Thread-like glass fiber, glass fiber fabric, and glass fiber reinforced resin composition

Abstract

The present invention provides a glass fiber having an extremely low dielectric loss tangent and with which it is possible to obtain a glass fiber woven fabric having sufficient handleability. The glass fiber according to the present invention is made of a glass composition containing, with respect to the total amount of the glass composition, 92.50-99.99% by mass of SiO2, 0.01-5.00% by mass of TiO2, and 0.00-2.50% by mass of Al2O3. The tensile breaking stress is 1.0-100.0 MPa. The content S of SiO2, the content T of TiO2, and the tensile breaking stress BS satisfy the following formula (1).　(1) 5.2≤BS×(T / (100-S))2≤33.8

Description

[Technical field]

[0001] The present invention relates to Filamentous Glass fiber, glass fiber fabric, and glass fiber reinforced resin composition Regarding. [Background technology]

[0002] Conventionally, glass fibers have been widely used in various applications to improve the strength of resin molded products, and the resin molded products are used in components such as housings or printed wiring boards for electronic devices such as servers, smartphones, and notebook computers.

[0003] In general, dielectric materials such as glass absorb part of the energy of an AC electric field as heat (called dielectric loss), so when the resin molded product is used as a housing or part for the electronic device, there is a problem that the resin molded product generates heat.

[0004] Here, the dielectric loss absorbed by the glass is proportional to the dielectric constant and dielectric loss tangent determined by the components and structure of the glass, and is expressed by the following formula: W=kf×ε 1 / 2 ×tan δ

[0005] Here, W is the dielectric loss, k is a constant, f is the frequency, ε is the dielectric constant, and tan δ is the dielectric tangent. From the above formula, it can be seen that the larger the dielectric constant and the dielectric tangent, and the higher the frequency, the larger the dielectric loss and the greater the heat generation of the resin molded product.

[0006] In recent years, as the frequency of the alternating current used in the electronic devices (f in the above formula) has been increasing, there has been a demand for glass fibers used in the housings or parts of the electronic devices to have lower dielectric constants and lower dielectric dissipation factor in order to reduce dielectric loss. In addition, compared to the dielectric constant ε, which is raised to the power of 1 / 2 in the above formula, a reduction in ε has a greater impact on reducing dielectric loss energy, and therefore there is a particular demand for a lower dielectric dissipation factor.

[0007] Known glass fibers with an extremely low dielectric tangent include those having a quartz glass composition in which the SiO2 content relative to the total amount of the glass composition is 90 mass% or more, particularly 99 mass% or more (see, for example, Patent Document 1). Also known as a method for producing glass fibers having a glass composition with such a high SiO2 content is a method in which components other than SiO2 are dissolved in an acid solution from a mother glass composition that contains components other than SiO2 that are easily soluble in acid (see, for example, Patent Document 2).

[0008] Here, the extremely low dielectric tangent means that the dielectric tangent of the glass fiber at a measurement frequency of 28 GHz is less than 0.0010. The dielectric tangent of the glass fiber at a measurement frequency of 28 GHz can be measured by the method described below. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] JP 2009-263569 A [Patent Document 2] Japanese Patent Application Publication No. 9-169548 Summary of the Invention [Problem to be solved by the invention]

[0010] However, the glass fiber obtained by the method of Patent Document 2, which has a high SiO content relative to the total amount of the glass composition, does not necessarily have an extremely low dielectric tangent. Even if the glass fiber has an extremely low dielectric tangent, there is a disadvantage that a glass fiber product containing the glass fiber, particularly a light, thin, short and small glass fiber product, especially a glass fiber fabric, may not have sufficient handleability to withstand industrial processing and transportation.

[0011] An object of the present invention is to eliminate such inconveniences and to provide a glass fiber having an extremely low dielectric tangent and sufficient handleability.

[0012] Another object of the present invention is to provide a glass fiber fabric and a glass fiber reinforced resin composition containing the glass fiber of the present invention. [Means for solving the problem]

[0013] In order to achieve this object, the present invention Filamentous The glass fiber is made of a glass composition containing SiO2 in the range of 92.50 to 99.99 mass%, TiO2 in the range of 0.01 to 5.00 mass%, and Al2O3 in the range of 0.00 to 2.50 mass%, based on the total amount of the glass composition, Filamentous The tensile breaking stress of the glass fiber is in the range of 1.0 to 100.0 MPa, and the SiO2 content S and TiO2 content T are Filamentous Glass fiber Per bottle and the tensile breaking strength BS satisfy the following formula (1). 5.2 ≦ BS × (T / (100-S)) 2 ≦ 33.8 (1)

[0014] The present invention Filamentous The glass fiber has a glass composition in which the contents of SiO2, TiO2 and Al2O3 are in the above-mentioned ranges, Filamentous When the tensile breaking stress of the glass fiber is within the above range and the S, T and BS satisfy the formula (1), the glass fiber has an extremely low dielectric tangent and sufficient handleability.

[0015] In addition, the present invention Filamentous It is preferable that the S, T and BS of the glass fiber satisfy the following formula (2). 9.1 ≦ BS × (T / (100-S)) 2 ≦ 33.5 (2)

[0016] The present invention Filamentous When the S, T and BS of the glass fiber satisfy the formula (2), the glass fiber can more reliably have an extremely low dielectric tangent and excellent handleability.

[0017] Also 、 The present invention FilamentousIt is preferable that the S, T and BS of the glass fiber satisfy the following formula (3). 20.1 ≦ BS × (T / (100-S)) 2 ≦ 33.1 (3)

[0018] The present invention Filamentous When the S, T and BS satisfy the formula (3), the glass fiber has a particularly extremely low dielectric tangent and excellent handleability. Here, the term "having a particularly extremely low dielectric tangent" means that Filamentous This means that the dielectric tangent of the glass fiber at a measurement frequency of 28 GHz is 0.0005 or less. Filamentous The dielectric loss tangent of the glass fiber at a measurement frequency of 28 GHz can be measured by the method described below.

[0019] The glass fiber fabric of the present invention is Filamentous It is characterized by containing glass fibers.

[0020] The glass fiber reinforced resin composition of the present invention is Filamentous It is characterized by containing glass fibers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Next, the embodiment of the present invention will be described in more detail.

[0022] In this embodiment Filamentous The glass fiber is made of a glass composition containing SiO2 in the range of 92.50 to 99.99 mass%, TiO2 in the range of 0.01 to 5.00 mass%, and Al2O3 in the range of 0.00 to 2.50 mass%, based on the total amount of the glass composition, Filamentous The tensile breaking stress of the glass fiber is in the range of 1.0 to 100.0 MPa, and the SiO2 content S and TiO2 content T are Filamentous Glass fiber Per bottle and the tensile breaking stress BS satisfy the following formula (1). 5.2 ≦ BS × (T / (100-S)) 2 ≦ 33.8 (1)

[0023] In this embodiment Filamentous The glass fiber has a glass composition in which the contents of SiO2, TiO2 and Al2O3 are in the above-mentioned ranges, Filamentous When the tensile stress at break of the glass fiber is within the above range and the S, T and BS satisfy the formula (1), the glass fiber has an extremely low dielectric tangent and sufficient handleability, particularly handleability as a glass fiber fabric.

[0024] In this embodiment Filamentous In the glass composition constituting the glass fiber, if the content of SiO2 is less than 92.50 mass% with respect to the total amount of the glass composition, the Filamentous The dielectric loss tangent of the glass fiber cannot be sufficiently reduced. Filamentous When the SiO2 content of the glass fiber exceeds 99.99 mass% based on the total amount of the glass composition, Filamentous The flexibility of the glass fibers is lost, and handling properties, particularly handling properties as a glass fiber fabric, deteriorate.

