanks, composite materials for wind power, and the like.

[0174] As the electronic parts, printed wiring boards and the like can be listed.

[0175] As the vehicle exterior parts, bumpers, fenders, hoods, air dams, wheel covers, and the like can be listed.

[0176] As the vehicle interior parts, door trims, headliners, and the like can be listed.

[0177] As the vehicle engine peripheral parts, oil pans, engine covers, intake manifolds, exhaust manifolds, and the like can be listed.

[0178] As the muffler-related parts, muffler parts and the like can be listed.

[0179] As the composite materials for wind power, wind turbine blades and the like can be listed.

[0180] Note that the glass fiber of the present embodiment can be used not only for the glass fiber-reinforced resin composition of the present embodiment but also as a reinforcing material for inorganic materials such as gypsum and cement. For example, in the case of use as a reinforcing material for gypsum, particularly gypsum boards having a thickness in the range of 4 to 60 mm, the gypsum contains glass fibers having the above-described glass composition in the range of 0.1 to 4.0 mass% with respect to the total mass of the gypsum.

[0181] Next, an example and a comparative example of the present application are shown.

[0182] Example

[0183] [Examples 1 to 12, Comparative Examples 1 to 6]

[0184] Each glass batch was formulated so as to become the composition of each glass fiber- for-glass composition of Examples 1 to 12 and Comparative Examples 1 to 6 shown in Tables 1 to 3, and the elastic modulus, the linear expansion coefficient, the dielectric constant, and the dielectric loss tangent of each of the above- formulated glass materials were measured by the following measurement methods, and the fining property of the molten glass and the composition uniformity of the molten glass were evaluated by the following evaluation methods. The results are shown in Tables 1 to 3.

[0185] Note that the composition of Comparative Example 3 is the same as that of Example 1 in PCT / JP2023 / 014110, and the composition of Comparative Example 4 is the same as that of Example 2 in Japanese Patent Application 2023-029848.

[0186] In addition, the elastic modulus of the glass fiber obtained using the glass fiber-for-glass composition of Example 1 was 82.6 GPa, the linear expansion coefficient was 2.2 ppm / K, the dielectric constant at 10 GHz was 4.7, the dielectric loss tangent at 10 GHz was 0.0043, the dielectric constant at 28 GHz was 4.6, the dielectric loss tangent at 28 GHz was 0.0057, the dielectric constant at 56 GHz was 4.6, the dielectric loss tangent at 56 GHz was 0.0071, the fining property of the molten glass obtained from the composition was “A”, and the composition uniformity was 0.6%.

[0187] [Measurement method of elastic modulus]

[0188] First, the glass batch adjusted to the composition of the above glass fiber-for-glass composition was put into a platinum crucible having a diameter of 80 mm, and was heated at a temperature of 1650°C for 6 hours to be molten, and then was taken out of the platinum crucible to obtain a homogeneous glass block or glass chips. Next, the obtained glass block or glass chips was heated at a temperature of 750°C for 8 hours to be annealed, and a test piece was obtained. Next, the above test piece was processed into an elastic modulus measurement test piece having a size of 50 mm x 50 mm x 5 mm using a cutting machine, such as a diamond cutter, and a grinder, and the elastic modulus measurement test piece was used to measure the elastic modulus in accordance with JIS R 1602:1995 using an ultrasonic pulse method.

[0189] [Measurement method of linear expansion coefficient]

[0190] First, the test piece obtained in the same manner as in the measurement of the elastic modulus described above is processed into a test piece for measurement of linear expansion coefficient of 4 mm x 4 mm x 20 mm using a cutting machine such as a diamond tool and a grinder. Next, the test piece for measurement of linear expansion coefficient obtained above is heated at a temperature increase rate of 10°C / min, and the elongation is measured using a thermal dilatometer (NETZSCH Corporation, product name: DIL402) in a temperature range of 50°C to 200°C, and the linear expansion coefficient is calculated from the elongation.

