Classifications

• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D1/00—Woven fabrics designed to make specified articles
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C13/00—Fibre or filament compositions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/66—Chemical treatment, e.g. leaching, acid or alkali treatment
  • C03C25/68—Chemical treatment, e.g. leaching, acid or alkali treatment by etching
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
  • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
  • D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
  • D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
  • D03D15/267—Glass
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/30—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the fibres or filaments
  • D03D15/33—Ultrafine fibres, e.g. microfibres or nanofibres
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
  • D03D15/573—Tensile strength
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2101/00—Inorganic fibres
  • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
  • D10B2101/06—Glass
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/06—Load-responsive characteristics
  • D10B2401/063—Load-responsive characteristics high strength
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2505/00—Industrial
  • D10B2505/02—Reinforcing materials; Prepregs

Definitions

• the present invention relates to glass fibers, glass fiber fabrics, and glass fiber reinforced resin compositions.
• glass fibers have been widely used in a variety of applications to improve the strength of resin molded products, which are used in components such as the housings and printed wiring boards of electronic devices such as servers, smartphones, and laptops.
• dielectrics such as glass absorb part of the energy of an AC electric field as heat (called dielectric loss), so if the resin molded product is used for the housing or parts of the electronic device, there is a problem that the resin molded product generates heat.
• W is the dielectric loss
• k is a constant
• f is the frequency
• ⁇ is the dielectric constant
• tan ⁇ is the dielectric tangent
• Known glass fibers with an extremely low dielectric tangent include glass fibers having a quartz glass composition in which the content of SiO 2 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, as a method for producing glass fibers having a glass composition with such a high content of SiO 2 , a method is known in which components other than SiO 2 are dissolved in an acid solution from a mother glass composition containing components other than SiO 2 that are easily soluble in acid (see, for example, Patent Document 2).
• an 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 using the method described below.
• JP 2009-263569 A Japanese Patent Application Publication No. 9-169548
• the glass fiber having a high SiO2 content relative to the total amount of the glass composition obtained by the method of Patent Document 2 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.
• the present invention aims to eliminate these disadvantages and provide glass fibers that have an extremely low dielectric tangent and are easy to handle.
• the present invention also aims to provide a glass fiber fabric and a glass fiber reinforced resin composition that contain the glass fiber of the present invention.
• the glass fiber of the present invention is characterized in that it comprises a glass composition containing, relative to the total amount of the glass composition, SiO 2 in the range of 92.50 to 99.99 mass %, TiO 2 in the range of 0.01 to 5.00 mass %, and Al 2 O 3 in the range of 0.00 to 2.50 mass %, and that the tensile breaking stress of the glass fiber is in the range of 1.0 to 100.0 MPa, and the SiO 2 content S, TiO 2 content T, and tensile breaking stress BS of the glass fiber satisfy the following formula (1): 5.2 ⁇ BS ⁇ (T/(100-S)) 2 ⁇ 33.8 ... (1)
• the glass fiber of the present invention has a glass composition in which the contents of SiO 2 , TiO 2 and Al 2 O 3 are within the above-mentioned ranges, the tensile breaking stress of the glass fiber is within the above-mentioned ranges, and the S, T and BS satisfy the formula (1), thereby providing an extremely low dielectric tangent and sufficient handleability.
• the S, T and BS satisfy the following formula (2). 9.1 ⁇ BS ⁇ (T/(100-S)) 2 ⁇ 33.5 ... (2)
• the glass fiber of the present invention with S, T, and BS satisfying formula (2), can more reliably have an extremely low dielectric tangent and excellent handleability.
• the S, T and BS satisfy the following formula (3). 20.1 ⁇ BS ⁇ (T/(100-S)) 2 ⁇ 33.1 ... (3)
• the glass fiber of the present invention has an extremely low dielectric tangent and excellent handleability because the S, T, and BS satisfy formula (3).
• "having an extremely low dielectric tangent” means that the dielectric tangent of the glass fiber at a measurement frequency of 28 GHz is 0.0005 or less.
• the dielectric tangent of the glass fiber at a measurement frequency of 28 GHz can be measured by the method described below.
• the glass fiber fabric of the present invention is characterized by containing the glass fiber of the present invention described above.
• the glass fiber reinforced resin composition of the present invention is characterized by containing the glass fiber of the present invention described above.
• the glass fiber of the present embodiment has a glass composition containing, relative to the total amount of the glass composition, SiO 2 in the range of 92.50 to 99.99 mass %, TiO 2 in the range of 0.01 to 5.00 mass %, and Al 2 O 3 in the range of 0.00 to 2.50 mass %, and the tensile breaking stress of the glass fiber is in the range of 1.0 to 100.0 MPa, and the SiO 2 content S, the TiO 2 content T, and the tensile breaking stress BS of the glass fiber satisfy the following formula (1): 5.2 ⁇ BS ⁇ (T/(100-S)) 2 ⁇ 33.8 ... (1)
• the glass fiber of the present embodiment has a glass composition in which the contents of SiO 2 , TiO 2 and Al 2 O 3 are within the above-mentioned ranges, the tensile breaking stress of the glass fiber is within the above-mentioned ranges, and the S, T and BS satisfy the formula (1), so that the glass fiber has an extremely low dielectric tangent and is sufficiently easy to handle, particularly as a glass fiber fabric.