[0025] In this embodiment Filamentous In the glass composition constituting the glass fiber, Filamentous Reduction of the dielectric tangent of glass fiber and Filamentous From the viewpoint of compatibility with the handleability of the glass fiber, the content of SiO2 is preferably in the range of 97.10 to 99.40 mass %, more preferably in the range of 98.10 to 98.90 mass %, based on the total amount of the glass composition.

[0026] In this embodiment Filamentous In the glass composition constituting the glass fiber, when the content of TiO2 is less than 0.01 mass% with respect to the total amount of the glass composition, Filamentous The handling of the glass fiber, particularly the handling of the glass fiber fabric, is deteriorated. Filamentous When the TiO2 content of the glass fiber exceeds 5.00 mass% based on the total amount of the glass composition, Filamentous The dielectric tangent of the glass fiber cannot be reduced sufficiently.

[0027] In this embodiment Filamentous In the glass composition constituting the glass fiber, Filamentous Reduction of the dielectric tangent of glass fiber and Filamentous From the viewpoint of compatibility with the handleability of the glass fiber, the content of TiO2 is preferably in the range of 0.11 to 3.50 mass%, more preferably in the range of 0.31 to 1.94 mass%, and further preferably in the range of 0.51 to 1.94 mass%, based on the total amount of the glass composition. The range is preferably 0.71 to 1.64 mass%, more preferably 0.72 to 1.44 mass%, particularly preferably 0.73 to 1.20 mass%, and most preferably 0.75 to 0.99 mass%.

[0028] In this embodiment Filamentous In the glass composition constituting the glass fiber, if the content of Al2O3 exceeds 2.50 mass% with respect to the total amount of the glass composition, Filamentous The dielectric loss tangent of the glass fiber cannot be reduced sufficiently.

[0029] In this embodiment Filamentous In the glass composition constituting the glass fiber, Filamentous Reduction of the dielectric tangent of glass fiber and Filamentous From the viewpoint of compatibility with ease of handling of the glass fiber, the content of Al2O3 is preferably in the range of 0.00 to 0.34 mass%, more preferably in the range of 0.00 to 0.24 mass%, even more preferably in the range of 0.00 to 0.20 mass%, particularly preferably in the range of 0.00 to 0.14 mass%, particularly preferably in the range of 0.00 to 0.10 mass%, particularly preferably in the range of 0.00 to 0.09 mass%, and most preferably in the range of 0.01 to 0.09 mass%, based on the total amount of the glass composition.

[0030] In this embodiment FilamentousThe glass composition constituting the glass fiber may contain, as impurities, oxides of Li, Na, K, Mg, Ca, B, P, Fe, Sn, Sr, Ba, Mn, Co, Ni, Cu, Cr, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb in a total amount of less than 1.00 mass%, preferably less than 0.50 mass%, and more preferably less than 0.20 mass%, based on the total amount of the glass composition.

[0031] In particular, in this embodiment Filamentous When the glass composition constituting the glass fiber contains Li2O, Na2O, K2O, MgO, CaO, B2O3, P2O5, FeO, Fe2O3, SnO2, SrO, BaO, CeO2, Y2O3, La2O3, Bi2O3, Gd2O3, Pr2O3, Sc2O3, or Yb2O3 as an impurity, the content thereof is preferably independently less than 0.40 mass%, more preferably less than 0.20 mass%, even more preferably less than 0.10 mass%, particularly preferably less than 0.05 mass%, particularly preferably less than 0.03 mass%, and most preferably less than 0.01 mass%, based on the total amount of the glass composition.

[0032] In this embodiment Filamentous The glass composition constituting the glass fiber may contain, as impurities, F2, Cl2, and SO3, each independently in a range of less than 0.20 mass%, preferably less than 0.10 mass%, more preferably less than 0.05 mass%, even more preferably less than 0.03 mass%, and most preferably less than 0.01 mass%, based on the total amount of the glass composition.

[0033] In this embodiment Filamentous The content of each component in the glass composition constituting the glass fiber can be measured using an ICP optical emission spectrometer for the light element Li, and the content of other elements can be measured using a wavelength dispersive X-ray fluorescence analyzer.

[0034] The measurement method can be the following. Filamentous The glass fibers are pulverized to obtain glass powder. Filamentous The glass fiber is Filamentous When organic matter is attached to the surface of glass fiber, or Filamentous When glass fibers are contained mainly as a reinforcing material in an organic matter (resin), the organic matter is removed before use, for example, by heating in a muffle furnace at 300 to 650° C. for about 0.5 to 24 hours.

[0035] Next, the glass powder, which is a light element, is decomposed by heating with an acid, and then quantitatively analyzed for Li using an ICP emission spectrometer. The glass powder is molded into a disk shape using a press, and the other elements are quantitatively analyzed using a wavelength-dispersive X-ray fluorescence analyzer. Specifically, the quantitative analysis using a wavelength-dispersive X-ray fluorescence analyzer can be performed by preparing a calibration curve sample based on the results measured using the fundamental parameter method, and analyzing the calibration curve method. The content of each component in the calibration curve sample can be quantitatively analyzed using an ICP emission spectrometer. The results of these quantitative analyses are converted into oxides to calculate the content and total amount of each component, and the content (mass%) of each component described above can be calculated from these values.

[0036] In this embodiment Filamentous In the glass composition constituting the glass fiber, the ratio of the Al2O3 content to the TiO2 content (Al2O3 / TiO2) is Filamentous The ease of handling of glass fibers, especially that of handling as a glass fiber fabric, is maintained while Filamentous From the viewpoint of further reducing the dielectric loss tangent of the glass fiber, it is preferably in the range of 0.00 to 0.30, more preferably in the range of 0.00 to 0.20, further preferably in the range of 0.00 to 0.14, and particularly preferably in the range of 0.03 to 0.12. Here, the lower the content of Al2O3, the Filamentous The dielectric loss tangent of glass fiber is reduced, but FilamentousThe handling of glass fibers tends to deteriorate. If the Al2O3 content is low, Filamentous The high-temperature viscosity of the glass fiber is reduced, and the Filamentous Glass fibers tend to fuse together, Filamentous The flexibility of the glass fiber is lost. On the other hand, the same is true for TiO2. Filamentous The dielectric loss tangent of glass fiber is reduced, but Filamentous Glass fiber tends to be difficult to handle. However, the glass fiber content is Filamentous Dielectric tangent of glass fiber and Filamentous The degree of effect on the handling of glass fiber is different from that of Al2O3. That is, if the content of TiO2 is low, it becomes difficult to suppress the generation of cristobalite crystals in the glass fiber when it is fired at high temperatures, and the glass fiber becomes brittle. The ratio of the content of Al2O3 to the content of TiO2 (Al2O3 / TiO2) is a combination of these tendencies, and Filamentous Reduction of the dielectric tangent of glass fiber and Filamentous It is presumed that this ratio is suitable for achieving both ease of handling of the glass fiber, and in particular ease of handling as a glass fiber fabric.

[0037] In this embodiment Filamentous In the glass composition constituting the glass fiber, Filamentous The value of T / (100-S), calculated from the SiO2 content S of the glass fiber and the TiO2 content T of the glass fiber, is in the range of, for example, 0.05 to 1.00. Filamentous Reduction of the dielectric tangent of glass fiber and Filamentous From the viewpoint of compatibility with the handleability of the glass fiber, the ratio is preferably in the range of 0.55 to 0.95, more preferably in the range of 0.60 to 0.94, even more preferably in the range of 0.66 to 0.90, particularly preferably in the range of 0.72 to 0.89, and most preferably in the range of 0.78 to 0.88.

[0038] In this embodiment Filamentous If the tensile breaking stress of the glass fiber is less than 1.0 MPa, Filamentous It becomes difficult to process the glass fiber into a glass fiber product such as the glass fiber fabric. Filamentous The dielectric loss tangent of the glass fiber cannot be reduced sufficiently.