[0191] [Method for evaluating clarity]

[0192] First, a glass batch adjusted to the composition of the glass fiber glass composition described above is put into a platinum crucible of 80 mm in diameter, and after being melted at a temperature of 1600°C for 3 hours, it is taken out of the platinum crucible to obtain a glass block. Next, after the obtained glass block is heated at a temperature of 750°C for 2 hours, it is cooled to room temperature over 8 hours to perform annealing, and a test piece is obtained. Next, the center part of the obtained test piece is cut out to be 10 mm x 15 mm in size using a cutting machine such as a diamond tool, and the surface thereof is polished with #2000 polishing paper. Next, the number of bubbles contained in the test piece whose surface is polished is measured using an optical microscope, and the case where the number of bubbles per g of glass block is less than 150 is evaluated as "A", the case where the number of bubbles is 150 or more and less than 1000 is evaluated as "B", and the case where the number of bubbles is 1000 or more is evaluated as "C".

[0193] [Method for evaluating composition uniformity]

[0194] First, the center part of the test piece obtained in the same manner as in the method for evaluating clarity described above is cut out to be a test piece of 10 mm x 15 mm in size for the upper surface and the bottom surface using a cutting machine such as a diamond tool, and the surface thereof is polished with #2000 polishing paper. Next, the composition of the side surface of the test piece whose surface is polished is analyzed by EDS (energy dispersive spectroscopy), and the difference in composition between the upper surface region and the bottom surface region is evaluated. Specifically, a field emission type scanning electron microscope (FE-SEM, manufactured by JEOL Ltd., model number: JSM-IT800) and an energy dispersive spectrometer (manufactured by JEOL Ltd., model number: EDS30mm 2The detector), in any 100 μm or more field of view, the area of the respective height of 1 mm from the top surface and the bottom surface range of the region implementing area measurement, measuring the glass fiber glass composition containing each element of the oxide conversion of the content (%). Note that, for the top surface area and the bottom surface area of the respective three different area of the element of the oxide conversion of the content, the average of the three areas of the measured results as the oxide conversion of the content of the respective elements. For each element, the oxide conversion of the content in the top surface area and the oxide conversion of the content in the bottom surface area of the absolute value of the difference, the detected all elements. The value obtained by adding the absolute value of the difference of the above content of all elements as the composition uniformity. Note that, the smaller the numerical value of the composition uniformity, the smaller the composition of the molten glass deviation (the more excellent uniformity) means.

[0195] 〔Measurement method of dielectric constant and dielectric loss tangent〕

[0196] Regarding the measurement of the dielectric constant (dielectric constant Dk) and the dielectric loss tangent (dissipation factor Df) at 10 GHz or less, first, the test piece is polished to a polished test piece of 80 mm x 3 mm (thickness 1 mm). Next, the obtained polished test piece is subjected to absolute drying, and then stored in a room at 23°C, 60% humidity for 24 hours. Next, the dielectric constant (dielectric constant Dk) and the dielectric loss tangent (dissipation factor Df) of the obtained polished test piece at 10 GHz are measured using the hollow resonator method dielectric constant measuring device ADMS010cl (product name) manufactured by AET, Inc. (AET, Inc.) in accordance with JIS C 2565:1992.

[0197] Regarding the measurement of the dielectric constant (dielectric constant Dk) and the dielectric loss tangent (dissipation factor Df) at 10 GHz or more, first, the test piece is polished to a polished test piece of 37 mm x 37 mm (thickness 0.3 mm). Next, the obtained polished test piece is subjected to absolute drying, and then stored in a room at 25°C, 50% humidity for 24 hours. Next, the dielectric constant (dielectric constant Dk) and the dielectric loss tangent (dissipation factor Df) of the obtained polished test piece at 28 GHz and 56 GHz are measured by the balanced circular plate resonator method.