• the dielectric tangent of the glass fiber cannot be sufficiently reduced.
• the content of SiO2 in the glass fiber is more than 99.99 mass% based on the total amount of the glass composition, the flexibility of the glass fiber is lost, and the handling properties, particularly the handling properties as a glass fiber fabric, are deteriorated.
• the content of SiO 2 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.
• the handling of the glass fiber particularly the handling of the glass fiber fabric, deteriorates. Also, if the content of TiO2 in the glass fiber exceeds 5.00 mass% relative to the total amount of the glass composition, the dielectric loss tangent of the glass fiber cannot be sufficiently reduced.
• the content of TiO 2 is preferably in the range of 0.11 to 3.50 mass%, more preferably in the range of 0.31 to 1.94 mass%, even more preferably in the range of 0.51 to 1.80 mass%, particularly preferably in the range of 0.71 to 1.64 mass%, particularly preferably in the range of 0.72 to 1.44 mass%, particularly preferably in the range of 0.73 to 1.20 mass%, and most preferably in the range of 0.75 to 0.99 mass%, based on the total amount of the glass composition.
• the dielectric loss tangent of the glass fiber cannot be sufficiently reduced.
• the content of Al 2 O 3 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.
• the glass composition constituting the glass fiber of this embodiment 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% relative to the total amount of the glass composition, preferably less than 0.50 mass%, and more preferably less than 0.20 mass%.
• the glass composition constituting the glass fiber of this embodiment does not contain , as impurities, Li2O , Na2O , K2O , MgO, CaO, B2O3 , P2O5 , FeO , Fe2O3 , SnO2 , SrO, BaO , CeO2 , Y2O3 , La2O3 , Bi2O3 , Gd2O3 , Pr2O3 , Sc2O3 , or Yb2O .
• the content thereof is preferably, each 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%, relative to the total amount of the glass composition.
• the glass composition constituting the glass fiber of this embodiment may contain, as impurities, F 2 , Cl 2 , and SO 3 , each independently in a range of less than 0.20 mass % relative to the total amount of the glass composition, preferably in a range of less than 0.10 mass %, more preferably in a range of less than 0.05 mass %, even more preferably in a range of less than 0.03 mass %, and most preferably in a range of less than 0.01 mass %.
• each component in the glass composition that constitutes the glass fiber of this embodiment can be measured using an ICP optical emission spectrometer for the light element Li.
• the content of other elements can be measured using a wavelength dispersive X-ray fluorescence analyzer.
• the following method can be used as a measurement method.
• the glass fibers are crushed and powdered to obtain glass powder. If organic matter is attached to the surface of the glass fibers, or if the glass fibers are contained in an organic matter (resin) mainly as a reinforcing material, the glass fibers are used after removing the organic matter by, for example, heating in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours.
• organic matter mainly as a reinforcing material
• the light element Li is quantitatively analyzed using an ICP optical emission spectrometer after the glass powder is heated and decomposed with acid.
• the other elements are quantitatively analyzed using a wavelength-dispersive X-ray fluorescence analyzer after the glass powder is formed into a disk shape using a press.
• 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 it using the calibration curve method.
• the content of each component in the calibration curve sample can be quantitatively analyzed using an ICP optical 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 of the aforementioned components can be calculated from these values.
• the ratio of the content of Al 2 O 3 to the content of TiO 2 is preferably in the range of 0.00 to 0.30, more preferably in the range of 0.00 to 0.20, even more preferably in the range of 0.00 to 0.14, and particularly preferably in the range of 0.03 to 0.12, from the viewpoint of further reducing the dielectric tangent of the glass fiber while maintaining the handleability of the glass fiber, particularly the handleability as a glass fiber fabric.
• the lower the content of Al 2 O 3 the lower the dielectric tangent of the glass fiber, but the worse the handleability of the glass fiber tends to be.
• the content of Al 2 O 3 is low, the high-temperature viscosity of the glass fiber decreases, and the glass fibers are more likely to fuse to each other when fired at a high temperature, causing the glass fiber to lose its flexibility.
• the lower the content of TiO2 the lower the dielectric loss tangent of the glass fiber, but the worse the handling of the glass fiber.
• the degree of effect of the content on the dielectric loss tangent of the glass fiber and the handling of the glass fiber is different from that of Al2O3 . That is, if the content of TiO2 is low, it becomes difficult to suppress the cristobalite crystals generated in the glass fiber during high-temperature firing, 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 shows a suitable ratio for achieving both the reduction of the dielectric loss tangent of the glass fiber and the handling of the glass fiber, especially the handling of the glass fiber fabric.
• 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, for example, in the range of 0.05 to 1.00.
• the value of T/(100-S) 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.