[0039] In this embodiment Filamentous The tensile breaking stress of the glass fiber is Filamentous From the viewpoint of achieving both a reduction in the dielectric tangent of the glass fiber and the processability into glass fiber products, the pressure is preferably in the range of 8.8 to 60.0 MPa, more preferably in the range of 15.0 to 55.0 MPa, and even more preferably in the range of 25.0 to 50.0 MPa.

[0040] In this embodiment Filamentous The tensile breaking stress of the glass fiber can be measured and calculated by the following method. Filamentous In the case of a glass fiber fabric having glass fibers as warp yarns, first, four rectangular test pieces each having a length of 200 mm in the warp direction and a length of 25 mm in the weft direction are cut out from the glass fiber fabric, and then, a pressure-sensitive adhesive tape is attached to each of both ends of the test piece in the longitudinal direction so that the length between the tabs is 100 mm, thereby preparing a test piece with tabs.

[0041] Next, the tensile strength of each test piece is measured using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Strofluff VE20D) under conditions conforming to JIS R3420: 2013, and the average value is calculated. The tensile breaking stress of the glass fiber is calculated from the obtained average tensile strength value by the following formula. Tensile breaking stress = average tensile strength (unit: N / 25 mm) x density (unit: g / μm 3 ) / mass per unit length of warp thread (unit: g / μm) / density of warp thread (unit: thread / 25mm)

[0042] In this embodiment Filamentous In the measurement and calculation of the tensile breaking stress of the glass fiber, the measurement object is the present embodiment FilamentousIn the case of a glass fiber fabric having glass fibers as weft yarns, the measurement object is the same as that of this embodiment except that four rectangular test pieces each having a length of 200 mm in the weft direction and a length of 25 mm in the warp direction are cut out from the glass fiber fabric. Filamentous The tensile breaking stress is calculated in the same manner as in the case of a glass fiber fabric having glass fibers as warp yarns.

[0043] In addition, the measurement object is Filamentous In the case of a glass fiber fabric having glass fibers as warp and weft, the measurement object is the same as that of this embodiment except that two rectangular test pieces having a length of 200 mm in the warp direction and a length of 25 mm in the weft direction and two rectangular test pieces having a length of 200 mm in the weft direction and a length of 25 mm in the warp direction are cut out from the glass fiber fabric. Filamentous The tensile breaking stress is calculated in the same manner as in the case of a glass fiber fabric having glass fibers as warp yarns.

[0044] In addition, the measurement object is Filamentous In the case of a glass yarn or glass roving made of glass fiber, the test specimen is formed by attaching adhesive tape to both ends of the glass yarn or glass roving so that the length between the tabs is 100 mm, but the same procedure as in this embodiment is used for the measurement object. Filamentous The average value of the tensile strength is measured in the same manner as in the case of a glass fiber fabric made of glass fibers, and the tensile breaking stress is calculated by the following formula. Tensile breaking stress = average tensile strength (unit: N) x density (unit: g / μm 3 ) / Mass per unit length of glass yarn or glass roving (unit: g / μm)

[0045] In this embodiment Filamentous The SiO2 content S in the glass composition constituting the glass fiber, the TiO2 content T in the glass composition, and Filamentous Glass fiber Per bottle The tensile breaking stress BS satisfies the following formula (1). 5.2 ≦ BS × (T / (100-S)) 2 ≦ 33.8 (1)

[0046] In this embodiment Filamentous For glass fibers, BS × (T / (100-S)) 2 If the value is less than 5.2, Filamentous Glass fiber cannot have a very low dielectric tangent or sufficient handling properties, especially as a glass fiber fabric. On the other hand, BS×(T / (100-S)) 2 If the value is greater than 33.8, Filamentous Glass fibers cannot have an extremely low dielectric tangent. Filamentous The glass fiber has an extremely low dielectric tangent. Filamentous This means that the dielectric tangent of the glass fiber at a measurement frequency of 28 GHz is less than 0.0010.

[0047] In this embodiment Filamentous The dielectric loss tangent of the glass fiber at a measurement frequency of 28 GHz can be measured by the following method. Filamentous In the case of a glass fiber fabric having glass fibers as warp and weft, two test pieces of 5 cm x 5 cm are cut out from positions spaced apart from each other in the glass fiber fabric. Then, each test piece is heated, for example, in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours, Filamentous Remove organic matter and moisture from the surface of the glass fiber, such as surface treatment agents including silane coupling agents and sizing agents.

[0048] Then, for each of the test pieces obtained, the mass per unit area and density were measured in accordance with JIS R 3420:2013, and the mass per unit area (unit: g / μm 2 ) / density (unit: g / μm 3) to calculate the equivalent thickness (unit: μm). Next, for each test piece, a dielectric constant measuring device (manufactured by Anritsu Corporation, product name: MS46122B) is used to calculate the volume of the test piece using the calculated equivalent thickness, and the resonance frequency when the test piece is inserted and when it is not inserted, as well as the Q value when the test piece is inserted and when it is not inserted, are measured eight times at a measurement frequency of 28 GHz, and the average value of the obtained measured values ​​is calculated.

[0049] Next, the average value of the measured values ​​is used to calculate the following cylindrical cavity resonator method (A): thread Condition The dielectric tangent (tan δ) of the glass fiber is calculated. In the formula (A), α is a perturbation constant, fL is the resonance frequency when the test piece is inserted, f0 is the resonance frequency when the test piece is not inserted, V is the volume of the cylindrical cavity resonator, ΔV is the volume of the test piece, QL is the Q value when the test piece is inserted, and Q0 is the Q value when the test piece is not inserted.

[0050]

number

[0051] The measurement object is the Filamentous In the case where the glass yarn or glass roving is made of glass fiber, the measurement object is a glass fiber fabric obtained by weaving the glass yarn or glass roving. Filamentous The dielectric loss tangent is measured in the same manner as in the case of a glass fiber fabric made of glass fibers.

[0052] In addition, the measurement object is Filamentous In the case of a glass fiber fabric containing glass yarn or glass roving made of glass fiber as a part of the warp or weft, the glass fiber fabric to be measured is Filamentous A glass yarn or a glass roving made of glass fibers is extracted, and the above-mentioned measurement object of the extracted glass yarn or glass roving is Filamentous The dielectric loss tangent is measured in the same manner as in the case of glass yarn or glass roving made of glass fibers.

[0053] Here, the higher the BS value, the Filamentous The handling of the glass fiber, particularly the handling of the glass fiber fabric, is improved. Filamentous The dielectric tangent of the glass fiber tends to increase, and the lower the BS value, the Filamentous The handling of the glass fiber, especially the handling of the glass fiber fabric, tends to deteriorate. On the other hand, the higher the T / (100-S) value, the Filamentous The dielectric tangent of glass fiber tends to increase, and the lower the T / (100-S) value, the Filamentous The dielectric tangent of glass fiber tends to decrease. BS x (T / (100-S)) 2 The value of reflects these trends. Filamentous The handling of glass fibers, particularly the handling of glass fiber fabrics and the above Filamentous It is presumed that this represents a balance with the dielectric tangent of the glass fiber.

[0054] In this embodiment Filamentous In the glass fiber, it is preferable that S, T, and BS satisfy the following formula (2). 9.1 ≦ BS × (T / (100-S)) 2 ≦ 33.5 (2)

[0055] In this embodiment Filamentous In the glass fiber, when the S, T, and BS satisfy the formula (2), the Filamentous Glass fibers can reliably have an extremely low dielectric tangent and can also have excellent handleability, particularly as a glass fiber fabric.