[0198] (Table 1)

[0199]

[0200] (Table 2)

[0201]

[0202] (Table 3)

[0203]

[0204] From Tables 1 and 2, it is known that, according to the glass compositions for glass fibers of Examples 1 to 10 described below, it is possible to achieve both high elastic modulus and low linear expansion coefficient, to improve fining of molten glass, and to achieve composition uniformity of molten glass. In Examples 1 to 10, SiO2is contained in an amount of 42.00 to 70.00 mass%, Al2O3is contained in an amount of 10.00 to 30.00 mass%, MgO is contained in an amount of 0.00 to 8.00 mass%, CaO is contained in an amount of 0.00 to 5.00 mass%, ZnO is contained in an amount of 2.00 to 25.00 mass%, TiO2is contained in an amount of 0.00 to 5.00 mass%, P2O5is contained in an amount of 2.00 to 17.30 mass%, and MxOyis contained in an amount of 0.01 to 2.00 mass% in total, and the content ratio Z of ZnO, the content ratio P of P2O5, and the content ratio M of MxOy satisfy the formula (1).

[0205] On the other hand, from Table 3, it is known that, according to the glass composition for glass fibers of Comparative Example 1 in which the value of (Z / P) x M 1 / 2 exceeds 3.554 and is outside the range of the formula (1) described above, fining is low, and it is not possible to achieve composition uniformity of molten glass. In addition, it is known that, according to the glass composition for glass fibers of Comparative Example 2 in which the value of (Z / P) x M 1 / 2 is less than 0.088 and is outside the range of the formula (1) described above, fining is low. In addition, it is known that, according to the glass compositions for glass fibers of Comparative Examples 3 and 4 in which the content ratio of MxOy is 0.00%, fining is low, and it is not possible to achieve composition uniformity of molten glass. Furthermore, it is known that, according to the glass composition for glass fibers of Comparative Example 5 in which the content ratio of ZnO is 0.00%, it is not possible to produce glass fibers having high elastic modulus. In addition, it is known that, according to the glass composition for glass fibers of Comparative Example 6 in which the content ratio of P2O5 is 0.01%, it is not possible to produce glass fibers having low linear expansion coefficient.

Claims

1. A glass composition for glass fiber, characterized in that, Compared to the total amount of SiO2 ranging from 42.00% to 70.00% by mass, Al2O3 in the range of 10.00–30.00% by mass MgO in the range of 0.00 to 8.00% by mass CaO in the range of 0.00 to 5.00% by mass ZnO in the range of 2.00 to 25.00% by mass TiO2 in the range of 0.00 to 5.00% by mass P2O5 in the range of 2.00–17.30% by mass And MxOy in a total range of 0.01 to 2.00% by mass, wherein MxOy is at least one oxide selected from the group consisting of Fe2O3, SnO2, CeO2, MnO2, Sb2O3, and As2O3. The content of ZnO Z, the content of P2O5 P, and the content of MxOy M satisfy the following formula (1). 0.088≤(Z / P)×M 1 / 2 ≤3.554 … (1)。 2. The glass composition for glass fiber according to claim 1, characterized in that, The content of ZnO Z, the content of P2O5 P, and the content of MxOy M satisfy the following formula (2). 0.183≤(Z / P)×M 1 / 2 ≤1.775 … (2)。 3. The glass composition for glass fiber according to claim 2, characterized in that, Containing 0.01–1.50% by mass of Fe₂O₃ and 0.01–1.50% by mass of SnO₂, The content of Fe2O3, F, and the content of SnO2, S satisfy the following formula (3). 0.06≤S / F≤40.75 … (3)。 4. The glass composition for glass fiber according to claim 1, characterized in that, The content of ZnO Z, the content of P2O5 P, and the content of MxOy M satisfy the following formula (4). 0.183≤(Z / P)×M 1 / 2 ≤0.582 … (4)。 5. A type of glass fiber, characterized in that, It comprises glass filaments formed from the glass composition for glass fibers as described in claim 1.

6. A glass fiber fabric, characterized in that, It contains the glass fiber as described in claim 5.

7. A glass fiber reinforced resin composition, characterized in that, It contains the glass fiber as described in claim 5.

Images