• the tensile breaking stress of the glass fiber of this embodiment is less than 1.0 MPa, it becomes difficult to process the glass fiber into a glass fiber product such as the glass fiber fabric. Furthermore, if the tensile breaking stress is more than 100.0 MPa, the dielectric tangent of the glass fiber cannot be sufficiently reduced.
• the tensile breaking stress of the glass fiber of this embodiment 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, from the viewpoint of achieving both a reduction in the dielectric tangent of the glass fiber and processability into glass fiber products.
• the tensile breaking stress of the glass fiber of this embodiment can be measured and calculated by the following method.
• the measurement object is a glass fiber fabric made of the glass fiber of this embodiment as a warp thread
• 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 in accordance with JIS R 3420: 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/ ⁇ m 3 ) / mass per unit length of warp thread (unit: g/ ⁇ m) / weaving density of warp thread (unit: thread/25 mm)
• the tensile breaking stress is calculated in the same manner as when the object to be measured is a glass fiber fabric made of the glass fiber of this embodiment as the warp, 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 of the glass fiber fabric.
• the tensile breaking stress is calculated in the same manner as when the object to be measured is a glass fiber fabric having the glass fibers of this embodiment as the warp, 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.
• the average value of the tensile strength is measured in the same manner as when the measurement subject is a glass fiber fabric made of the glass fiber of this embodiment, except for using a test specimen in which tabs are formed by adhering adhesive tape to both ends of the glass yarn or glass roving so that the tab-to-tab length is 100 mm, and the tensile breaking stress is calculated by the following formula.
• Tensile breaking stress average tensile strength (unit: N) x density (unit: g/ ⁇ m 3 ) / mass per unit length of glass yarn or glass roving (unit: g/ ⁇ m)
• the SiO 2 content S in the glass composition constituting the glass fiber of this embodiment, the TiO 2 content T in the glass composition, and the tensile breaking stress BS of the glass fiber satisfy the following formula (1). 5.2 ⁇ BS ⁇ (T/(100-S)) 2 ⁇ 33.8 ... (1)
• the glass fiber of this embodiment when the value of BS ⁇ (T/(100 ⁇ S)) 2 is less than 5.2, the glass fiber cannot have an extremely low dielectric tangent or cannot have sufficient handleability, particularly handleability as a glass fiber fabric. On the other hand, when the value of BS ⁇ (T/(100 ⁇ S)) 2 is more than 33.8, the glass fiber of this embodiment cannot have an extremely low dielectric tangent.
• the expression "the glass fiber of this embodiment has an 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 loss tangent of the glass fiber of this embodiment at a measurement frequency of 28 GHz can be measured by the following method.
• the measurement object is a glass fiber fabric made of the glass fiber of this embodiment 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.
• each test piece is heated, for example, in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours to remove organic matter such as surface treatment agents containing silane coupling agents and sizing agents adhering to the glass fiber surface, as well as moisture.
• the mass and density per unit area are measured in accordance with JIS R 3420:2013, and the converted thickness (unit: ⁇ m) is calculated by mass per unit area (unit: g/ ⁇ m 2 )/density (unit: g/ ⁇ m 3 ).
• 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 converted thickness, and the resonance frequency when the test piece is inserted and when it is not inserted, and 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.
• the dielectric loss tangent (in the formula: tan ⁇ ) of the glass fiber is calculated using the average value of the obtained measured values and the following calculation formula (A) of the cylindrical cavity resonator method.
• ⁇ is a perturbation constant
• f L is the resonance frequency when the test piece is inserted
• f 0 is the resonance frequency when the test piece is not inserted
• V is the volume of the cylindrical cavity resonator
• ⁇ V is the volume of the test piece
• Q L is the Q value when the test piece is inserted
• Q 0 is the Q value when the test piece is not inserted.
• the dielectric tangent is measured for the glass fiber fabric obtained by weaving the glass yarn or glass roving in the same manner as when the measurement object is a glass fiber fabric made of the glass fiber of this embodiment.
• the measurement object is a glass fiber fabric containing a glass yarn or glass roving made of the glass fiber of this embodiment as part of the warp or weft
• the glass yarn or glass roving made of the glass fiber of this embodiment is extracted from the glass fiber fabric to be measured, and the dielectric loss tangent of the extracted glass yarn or glass roving is measured in the same manner as in the case where the measurement object is a glass yarn or glass roving made of the glass fiber of this embodiment.
• the higher the BS value the better the handleability of the glass fiber, particularly as a glass fiber fabric, but the dielectric loss tangent of the glass fiber tends to increase, and the lower the BS value, the worse the handleability of the glass fiber, particularly as a glass fiber fabric.
• the higher the T/(100-S) value the greater the dielectric loss tangent of the glass fiber tends to increase, and the lower the T/(100-S) value, the greater the dielectric loss tangent of the glass fiber tends to decrease. It is presumed that the value of BS ⁇ (T/(100-S)) 2 reflects these trends and indicates a balance between the handleability of the glass fiber, particularly as a glass fiber fabric, and the dielectric loss tangent of the glass fiber.