[0056] In this embodiment Filamentous In the glass fiber, it is more preferable that S, T, and BS satisfy the following formula (3). 20.1 ≦ BS × (T / (100-S)) 2 ≦ 33.1 (3)

[0057] In this embodiment FilamentousIn the glass fiber, when the S, T, and BS satisfy the formula (3), the Filamentous Glass fibers have a particularly low dielectric tangent and excellent handleability, particularly as a glass fiber fabric. thread Condition The glass fiber has a particularly extremely low dielectric tangent. Filamentous This means that the dielectric tangent of the glass fiber at a measurement frequency of 28 GHz is 0.0005 or less.

[0058] In this embodiment Filamentous The glass fiber can be formed, for example, as follows. First, glass raw materials are mixed to obtain a mother glass composition based on the components contained in the ore that is the glass raw material, the content of each component, and the amount of volatilization of each component during the melting process. Filamentous In the glass fiber, the mother glass composition contains, relative to the total amount of the glass composition, SiO2 in the range of 45.0 to 65.0 mass%, Al2O3 in the range of 5.0 to 20.0 mass%, TiO2 in the range of 0.1 to 3.0 mass%, and CaO, MgO, SrO, B2O3, and ZrO2 in the range of 10 to 40 mass% in total, and the ratio of the CaO content to the total content of CaO, MgO, SrO, B2O3, and ZrO2 is in the range of 0.10 to 1.00.

[0059] Next, the prepared glass raw material (glass batch) is fed into a melting furnace and melted at a temperature range of 1000 poise temperature or higher, specifically, at a temperature in the range of 1450 to 1650° C. Next, the glass batch (molten glass) melted at the temperature range is discharged from 10 to 8000 nozzle tips or holes of a bushing controlled at a predetermined temperature. The discharged molten glass is then cooled and solidified while being stretched by winding at high speed to form glass single fibers (glass filaments), and these glass filaments are collected into one or more bundles to obtain a glass fiber bundle (glass strand).

[0060] The resulting glass strands are then further subjected to various known processes to obtain glass fiber products having a mother glass composition in various forms, such as yarns, woven fabrics, knitted fabrics, nonwoven fabrics including chopped strand mats and multiaxial nonwoven fabrics, chopped strands, rovings, powders, and the like.

[0061] Next, the glass fiber product having the above-mentioned mother glass composition is placed in an acid solution and treated with the acid solution to dissolve components other than SiO2 constituting the mother glass composition, thereby obtaining acid-dissolved glass fibers. Here, the acid solution may be an acid having a pH of 3.0 or less, and examples of the acid include nitric acid, hydrochloric acid, and sulfuric acid. The concentration of the acid solution is preferably 0.2 to 20.0 mass%.

[0062] Moreover, as a method for treating the glass fiber product with the acid solution, there can be mentioned a method in which the glass fiber product is placed in the acid solution and the acid solution is stirred or circulated. When the acid solution is stirred, the stirring speed is preferably in the range of 0.2 to 20 rps. When the acid solution is circulated, the flow rate is preferably in the range of 0.5 to 50 L / min. When treating the glass fiber product with the acid solution, the ratio of the mass of the glass fiber product to the volume of the acid solution is preferably in the range of 1.0 to 10.0 (g / L).

[0063] The treatment temperature when the glass fiber product is treated with the acid solution is preferably in the range of 40 to 95° C. The treatment time when the glass fiber product is treated with the acid solution is preferably in the range of 3 to 3000 minutes.

[0064] Next, the acid eluted glass fiber is subjected to a calcination treatment to obtain the glass fiber of this embodiment. FilamentousThe calcination treatment can be performed, for example, by placing the acid-eluted glass fiber in a heating device, heating it from room temperature to a calcination temperature in the range of 600 to 1200°C at a temperature increase rate in the range of 1.0 to 100.0°C / min, calcining it at the calcination temperature for a calcination time in the range of 0.8 to 80 hours, and then cooling it from the calcination temperature to room temperature at a temperature decrease rate of 1.0 to 100.0°C / min.

[0065] In this embodiment Filamentous In the glass composition constituting the glass fiber, the above-mentioned value of T / (100-S) can be controlled by the mother glass composition, the specific surface area of ​​the glass fiber product having the mother glass composition, and the treatment temperature and treatment time with the acid solution. For example, the value of T / (100-S) can be increased by increasing the TiO2 content of the mother glass composition or decreasing the ratio of the CaO content to the total content of CaO, MgO, SrO, B2O3 and ZrO2 in the mother glass composition. In addition, the value of T / (100-S) can be increased by reducing the diameter of the glass filaments constituting the glass fiber product having the mother glass composition and increasing the specific surface area of ​​the glass fiber product. In addition, the value of T / (100-S) can be increased by increasing the acid treatment temperature.

[0066] In this embodiment Filamentous Glass fiber Per bottle The tensile breaking stress BS can be controlled by the specific surface area of ​​the glass fiber product having the above-mentioned mother glass composition, the firing temperature and firing time of the firing treatment, and the above-mentioned value of T / (100-S). For example, the tensile breaking stress BS can be reduced by reducing the diameter of the glass filaments constituting the glass fiber product having the above-mentioned mother glass composition and increasing the specific surface area of ​​the glass fiber product. In addition, the tensile breaking stress BS can be reduced by increasing the firing temperature and lengthening the firing time. In addition, the tensile breaking stress BS can be reduced by reducing the value of T / (100-S).

[0067] In this embodiment Filamentous The glass filaments constituting the glass fiber usually have a circular cross-sectional shape and a diameter in the range of 2.0 to 35.0 μm. For applications requiring a low dielectric tangent, the glass filaments preferably have a diameter in the range of 2.5 to 9.0 μm, more preferably in the range of 2.8 to 6.0 μm, and even more preferably in the range of 3.0 to 4.5 μm.

[0068] When the glass filaments have an elliptical or oval 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 into that of a perfect circle (converted fiber diameter) is, for example, in the range of 2.0 to 35.0 μm.

[0069] In this embodiment Filamentous The glass fiber is usually in the form of a glass fiber bundle (glass strand) in which the glass filaments are bundled in a number ranging from 10 to 8000, and has a mass per unit length ranging from 0.3 to 10000.0 tex (g / km). Filamentous The glass fiber is preferably configured by bundling the glass filaments in a number ranging from 20 to 450, and has a mass per unit length ranging from 0.5 to 90.0 tex. Filamentous The glass fiber is preferably configured by bundling the glass filaments in a number ranging from 35 to 410, and has a mass per unit length ranging from 0.9 to 69.0 tex. Filamentous It is more preferable that the glass fiber is configured by bundling the glass filaments in a number ranging from 40 to 250, and has a mass per unit length ranging from 1.0 to 15.0 tex. Filamentous It is particularly preferable that the glass fiber is configured by bundling 50 to 220 of the above-mentioned glass filaments, and has a mass per unit length in the range of 1.1 to 7.0 tex.

[0070] In this embodiment Filamentous The glass fiber is Filamentous Improved adhesion between glass fibers and resin, Filamentous In a mixture of glass fiber and resin or inorganic material, Filamentous For the purpose of improving uniform dispersion of the glass fibers, the surface of the glass fibers may be coated with an organic material. Examples of such organic materials include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (particularly, carboxylic acid-modified polypropylene), and copolymers of (poly)carboxylic acid (particularly, maleic acid) and unsaturated monomers. Filamentous The glass fiber may be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, and the like in addition to these resins. Filamentous The glass fiber may be coated with a treatment composition that does not contain the above resin and that contains a silane coupling agent, a surfactant, and the like.