• S, T, and BS satisfy the following formula (2). 9.1 ⁇ BS ⁇ (T/(100-S)) 2 ⁇ 33.5 ... (2)
• the glass fiber of this embodiment by satisfying formula (2) for S, T, and BS, the glass fiber can more reliably have an extremely low dielectric tangent and excellent handleability, particularly as a glass fiber fabric.
• S, T, and BS satisfy the following formula (3). 20.1 ⁇ BS ⁇ (T/(100-S)) 2 ⁇ 33.1 ... (3)
• the S, T, and BS satisfy formula (3), so that the glass fiber has a particularly low dielectric tangent and excellent handleability, particularly handleability as a glass fiber fabric.
• the glass fiber of this embodiment has a particularly low dielectric tangent, which means that the dielectric tangent of the glass fiber at a measurement frequency of 28 GHz is 0.0005 or less.
• the glass fiber of this embodiment 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 contents of each component, and the volatilization amount of each component during the melting process.
• the mother glass composition contains SiO 2 in the range of 45.0 to 65.0 mass%, Al 2 O 3 in the range of 5.0 to 20.0 mass%, TiO 2 in the range of 0.1 to 3.0 mass%, and CaO, MgO, SrO, B 2 O 3, and ZrO 2 in the range of 10 to 40 mass% in total, relative to the total amount of the glass composition, and the ratio of the content of CaO to the total content of CaO, MgO, SrO, B 2 O 3, and ZrO 2 is in the range of 0.10 to 1.00.
• the prepared glass raw material (glass batch) is then fed into a melting furnace and melted at a temperature range of 1000 poise or higher, specifically, at a temperature in the range of 1450 to 1650°C.
• the glass batch (molten glass) melted at the above temperature range is then discharged from 10 to 8000 nozzle tips or holes in a bushing, which are controlled to 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 then collected into one or more bundles to obtain glass fiber bundles (glass strands).
• the obtained glass strands are further subjected to various known processes to obtain glass fiber products having a mother glass composition in various forms such as yarn, woven fabric, knitted fabric, nonwoven fabric including chopped strand mat and multiaxial nonwoven fabric, chopped strand, roving, powder, etc.
• the glass fiber product having the 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.
• an acid having a pH of 3.0 or less can be used as the acid solution, 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%.
• 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.
• the stirring speed is preferably in the range of 0.2 to 20 rps.
• the flow rate is preferably in the range of 0.5 to 50 L/min.
• 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).
• the treatment temperature when treating the glass fiber product with the acid solution is preferably in the range of 40 to 95°C. Furthermore, the treatment time when treating the glass fiber product with the acid solution is preferably in the range of 3 to 3000 minutes.
• the glass fiber of this embodiment can be obtained by subjecting the acid-eluted glass fiber to a firing treatment.
• the firing treatment can be performed, for example, by placing the acid-eluted glass fiber in a heating device, heating it from room temperature to a firing temperature in the range of 600 to 1200°C at a heating rate in the range of 1.0 to 100.0°C/min, firing it at the firing temperature for a firing time in the range of 0.8 to 80 hours, and then cooling it from the firing temperature to room temperature at a heating rate of 1.0 to 100.0°C/min.
• 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.
• the value of T/(100-S) can be increased by increasing the TiO 2 content of the mother glass composition or decreasing the ratio of the CaO content to the total content of CaO, MgO, SrO, B 2 O 3 and ZrO 2 in the mother glass composition.
• the value of T/(100-S) can be increased by, for example, 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.
• the value of T/(100-S) can be increased by increasing the acid treatment temperature.
• the tensile breaking stress BS of the glass fiber of this embodiment can be controlled by the specific surface area of the glass fiber product having the mother glass composition, the firing temperature and firing time of the firing treatment, and the above-mentioned value of T/(100-S).
• the tensile breaking stress BS can be reduced 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.
• the tensile breaking stress BS can also be reduced by increasing the firing temperature and lengthening the firing time.
• the tensile breaking stress BS can also be reduced by reducing the value of T/(100-S).
• the glass filaments constituting the glass fiber of this embodiment typically have a perfectly circular cross-sectional shape and a diameter in the range of 2.0 to 35.0 ⁇ m.
• the glass filaments preferably have a diameter in the range of 2.5 to 9.0 ⁇ m, more preferably in the range of 2.8 to 6.0 ⁇ m, and even more preferably in the range of 3.0 to 4.5 ⁇ m.
• the ratio of the major axis to the minor axis of the cross-sectional shape is, for example, in the range of 2.0 to 10.0
• the fiber diameter when the cross-sectional area is converted to a perfect circle is, for example, in the range of 2.0 to 35.0 ⁇ m.
• the glass fiber of this embodiment 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 in the range of 0.3 to 10000.0 tex (g/km).
• the glass fiber of this embodiment is preferably configured with the glass filaments bundled in a number ranging from 20 to 450, and has a mass per unit length in the range of 0.5 to 90.0 tex.
• the glass fiber of this embodiment is more preferably configured with the glass filaments bundled in a number ranging from 35 to 410, and has a mass per unit length in the range of 0.9 to 69.0 tex.