[0071] Such a resin composition or treatment composition is not coated with the resin composition or the treatment composition of the present embodiment. Filamentous The content of the glass fiber is in the range of 0.03 to 2.0% by mass. Filamentous Glass fiber is covered. Filamentous The coating of the glass fiber in this embodiment is in the form of a thread such as yarn or roving. Filamentous The resin solution (hereinafter referred to as "resin solution") or the resin composition solution (hereinafter referred to as "resin composition solution") is applied to the glass fiber using a known method such as a roller type applicator. Filamentous This can be achieved by applying the resin solution or the resin composition solution to glass fibers, and then drying the glass fibers to which the resin solution or the resin composition solution has been applied.

[0072] In addition, the organic matter Filamentous The glass fiber covering is in the form of a woven fabric in this embodiment. Filamentous The glass fiber is immersed in a solution of the treatment composition (hereinafter referred to as the treatment composition solution), and then the treatment composition solution is applied. Filamentous This can be done by drying the glass fibers.

[0073] In addition, the organic matter Filamentous The glass fiber coating of this embodiment is in the form of chopped strands or powder. Filamentous The glass fiber is immersed in the resin solution or the resin composition solution, stirred, and then the resin solution or the resin composition solution is applied. Filamentous This can be done by drying the glass fibers.

[0074] In addition, the organic matter Filamentous The glass fiber covering of this embodiment is in the form of a knitted fabric or nonwoven fabric. Filamentous This can be done by immersing glass fibers in the resin solution, the resin composition solution, or the treatment composition solution, and then drying the glass fibers to which the resin solution, the resin composition solution, or the treatment composition solution has been applied.

[0075] Here, examples of the silane coupling agent include aminosilane, chlorosilane, epoxysilane, mercaptosilane, vinylsilane, and (meth)acrylic silane. In this embodiment, the silane coupling agent may be used alone or in combination of two or more kinds.

[0076] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0077] An example of the chlorosilane is γ-chloropropyltrimethoxysilane.

[0078] Examples of epoxy silanes include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0079] An example of the mercaptosilane is γ-mercaptotrimethoxysilane.

[0080] Examples of vinyl silanes include vinyl trimethoxy silane and N-β-(N-vinylbenzyl aminoethyl)-γ-aminopropyl trimethoxy silane.

[0081] An example of the (meth)acrylsilane is γ-methacryloxypropyltrimethoxysilane.

[0082] Examples of the lubricant include modified silicone oil, animal oil and its hydrogenated product, vegetable oil and its hydrogenated product, animal wax, vegetable wax, mineral wax, condensation product of higher saturated fatty acid and higher saturated alcohol, polyethyleneimine, polyalkyl polyamine alkyl amide derivative, fatty acid amide, and quaternary ammonium salt. In this embodiment, the lubricant may be used alone or in combination of two or more kinds.

[0083] The animal oil may include beef tallow.

[0084] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, and the like.

[0085] Examples of animal waxes include beeswax and lanolin.

[0086] Examples of vegetable waxes include candelilla wax and carnauba wax.

[0087] Examples of mineral waxes include paraffin wax and montan wax.

[0088] Examples of the condensation products of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.

[0089] 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.

[0090] Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0091] Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. In this embodiment, the surfactant may be used alone or in combination of two or more kinds.

[0092] Examples of nonionic surfactants include ethylene oxide propylene oxide alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene block copolymers, alkyl polyoxyethylene-polyoxypropylene block copolymer ethers, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid monoesters, polyoxyethylene fatty acid diesters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid ester ethylene oxide adducts, polyoxyethylene castor oil ethers, hydrogenated castor oil ethylene oxide adducts, alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, glycerol fatty acid esters, polyglycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyhydric alcohol alkyl ethers, fatty acid alkanolamides, acetylene glycol, acetylene alcohol, ethylene oxide adducts of acetylene glycol, and ethylene oxide adducts of acetylene alcohol.

[0093] Examples of cationic surfactants include alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, alkyl dimethyl ethyl ammonium ethyl sulfate, higher alkyl amine salts, ethylene oxide adducts to higher alkyl amines, condensates of higher fatty acids and polyalkylene polyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline cationic surfactants, and alkyl pyridinium salts. Examples of higher alkyl amine salts include acetates and hydrochlorides.

[0094] Examples of anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfonates, α-olefin sulfonates, reaction products of fatty acid halides and N-methyltaurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphates of higher alcohol ethylene oxide adducts.

[0095] Examples of amphoteric surfactants include amino acid amphoteric surfactants, betaine amphoteric surfactants, and imidazoline amphoteric surfactants. Examples of amino acid amphoteric surfactants include alkali metal salts of alkylaminopropionic acid. Examples of betaine amphoteric surfactants include alkyldimethylbetaines.

[0096] The glass fiber fabric of this embodiment is Filamentous In the method for obtaining glass fibers, the glass fiber product having the above-mentioned mother glass composition can be obtained by using a glass fiber fabric having the above-mentioned mother glass composition. FilamentousIn the method for obtaining glass fibers, a glass fiber product having the above-mentioned mother glass composition can be obtained by using a glass yarn having the above-mentioned mother glass composition to obtain a glass yarn made of the glass fiber of this embodiment, and using this glass yarn as at least a part of the warp or weft, and weaving the glass yarn by a loom known per se.

[0097] Examples of the loom include a jet loom such as an air jet loom or a water jet loom, a shuttle loom, a rapier loom, etc. In the glass fiber fabric of the present embodiment, all of the warp and weft yarns are the same as those of the present embodiment described above. Filamentous It is preferably made of glass fiber.

[0098] Examples of weave patterns of the glass fiber fabric of the present embodiment include plain weave, satin weave, chevron weave, and twill weave. From the viewpoint of handling of the glass fiber fabric, plain weave is preferred.

[0099] In the glass fiber fabric of this embodiment, Filamentous The glass fiber preferably has glass filaments with a filament diameter in the range of 2.5 to 9.0 μm bundled in a number of 35 to 410, has a twist in the range of 0 to 1.0 turns / 25 mm, and has a mass per unit length in the range of 0.9 to 69.0 tex (g / 1000 m).

[0100] In the glass fiber fabric of this embodiment, Filamentous When glass fibers are contained as warp or weft, the warp weave density is preferably in the range of 40 to 130 threads / 25 mm, and the weft weave density is preferably in the range of 40 to 130 threads / 25 mm.

[0101] The glass fiber fabric of the present embodiment may be subjected to a surface treatment and a fiber opening treatment.

[0102] The surface treatment can include a treatment in which the glass fiber fabric is immersed in a solution containing the silane coupling agent or the silane coupling agent and the surfactant, excess water is squeezed out, and the fabric is then heated and dried at a temperature in the range of 80 to 180° C. for a time period in the range of 1 to 30 minutes.

[0103] Examples of the opening treatment include a treatment for expanding the yarn width of the warp yarns and the weft yarns by applying a tension in the range of 30 to 200 N to the warp yarns of the glass fiber fabric and performing opening by water flow pressure, opening by high-frequency vibration using a liquid as a medium, opening by pressure of a fluid having a surface pressure, opening by pressure using a roll, or the like.

[0104] The glass fiber fabric of the present embodiment has a fiber thickness of 6.0 to 180.0 g / m 2 and a thickness in the range of 7.0 to 150.0 μm. In addition, the glass fiber fabric of the present embodiment has a mass in the range of 7.0 to 80.0 g / m 2 It is more preferable that the insulating layer has a mass in the range of 1.0 to 80.0 μm and a thickness in the range of 8.0 to 80.0 μm.

[0105] In the glass fiber fabric of the present embodiment, the yarn width of the warp yarns is preferably in the range of 90 to 500 μm, and the yarn width of the weft yarns is preferably in the range of 90 to 500 μm.

[0106] The glass fiber fabric of the present embodiment may have a surface treatment layer containing the silane coupling agent, or the silane coupling agent and the surfactant. When the glass fiber fabric of the present embodiment includes the surface treatment layer, the surface treatment layer preferably has a mass of, for example, 0.03 to 1.50 mass% based on the total mass of the glass fiber fabric including the surface treatment layer.