• the glass fiber of this embodiment is even more preferably configured with the glass filaments bundled in a number ranging from 40 to 250, and has a mass per unit length in the range of 1.0 to 15.0 tex.
• the glass fiber of this embodiment is particularly preferably configured with 50 to 220 glass filaments bundled together, and has a mass per unit length in the range of 1.1 to 7.0 tex.
• the glass fiber of this embodiment may be coated on its surface with an organic material for the purpose of improving the adhesion between the glass fiber and resin, improving the uniform dispersion of the glass fiber in a mixture of the glass fiber and resin or inorganic material, etc.
• organic materials include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (particularly carboxylic acid modified polypropylene), copolymers of (poly)carboxylic acid (particularly maleic acid) and unsaturated monomers, etc.
• the glass fiber of this embodiment may be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, etc. in addition to these resins.
• the glass fiber of this embodiment may be coated with a treatment composition that does not contain the above resins and contains a silane coupling agent, a surfactant, etc.
• the glass fiber is coated with such a resin composition or treatment composition at a ratio in the range of 0.03 to 2.0 mass % based on the mass of the glass fiber of this embodiment in a state where it is not coated with the resin composition or treatment composition.
• the coating of the glass fiber with an organic substance can be performed by applying a solution of the resin (hereinafter referred to as a resin solution) or a solution of the resin composition (hereinafter referred to as a resin composition solution) to the glass fiber of this embodiment in a thread-like form such as yarn or roving using a known method such as a roller-type applicator, and then drying the glass fiber to which the resin solution or resin composition solution has been applied.
• the coating of glass fibers with the organic matter can be carried out by immersing the glass fibers of this embodiment in the form of a woven fabric in a solution of the treatment composition (hereinafter referred to as the treatment composition solution) and then drying the glass fibers to which the treatment composition solution has been applied.
• the treatment composition solution a solution of the treatment composition
• the coating of glass fibers with the organic matter can be carried out by immersing the glass fibers of this embodiment in the form of chopped strands or powder in the resin solution or the resin composition solution, stirring, and then drying the glass fibers to which the resin solution or the resin composition solution has been applied.
• the coating of glass fiber with the organic matter can be performed by immersing the glass fiber of this embodiment in the form of a knitted fabric or nonwoven fabric in the resin solution, the resin composition solution, or the treatment composition solution, and then drying the glass fiber to which the resin solution, the resin composition solution, or the treatment composition solution has been applied.
• examples of the silane coupling agent include aminosilane, chlorosilane, epoxysilane, mercaptosilane, vinylsilane, and (meth)acrylic silane.
• the silane coupling agent may be used alone or in combination of two or more kinds.
• aminosilanes include ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)-N'- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, and ⁇ -anilinopropyltrimethoxysilane.
• chlorosilane is gamma-chloropropyltrimethoxysilane.
• epoxy silanes include ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane.
• Examples of mercaptosilanes include gamma-mercaptotrimethoxysilane.
• vinyl silanes examples include vinyltrimethoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane, etc.
• (Meth)acrylic silanes include ⁇ -methacryloxypropyltrimethoxysilane, etc.
• Lubricants include modified silicone oils, animal oils and their hydrogenated products, vegetable oils and their hydrogenated products, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimines, polyalkylpolyamine alkylamide derivatives, fatty acid amides, and quaternary ammonium salts.
• the lubricants may be used alone or in combination of two or more.
• An example of an animal oil is beef tallow.
• Vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, etc.
• animal waxes examples include beeswax and lanolin.
• Examples of vegetable waxes include candelilla wax and carnauba wax.
• mineral waxes examples include paraffin wax, montan wax, etc.
• condensation products of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.
• fatty acid amides include dehydrated condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid.
• Quaternary ammonium salts include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.
• Surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
• the surfactants may be used alone or in combination of two or more.
• 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
• 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 of 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-type cationic surfactants, and alkyl pyridinium salts.
• Higher alkyl amine salts include acetates and hydrochlorides.
• Anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, ⁇ -olefin sulfates, alkylbenzene sulfonates, ⁇ -olefin sulfonates, reaction products of fatty acid halides and N-methyltaurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphates of higher alcohol ethylene oxide adducts.
• amphoteric surfactants include amino acid amphoteric surfactants, betaine amphoteric surfactants, and imidazoline amphoteric surfactants.
• amino acid amphoteric surfactants include alkali metal salts of alkylaminopropionic acid.
• betaine amphoteric surfactants include alkyldimethylbetaines.
• the glass fiber fabric of this embodiment can be obtained by using a glass fiber fabric having the above-mentioned mother glass composition as the glass fiber product having the above-mentioned mother glass composition in the method for obtaining the glass fiber of this embodiment described above.
• the glass fiber fabric of this embodiment can also be obtained by using a glass yarn having the above-mentioned mother glass composition as the glass fiber product having the above-mentioned mother glass composition in the method for obtaining the glass fiber of this embodiment described above 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 threads and weaving with a loom known per se.
• the loom examples include jet looms such as air jet or water jet looms, shuttle looms, and rapier looms.