[0107] The glass fiber reinforced resin composition of the present embodiment is FilamentousSpecifically, the glass fiber reinforced resin composition of the present embodiment is a glass fiber reinforced resin composition containing a thermoplastic resin or a thermosetting resin, glass fibers, and other additives, and the glass fiber reinforced resin composition contains 10 to 90 mass % of the above based on the total amount of the glass fiber reinforced resin composition. Filamentous The glass fiber reinforced resin composition of the present embodiment contains a resin in a range of 90 to 10 mass % and other additives in a range of 0 to 40 mass % based on the total amount of the glass fiber reinforced resin composition.

[0108] Here, examples of the thermoplastic resin 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), polycarbonate, and the like. Examples of suitable resins include carbonate, polyarylene sulfide, polyethersulfone (PES), polyphenylsulfone (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, polybutylene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, and polylactic acid.

[0109] 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.

[0110] Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0111] Examples of polystyrene include general-purpose polystyrene (GPPS), which is an atactic polystyrene having an atactic structure, high impact polystyrene (HIPS), which is GPPS with a rubber component added, and syndiotactic polystyrene having a syndiotactic structure.

[0112] Examples of the methacrylic resin include a homopolymer of one of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and a fatty acid vinyl ester, or a copolymer of two or more of them.

[0113] Examples of polyvinyl chloride include vinyl chloride homopolymers polymerized by conventional methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization; copolymers of vinyl chloride monomers with monomers copolymerizable therewith; and graft copolymers in which vinyl chloride monomers are graft-polymerized onto a polymer.

[0114] Polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), polydecamethylene adipamide (nylon 106), polytetramethylene sebacamide (nylon 106), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), polytetramethylene sebac ... Polyethylene sebacamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polyundecane amide (nylon 11), polyundecamethylene adipamide (nylon 116), polydodecanamide (nylon 12), polyxylene adipamide (nylon XD6), polyxylene sebacamide (nylon XD10), polymeta-xylylene adipamide (nylon MXD6), polypara-xylylene 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 of the polybis(3-methyl-4-aminohexyl)methane terephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methane isophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methanendodecamide (nylon PACM12), polybis(3-methyl-4-aminohexyl)methane tetradecamide (nylon PACM14), and the like, or copolymers of two or more of these components, or mixtures thereof, can be mentioned.

[0115] Examples of polyacetals include homopolymers having oxymethylene units as the main repeating units, and copolymers mainly composed of oxymethylene units and containing oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0116] Examples of polyethylene terephthalate include polymers obtained by polycondensing terephthalic acid or a derivative thereof with ethylene glycol.

[0117] Examples of polybutylene terephthalate include a polymer obtained by polycondensation of terephthalic acid or a derivative thereof with 1,4-butanediol.

[0118] Examples of polytrimethylene terephthalate include a polymer obtained by polycondensation of terephthalic acid or a derivative thereof with 1,3-propanediol.

[0119] 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, and polymers obtained by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

[0120] Examples of polyarylene sulfide include linear polyphenylene sulfide, crosslinked polyphenylene sulfide which has been polymerized and then cured, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.

[0121] Examples of polyphenylene ether include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl-1,4-phenylene ether), Examples of such poly(2-chloro-1,4-phenylene ether) 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).

[0122] Examples of modified polyphenylene ethers include a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / butadiene copolymer, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / maleic anhydride copolymer, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a polyamide, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / butadiene / acrylonitrile copolymer, the polyphenylene ether having a functional group such as an amino group, an epoxy group, a carboxy group, or a styryl group introduced at the polymer chain end, and the polyphenylene ether having a functional group such as an amino group, an epoxy group, a carboxy group, a styryl group, or a methacryl group introduced at the polymer chain side chain.

[0123] Examples of polyaryletherketones include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).

[0124] Examples of liquid crystal polymers (LCPs) include thermotropic liquid crystal polyesters, such as (co)polymers composed of one or more structural units selected from aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, and the like.

[0125] Examples of fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0126] Examples of ionomer (IO) resins include copolymers of olefin or styrene with unsaturated carboxylic acid, in which a portion of the carboxyl groups is neutralized with metal ions.

[0127] Examples of the olefin / vinyl alcohol resin include an ethylene / vinyl alcohol copolymer, a propylene / vinyl alcohol copolymer, a saponified ethylene / vinyl acetate copolymer, and a saponified propylene / vinyl acetate copolymer.

[0128] Examples of the cyclic olefin resin include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0129] Examples of polylactic acid include poly-L-lactic acid, which is a homopolymer of the L-form, poly-D-lactic acid, which is a homopolymer of the D-form, and stereocomplex polylactic acid, which is a mixture thereof.

[0130] Examples of the cellulose resin include methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxy methyl cellulose, hydroxy ethyl cellulose, hydroxy ethyl methyl cellulose, hydroxy propyl methyl cellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0131] Examples of the thermosetting resin include unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenolic resin (PF), urethane resin (PU), polyisocyanate, polyisocyanurate, polyimide (PI), urea (UF) resin, silicone (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleimide triazine (BT) resin, diallyl phthalate resin (PDAP), thermosetting polyphenylene ether, and thermosetting modified polyphenylene ether.

[0132] As the unsaturated polyester resin, there can be mentioned a resin obtained by subjecting an aliphatic unsaturated dicarboxylic acid and an aliphatic diol to an esterification reaction.

[0133] Examples of the vinyl ester resin include bis-based vinyl ester resins and novolac-based vinyl ester resins.

[0134] 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, tetraphenol group ethane type novolac type epoxy resin, etc. Examples of epoxy resins 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, naphthalene diol-type epoxy resins, difunctional to tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalene aralkyl-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.

[0135] The melamine resin may be a polymer obtained by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0136] Examples of the phenol resin include novolac-type phenol resins such as phenol novolac resin, cresol novolac resin, and bisphenol A-type novolac resin; resole-type phenol resins such as methylol-type resole resin and dimethylene ether-type resole resin; and aryl alkylene-type phenol resins; and the like. One or a combination of two or more of these may be used.

[0137] Urea resins include resins obtained by condensation of urea and formaldehyde.

[0138] The thermoplastic resins or thermosetting resins may be used alone or in combination of two or more kinds.

[0139] Since the glass fiber reinforced resin composition of the present embodiment is used for applications requiring a low dielectric tangent, the resin is preferably an epoxy resin, a modified polyphenylene ether, a thermosetting modified polyphenylene ether, a polybutylene terephthalate, a polypropylene, a fluororesin, or a liquid crystal polymer (LCP).

[0140] Examples of 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.

[0141] Examples of reinforcing fibers other than glass fibers include carbon fibers and metal fibers.

[0142] Examples of fillers other than glass fiber include glass powder, talc, and mica.

[0143] The glass fiber reinforced resin composition of the present embodiment may be a prepreg obtained by impregnating the glass fiber fabric of the present embodiment with the resin by a method known per se and semi-curing the impregnated glass fiber fabric.

[0144] The glass fiber reinforced resin composition of this embodiment can be molded by 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 molding, infusion, hand lay-up, spray-up, resin transfer molding, sheet molding compound method, bulk molding compound method, pultrusion method, filament winding method, etc. to obtain various glass fiber reinforced resin molded products. In addition, a glass fiber reinforced resin molded product can also be obtained by curing the prepreg.

[0145] Examples of applications of such molded articles include electronic device housings, electronic components, vehicle exterior parts, vehicle interior parts, vehicle engine peripheral parts, muffler-related parts, and high-pressure tanks.

[0146] An example of the electronic component is a printed wiring board.