• the warp and weft threads are made of the glass fiber of this embodiment.
• the weave of the glass fiber fabric of this embodiment can be, for example, a plain weave, a satin weave, a sash weave, a twill weave, etc., and from the viewpoint of the handling properties of the glass fiber fabric, a plain weave is preferred.
• the glass fiber of this embodiment described above is preferably composed of glass filaments having a filament diameter in the range of 2.5 to 9.0 ⁇ m bundled in a number of fibers in the range of 35 to 410, with a twist in the range of 0 to 1.0 turns/25 mm, and a mass per unit length in the range of 0.9 to 69.0 tex (g/1000 m).
• 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.
• the glass fiber fabric of this embodiment may be subjected to a surface treatment and a fiber opening treatment.
• the surface treatment may involve immersing the glass fiber fabric in a solution containing the silane coupling agent or the silane coupling agent and the surfactant, squeezing out excess water, and then drying by heating at a temperature in the range of 80 to 180°C for a period of time in the range of 1 to 30 minutes.
• Examples of the opening process include processes in which a tension in the range of 30 to 200 N is applied to the warp threads of the glass fiber fabric, and the warp threads are opened by water flow pressure, opened by high-frequency vibration using a liquid as a medium, opened by the pressure of a fluid with surface pressure, or opened by pressure applied by a roll, thereby expanding the thread width of the warp and weft threads.
• the glass fiber fabric of this embodiment preferably has a mass in the range of 6.0 to 180.0 g/ m2 and a thickness in the range of 7.0 to 150.0 ⁇ m. More preferably, the glass fiber fabric of this embodiment has a mass in the range of 7.0 to 80.0 g/ m2 and a thickness in the range of 8.0 to 80.0 ⁇ m.
• the warp thread width is preferably in the range of 90 to 500 ⁇ m, and the weft thread width is preferably in the range of 90 to 500 ⁇ m.
• the glass fiber fabric of this embodiment may have a surface treatment layer containing the silane coupling agent, or the silane coupling agent and the surfactant.
• the surface treatment layer has a mass in the range of, for example, 0.03 to 1.50 mass% relative to the total amount of the glass fiber fabric including the surface treatment layer.
• the glass fiber reinforced resin composition of this embodiment contains the glass fiber of this embodiment described above. Specifically, the glass fiber reinforced resin composition of this embodiment contains 10 to 90 mass% of the glass fiber relative to the total amount of the glass fiber reinforced resin composition in a glass fiber reinforced resin composition containing a thermoplastic resin or thermosetting resin, glass fiber, and other additives. The glass fiber reinforced resin composition of this embodiment also contains 90 to 10 mass% of resin relative to the total amount of the glass fiber reinforced resin composition, and contains 0 to 40 mass% of other additives.
• thermoplastic resin examples 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, Examples of suitable resins include carbon
• polyethylene examples include high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra-high molecular weight polyethylene, etc.
• HDPE high density polyethylene
• LDPE low density polyethylene
• LLDPE linear low density polyethylene
• ultra-high molecular weight polyethylene etc.
• polypropylene examples include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.
• polystyrene examples include general-purpose polystyrene (GPPS), which is an atactic polystyrene with an atactic structure, high impact polystyrene (HIPS), which is GPPS with a rubber component added, and syndiotactic polystyrene, which has a syndiotactic structure.
• GPPS general-purpose polystyrene
• HIPS high impact polystyrene
• syndiotactic polystyrene which has a syndiotactic structure.
• Methacrylic resins include polymers obtained by homopolymerizing one of the following: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl esters, or copolymers obtained by copolymerizing two or more of these.
• polyvinyl chloride examples 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 copolymerizable monomers, and graft copolymers in which vinyl chloride monomers are graft-polymerized onto a polymer.
• 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), polydeca Methylene 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
• Polyacetals include homopolymers whose main repeating unit is oxymethylene units, and copolymers that are mainly composed of oxymethylene units and contain oxyalkylene units with 2 to 8 adjacent carbon atoms in the main chain.
• polyethylene terephthalate examples include polymers obtained by polycondensing terephthalic acid or its derivatives with ethylene glycol.
• polybutylene terephthalate examples include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,4-butanediol.
• polytrimethylene terephthalate examples include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,3-propanediol.
• polycarbonates examples include polymers obtained by the transesterification method, in which a dihydroxy diaryl compound is reacted in a molten state with a carbonate ester such as diphenyl carbonate, and polymers obtained by the phosgene method, in which a dihydroxy diaryl compound is reacted with phosgene.
• polyarylene sulfides examples include linear polyphenylene sulfide, crosslinked polyphenylene sulfide that has been polymerized and then cured, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.
• Polyphenylene ethers include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl-1,4-phenyl Examples of such poly(2-chloro-1,4-phenylene ether),
• modified polyphenylene ethers include polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene/butadiene copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene/maleic anhydride copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polyamide, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene/butadiene/acrylonitrile copolymer, polyphenylene ethers having functional groups such as amino, epoxy, carboxy, and styryl groups introduced at the polymer chain ends, and polyphenylene ethers having functional groups such as amino, epoxy, carboxy, styryl,
• polyaryletherketones examples include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), etc.