[0147] Examples of vehicle exterior parts include bumpers, fenders, bonnets, air dams, wheel covers, and radomes.

[0148] Examples of vehicle interior parts include door trims and ceiling materials.

[0149] Examples of vehicle engine peripheral components include an oil pan, an engine cover, an intake manifold, an exhaust manifold, and the like.

[0150] Examples of muffler-related parts include heat-resistant sound-absorbing parts, dust-removing filters, and catalyst carriers.

[0151] In addition, in this embodiment FilamentousIn addition to the glass fiber reinforced resin composition of the present embodiment, the glass fiber can also be suitably used as a reinforcing material for inorganic materials such as gypsum, cement, etc. For example, when used as a reinforcing material for gypsum (particularly, a gypsum board having a thickness of 4 to 60 mm), the glass fiber having the glass composition in the above range can be contained in an amount of 0.1 to 4.0 mass% with respect to the total mass of the gypsum.

[0152] Next, examples of the present invention and comparative examples will be described. EXAMPLES

[0153] [Example 1] First, a glass yarn having composition A shown in Table 1 as a mother glass composition and consisting of 204 bundles of glass filaments having a diameter of 7.0 μm and a thickness of 21.0 tex was used as the warp and weft yarns, and the warp weave density was 59 threads / 25 mm, the weft weave density was 57 threads / 25 mm, the thickness was 90 μm, and the mass per unit area was 97 g / m 2 A glass fiber fabric having the above structure (hereinafter referred to as glass fiber fabric A) was prepared.

[0154] Next, the glass fiber fabric A was placed in a liquid tank containing nitric acid with a concentration of 6.3 mass% as an acid solution, and while stirring the acid solution, an acid leaching treatment was performed at a leaching temperature of 60°C for a leaching time of 180 minutes to obtain an acid-leaching treated glass fiber fabric. The ratio of the mass of the glass fiber fabric A to the volume of the liquid tank was 5.0 g / L.

[0155] Next, the acid eluted glass fiber fabric was placed in a muffle furnace and heated from room temperature to the firing temperature of 950°C at a heating rate of 3.3°C / min., and fired at the firing temperature for 24 hours. Thereafter, the temperature was lowered from the firing temperature to room temperature at a heating rate of 3.3°C / min. to obtain the glass fiber fabric of this example.

[0156] The obtained glass fiber fabric of this example had a glass filament diameter of 5.8 μm constituting the warp and weft, a mass per unit length of the warp and weft of 12.0 tex, a warp weave density of 69 threads / 25 mm, a weft weave density of 66 threads / 25 mm, a thickness of 84 μm, and a mass per unit area of ​​75 g / m 2 It was.

[0157] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured by the methods described above. The results are shown in Table 2.

[0158] In addition, the glass fiber fabric of this example is evaluated according to the following criteria: Filamentous The handleability of the glass fiber was evaluated. When both ends of the glass fiber fabric cut into a size of 10 cm x 10 cm were held and the glass fiber fabric was folded 180° at the center, the glass fiber fabric was rated as A if it returned to its original position. When the cut glass fiber fabric was folded 180° at the center, it was rated as B if it did not return to its original position or if it broke at the bent portion. When the cut glass fiber fabric was folded 180° at the center, it was rated as C if the glass fiber fabric was cut before being folded 180°. The results are shown in Table 2.

[0159] [Example 2] The glass fiber fabric of this example was obtained in exactly the same manner as in Example 1, except that the acid eluted glass fiber fabric was fired at a firing temperature of 1100° C. for one hour.

[0160] The obtained glass fiber fabric of this example had a glass filament diameter of 5.8 μm constituting the warp and weft, a mass per unit length of the warp and weft of 12.0 tex, a warp weave density of 69 threads / 25 mm, a weft weave density of 66 threads / 25 mm, a thickness of 84 μm, and a mass per unit area of ​​75 g / m 2 It was.

[0161] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured by the above-mentioned methods. In addition, the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.

[0162] [Example 3] First, a glass yarn having composition A shown in Table 1 as a mother glass composition and consisting of 204 bundles of glass filaments having a diameter of 4.8 μm and a thickness of 10 tex was used as the warp and weft yarns, and the warp weave density was 53 threads / 25 mm, the weft weave density was 53 threads / 25 mm, the thickness was 50 μm, and the mass per unit area was 45 g / m 2 A glass fiber fabric having the above structure (hereinafter referred to as glass fiber fabric B) was prepared.

[0163] Next, the glass fiber fabric B was placed in a liquid tank containing nitric acid with a concentration of 6.3 mass% as an acid solution, and an acid leaching treatment was performed while stirring the acid solution at a leaching temperature of 50°C and a leaching time of 360 minutes to obtain an acid-leaching treated glass fiber fabric. The ratio of the mass of the glass fiber fabric B to the volume of the liquid tank was 2.5 g / L.

[0164] Next, the acid-eluted glass fiber fabric was placed in a muffle furnace, heated from room temperature to the firing temperature of 900° C. at a heating rate of 3.3° C. / min, and fired at the firing temperature for 24 hours. The temperature was then lowered from the firing temperature to room temperature at a heating rate of 3.3° C. / min. Noga A lath fiber fabric was obtained.

[0165] The obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 4.3 μm in diameter, a mass per unit length of the warp and weft of 6.5 tex, a warp weave density of 61 threads / 25 mm, a weft weave density of 61 threads / 25 mm, a thickness of 40 μm, and a mass per unit area of ​​34 g / m 2 It was.

[0166] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured by the above-mentioned methods. FilamentousThe handleability of the glass fiber was evaluated, and the results are shown in Table 2.

[0167] [Example 4] The glass fiber fabric of this example was obtained in exactly the same manner as in Example 3, except that in the acid leaching treatment, the leaching temperature was 60°C, the mass ratio of the glass fiber fabric B to the volume of the liquid tank was 5.0 g / L, the firing temperature when firing the acid leaching-treated glass fiber fabric was 850°C, and the firing time was 48 hours.

[0168] The obtained glass fiber fabric of this example had a glass filament diameter of 4.3 μm constituting the warp and weft, a mass per unit length of the warp and weft of 6.5 tex, a warp weave density of 61 threads / 25 mm, a weft weave density of 61 threads / 25 mm, a thickness of 40 μm, and a mass per unit area of ​​34 g / m 2 It was.

[0169] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured by the above-mentioned methods. Filamentous The handleability of the fibers was evaluated, and the results are shown in Table 2.

[0170] [Example 5] The glass fiber fabric of this example was obtained in exactly the same manner as in Example 3, except that in the acid leaching treatment, the leaching temperature was 60°C, the ratio of the mass of the glass fiber fabric B to the volume of the liquid tank was 5.0 g / L, the firing temperature when firing the acid leaching-treated glass fiber fabric was 870°C, and the firing time was 48 hours.

[0171] The obtained glass fiber fabric of this example had a glass filament diameter of 4.3 μm constituting the warp and weft, a mass per unit length of 6.5 tex of the warp and weft, a warp weave density of 61 threads / 25 mm, a weft weave density of 61 threads / 25 mm, a thickness of 40 μm, and a mass per unit area of ​​34 g / m 2 It was.

[0172] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 2.

[0173] [Example 6] The glass fiber fabric of this example was obtained in exactly the same manner as in Example 1, except that in the acid leaching treatment, the leaching time was 360 minutes and the firing temperature was 900°C.

[0174] The obtained glass fiber fabric of this example had a glass filament diameter of 5.8 μm constituting the warp and weft, a mass per unit length of the warp and weft of 12.0 tex, a warp weave density of 69 threads / 25 mm, a weft weave density of 66 threads / 25 mm, a thickness of 84 μm, and a mass per unit area of ​​75 g / m 2 It was.