• liquid crystal polymers examples include (co)polymers that are thermotropic liquid crystal polyesters and are composed of one or more structural units selected from aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, etc.
• Fluoroplastic resins 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).
• PTFE polytetrafluoroethylene
• PFA perfluoroalkoxy resin
• FEP fluorinated ethylene propylene resin
• ETFE fluorinated ethylene tetrafluoroethylene resin
• PVDF polyvinyl fluoride
• PVDF polyvinylidene fluoride
• PCTFE polychlorotrifluoroethylene resin
• ECTFE ethylene/chlorotrifluoroethylene resin
• Ionomer (IO) resins include copolymers of olefins or styrene with unsaturated carboxylic acids, in which some of the carboxyl groups have been neutralized with metal ions.
• olefin/vinyl alcohol resins examples include ethylene/vinyl alcohol copolymers, propylene/vinyl alcohol copolymers, saponified ethylene/vinyl acetate copolymers, and saponified propylene/vinyl acetate copolymers.
• Cyclic olefin resins include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.
• polylactic acid examples 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 of these.
• Cellulose resins 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, cellulose butyrate, etc.
• thermosetting resin examples 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.
• 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,
• Unsaturated polyester resins include those obtained by esterifying an aliphatic unsaturated dicarboxylic acid with an aliphatic diol.
• Vinyl ester resins include bis-vinyl ester resins and novolac-vinyl ester resins.
• 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.
• epoxy resins include 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, bifunctional 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.
• novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure biphenyl-type epoxy
• a melamine resin is a polymer formed by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.
• Phenol resins include novolac-type phenol resins such as phenol novolac resin, cresol novolac resin, and bisphenol A-type novolac resin; resol-type phenol resins such as methylol-type resol resin and dimethylene ether-type resol resin; and aryl alkylene-type phenol resins, and may be used alone or in combination of two or more of these.
• Urea resins include those obtained by condensation of urea and formaldehyde.
• thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more kinds.
• the resin is preferably an epoxy resin, modified polyphenylene ether, thermosetting modified polyphenylene ether, polybutylene terephthalate, polypropylene, fluororesin, or liquid crystal polymer (LCP).
• additives include reinforcing fibers other than glass fiber, fillers other than glass fiber, flame retardants, UV absorbers, heat stabilizers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments, etc.
• reinforcing fibers besides glass fiber include carbon fiber, metal fiber, etc.
• Fillers other than glass fiber include glass powder, talc, mica, etc.
• the glass fiber reinforced resin composition of this embodiment may be a prepreg obtained by impregnating the glass fiber fabric of this embodiment with the resin by a method known per se and semi-curing it.
• 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, laminate molding, press molding, blow molding, stamping molding, infusion, hand layup, spray-up, resin transfer molding, sheet molding compounding, bulk molding compounding, pultrusion, and filament winding to obtain various glass fiber reinforced resin molded products. Glass fiber reinforced resin molded products can also be obtained by curing the prepreg.
• molded products include, for example, electronic device housings, electronic components, vehicle exterior parts, vehicle interior parts, vehicle engine peripheral parts, muffler-related parts, high-pressure tanks, etc.
• Examples of electronic components include printed wiring boards.
• Vehicle exterior components include bumpers, fenders, bonnets, air dams, wheel covers, radomes, etc.
• Vehicle interior components include door trims, ceiling materials, etc.
• vehicle engine-related components examples include oil pans, engine covers, intake manifolds, exhaust manifolds, etc.
• Muffler-related materials include heat-resistant sound-absorbing materials, filtration and dust-removal filters, catalyst carrier materials, etc.
• the glass fibers of this embodiment can be suitably used as a reinforcing material for inorganic materials such as gypsum and cement, in addition to the glass fiber reinforced resin composition of this embodiment.
• the glass fibers having the above-mentioned glass composition can be contained in an amount of 0.1 to 4.0 mass% relative to the total mass of the gypsum.
• glass fiber fabric A a glass fiber fabric (hereinafter referred to as glass fiber fabric A) was prepared, which had a mother glass composition of composition A shown in Table 1, and which had warp and weft yarns of 21.0 tex glass yarns each composed of 204 bundled glass filaments each having a diameter of 7.0 ⁇ m, a warp weave density of 59 threads/25 mm, a weft weave density of 57 threads/25 mm, a thickness of 90 ⁇ m, and a mass per unit area of 97 g/ m2 .
• the glass fiber fabric A was placed in a liquid tank containing nitric acid with a concentration of 6.3% by mass as an acid solution, and an acid leaching process was carried out while stirring the acid solution at a leaching temperature of 60°C and a leaching time of 180 minutes to obtain an acid-leached 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.
• 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. After that, 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.
• the obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 5.8 ⁇ m in diameter, 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 ⁇ m, and a mass per unit area of 75 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured using the methods described above. The results are shown in Table 2.