[0175] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 2.

[0176] [Example 7] The glass fiber fabric of this example was obtained in exactly the same manner as in Example 3, except that the elution temperature in the acid elution treatment was 60°C.

[0177] The obtained glass fiber fabric of this example had a glass filament diameter of 4.3 μm constituting the warp and weft, a mass per unit length of the warp and weft of 6.5 tex, a warp weave density of 61 threads / 25 mm, a weft weave density of 61 threads / 25 mm, a thickness of 40 μm, and a mass per unit area of ​​34 g / m 2 It was.

[0178] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 2.

[0179] [Comparative Example 1] The glass fiber fabric of this comparative example was obtained in exactly the same manner as in Example 4, except that the acid eluted glass fiber fabric was fired at a firing temperature of 800° C. and for a firing time of 72 hours.

[0180] The obtained glass fiber fabric of this comparative example had a glass filament diameter of 4.3 μm constituting the warp and weft, a mass per unit length of the warp and weft of 6.5 tex, a warp weave density of 61 threads / 25 mm, a weft weave density of 61 threads / 25 mm, a thickness of 40 μm, and a mass per unit area of ​​34 g / m 2 It was.

[0181] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 3.

[0182] [Comparative Example 2] The glass fiber fabric of this comparative example was obtained in exactly the same manner as in Example 4, except that the acid eluted glass fiber fabric was fired at a firing temperature of 900° C. for a firing time of 24 hours.

[0183] The obtained glass fiber fabric of this comparative example had a glass filament diameter of 4.3 μm constituting the warp and weft, a mass per unit length of the warp and weft of 6.5 tex, a warp weave density of 61 threads / 25 mm, a weft weave density of 61 threads / 25 mm, a thickness of 40 μm, and a mass per unit area of ​​34 g / m 2 It was.

[0184] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 3.

[0185] [Comparative Example 3] The glass fiber fabric of this comparative example was obtained in exactly the same manner as in Example 3, except that the elution temperature in the acid elution treatment was 40°C.

[0186] The obtained glass fiber fabric of this comparative example had a glass filament diameter of 4.3 μm constituting the warp and weft, a mass per unit length of the warp and weft of 6.5 tex, a warp weave density of 61 threads / 25 mm, a weft weave density of 61 threads / 25 mm, a thickness of 40 μm, and a mass per unit area of ​​34 g / m 2 It was.

[0187] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 3.

[0188] [Comparative Example 4] First, a glass yarn having composition B shown in Table 1 as a mother glass composition and consisting of 204 bundles of glass filaments having a diameter of 7.4 μm and a thickness of 22 tex was used as the warp and weft yarns, and the warp weave density was 59 threads / 25 mm, the weft weave density was 57 threads / 25 mm, the thickness was 90 μm, and the mass per unit area was 101 g / m 2 A glass fiber fabric (hereinafter referred to as glass fiber fabric C) was prepared.

[0189] Next, the glass fiber fabric C was placed in a liquid tank containing nitric acid with a concentration of 6.3 mass% as an acid solution, and while stirring the acid solution, an acid leaching treatment was performed at a leaching temperature of 60°C and a leaching time of 2880 minutes to obtain an acid-leaching treated glass fiber fabric. The ratio of the mass of the glass fiber fabric C to the volume of the liquid tank was 5.0 g / L.

[0190] Next, the acid eluted glass fiber fabric was placed in a muffle furnace and heated from room temperature to the firing temperature of 900°C at a heating rate of 3.3°C / min., and fired at the firing temperature for 24 hours. Thereafter, the temperature was lowered from the firing temperature to room temperature at a heating rate of 3.3°C / min. to obtain the glass fiber fabric of this comparative example.

[0191] The obtained glass fiber fabric of this comparative example had a glass filament diameter of 6.3 μm constituting the warp and weft, a mass per unit length of the warp and weft of 14 tex, a warp weave density of 68 threads / 25 mm, a weft weave density of 65 threads / 25 mm, a thickness of 87 μm, and a mass per unit area of ​​79 g / m 2 It was.

[0192] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 3.

[0193] [Comparative Example 5] The glass fiber fabric of this comparative example was obtained in exactly the same manner as in Comparative Example 4, except that in the acid leaching treatment, nitric acid with a concentration of 18.0 mass % was used as the acid solution and the leaching time was 360 minutes.

[0194] The obtained glass fiber fabric of this comparative example had glass filaments constituting the warp and weft of 6.3 μm in diameter, a mass per unit length of the warp and weft of 14 tex, a warp weave density of 68 threads / 25 mm, a weft weave density of 65 threads / 25 mm, a thickness of 87 μm, and a mass per unit area of ​​79 g / m 2 It was.

[0195] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 3.

[0196] [Comparative Example 6] The glass fiber fabric of this comparative example was obtained in exactly the same manner as in Comparative Example 4, except that in the acid leaching treatment, hydrochloric acid having a concentration of 3.6 mass % was used as the acid solution.

[0197] The obtained glass fiber fabric of this comparative example had a glass filament diameter of 6.3 μm constituting the warp and weft, a mass per unit length of the warp and weft of 14 tex, a warp weave density of 68 threads / 25 mm, a weft weave density of 65 threads / 25 mm, a thickness of 87 μm, and a mass per unit area of ​​79 g / m 2 It was.

[0198] The glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured by the above-mentioned methods. Filamentous The handleability of the glass fiber was evaluated, and the results are shown in Table 3.

[0199] [Table 1]

[0200] [Table 2]

[0201] [Table 3]

[0202] From Table 2, the BS × (T / (100-S)) 2 The glass fibers of Examples 1 to 7, in which the value is in the range of 5.2 to 33.8, have a dielectric loss tangent of less than 0.0010 at a measurement frequency of 28 GHz and are excellent in handleability. Filamentous It is clear that glass fibers can be obtained.

[0203] On the other hand, from Table 3, the BS×(T / (100−S)) 2 The value of Comparative Example 1 is more than 33.8. Filamentous It is clear that the glass fiber has a dielectric loss tangent of more than 0.0010 at a measurement frequency of 28 GHz.

[0204] Also, from Table 3, the BS×(T / (100−S))2 The glass fibers of Comparative Examples 2 to 6, in which the value is less than 5.2, have a dielectric tangent of more than 0.0010 at a measurement frequency of 28 GHz or have sufficient handleability. Filamentous It is clear that glass fibres cannot be obtained.

Claims

1. A filamentous glass fiber, SiO in the range of 92.50 to 99.99 mass% based on the total amount of the glass composition ２ and, TiO in the range of 0.01 to 5.00 mass% ２ and, Al in the range of 0.00 to 2.50 mass% ２ O ３ and a glass composition comprising: The tensile breaking stress of the filamentous glass fiber is in the range of 1.0 to 100.0 MPa; The SiO ２ The content S of TiO ２ and a tensile breaking stress BS per one of the filamentous glass fibers satisfy the following formula (1): 5.2 ≦ BS × (T / (100-S)) ２ ≦ 33.8 ・・・(1)

2. The SiO ２ The content S of TiO ２ 2. The filamentous glass fiber according to claim 1 , wherein the content T of and the tensile breaking stress BS satisfy the following formula (2): 9.1 ≦ BS × (T / (100-S)) ２ ≦ 33.5 ・・・(2)

3. The SiO ２ The content S of TiO ２ 2. The filamentous glass fiber according to claim 1 , wherein the content T of and the tensile breaking stress BS satisfy the following formula (3): 20.1 ≦ BS × (T / (100-S)) ２ ≦ 33.1 ・・・(3)

4. A glass fiber fabric comprising the filamentous glass fiber according to any one of claims 1 to 3.

5. A glass fiber reinforced resin composition comprising the filamentous glass fiber according to any one of claims 1 to 3.

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