• the glass fiber fabric of this example was evaluated for its handleability according to the following criteria. When both ends of the glass fiber fabric cut to a size of 10 cm x 10 cm were held and the fabric was bent 180 degrees at the center, the fabric was rated as A if it returned to its original position. When the cut glass fiber fabric was bent 180 degrees at the center, it was rated as B if it did not return to its original position or if it broke at the bent part. When the cut glass fiber fabric was bent 180 degrees at the center, it was rated as C if the glass fiber fabric broke before being bent 180 degrees. The results are shown in Table 2.
• 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.
• the obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 5.8 ⁇ m in diameter, 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 ⁇ m, and a mass per unit area of 75 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.
• glass fiber fabric B a glass fiber fabric (hereinafter referred to as glass fiber fabric B) was prepared, which had a mother glass composition of composition A shown in Table 1, and which had warp and weft yarns of 10 tex glass yarns each composed of 204 bundled glass filaments each having a diameter of 4.8 ⁇ m, a warp weave density of 53 threads/25 mm, a weft weave density of 53 threads/25 mm, a thickness of 50 ⁇ m, and a mass per unit area of 45 g/ m2 .
• the glass fiber fabric B was placed in a liquid tank containing nitric acid with a concentration of 6.3% by 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-leached 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.
• 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. After that, 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.
• the obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 4.3 ⁇ m 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 ⁇ m, and a mass per unit area of 34 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.
• 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 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 850° C., and the firing time was 48 hours.
• the obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 4.3 ⁇ m 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 ⁇ m, and a mass per unit area of 34 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.
• 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.
• the obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 4.3 ⁇ m 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 ⁇ m, and a mass per unit area of 34 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.
• 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 baking temperature was 900°C.
• the obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 5.8 ⁇ m in diameter, 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 ⁇ m, and a mass per unit area of 75 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.
• Example 7 The glass fiber fabric of this example was obtained in exactly the same manner as in Example 3, except that the leaching temperature in the acid leaching treatment was 60°C.
• the obtained glass fiber fabric of this example had glass filaments constituting the warp and weft of 4.3 ⁇ m 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 ⁇ m, and a mass per unit area of 34 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.
• 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.
• the obtained glass fiber fabric of this comparative example had glass filaments constituting the warp and weft of 4.3 ⁇ m 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 ⁇ m, and a mass per unit area of 34 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 3.
• 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.
• the obtained glass fiber fabric of this comparative example had glass filaments constituting the warp and weft of 4.3 ⁇ m 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 ⁇ m, and a mass per unit area of 34 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 3.
• the obtained glass fiber fabric of this comparative example had glass filaments constituting the warp and weft of 4.3 ⁇ m 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 ⁇ m, and a mass per unit area of 34 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 3.
• glass fiber fabric C a glass fiber fabric (hereinafter referred to as glass fiber fabric C) was prepared, which had a mother glass composition of composition B shown in Table 1 , and was made of 22 tex glass yarns formed by bundling 204 glass filaments having a diameter of 7.4 ⁇ m, a warp weave density of 59 threads/25 mm, a weft weave density of 57 threads/25 mm, a thickness of 90 ⁇ m, and a mass per unit area of 101 g/m2.
• the glass fiber fabric C was placed in a liquid tank containing nitric acid with a concentration of 6.3% by mass as an acid solution, and an acid leaching process was carried out while stirring the acid solution at a leaching temperature of 60°C and a leaching time of 2880 minutes to obtain an acid-leached 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.
• the acid-eluted glass fiber fabric was then 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. The temperature was then 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.
• the obtained glass fiber fabric of this comparative example had glass filaments constituting the warp and weft of 6.3 ⁇ m 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 ⁇ m, and a mass per unit area of 79 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 3.
• 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 having a concentration of 18.0 mass % was used as the acid solution and the leaching time was 360 minutes.
• the obtained glass fiber fabric of this comparative example had glass filaments constituting the warp and weft yarns with a diameter of 6.3 ⁇ m, a mass per unit length of the warp and weft yarns of 14 tex, a warp weave density of 68 yarns/25 mm, a weft weave density of 65 yarns/25 mm, a thickness of 87 ⁇ m, and a mass per unit area of 79 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 3.
• 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.
• the obtained glass fiber fabric of this comparative example had glass filaments constituting the warp and weft of 6.3 ⁇ m 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 ⁇ m, and a mass per unit area of 79 g/ m2 .
• the glass composition, tensile breaking stress, and dielectric tangent of the glass fiber fabric of this comparative example were measured using the methods described above.
• the handleability of the glass fiber was evaluated in exactly the same manner as in Example 1. The results are shown in Table 3.
• the glass fibers of Examples 1 to 7 in which the value of BS ⁇ (T/(100 ⁇ S)) 2 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 thus it is possible to obtain glass fibers having excellent handleability.
• the glass fiber of Comparative Example 1 in which the value of BS ⁇ (T/(100 ⁇ S)) 2 exceeds 33.8, has a dielectric loss tangent exceeding 0.0010 at a measurement frequency of 28 GHz.

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