Classifications

• • 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
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
  • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
  • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
  • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
• • 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
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
• • 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
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/255—Oils, waxes, fats or derivatives thereof
• • 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
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
• • 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
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/40—Organo-silicon compounds
• • 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
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
  • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
• • 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
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—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
  • D03D15/20—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
• • 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
  • C03C2213/00—Glass fibres or filaments

Definitions

• the present invention relates to glass compositions for glass fibers, glass fibers, glass fiber fabrics, and glass fiber reinforced resin compositions.
• the glass fiber is obtained by melting in a glass melting furnace a glass raw material prepared so as to obtain a glass composition for glass fiber having a desired composition to obtain molten glass (melt of the glass composition for glass fiber), and the molten glass is is discharged from a container (bushing) having a nozzle plate on which several to several thousand nozzle tips are formed, cooled while being stretched by being wound up at high speed, and solidified into a fibrous form (hereinafter, this operation is referred to as " It is sometimes called "spinning").
• the bushing is made of noble metal such as platinum.
• glass fibers have been widely used in various applications in order to improve the strength of resin molded products, and the resin molded products are used for housings or parts of electronic devices such as servers, smartphones and laptop computers. ing.
• glass absorbs the energy of alternating current as heat, 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.
• the dielectric loss energy 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 represented by the following formula (A).
• W kfv2 ⁇ 1/ 2 ⁇ tan ⁇ (A)
• the present applicant has proposed glass as a glass composition for glass fibers, which has a low dielectric constant and a low dielectric loss tangent, suppresses the occurrence of phase separation, and has a reduced viscosity at high temperatures.
• SiO 2 in the range of 52.0 to 59.5% by weight
• B 2 O 3 in the range of 17.5 to 25.5% by weight, and 9.0 to 14.0, based on the total amount of the fiber glass composition.
• Al 2 O 3 in the range of wt.%, SrO in the range of 0.5 to 6.0 wt.%, MgO in the range of 1.0 to 5.0 wt.%, and 1.0 to 5.0 wt.%. and a total of F 2 and Cl 2 in the range of 0.1 to 2.5 mass % (see Patent Document 1).
• a glass composition for glass fiber that can provide a glass fiber having a lower dielectric constant and a lower dielectric loss tangent, especially in a high frequency range of about 10 GHz.
• the content of Al 2 O 3 and alkaline earth metal oxides (CaO, MgO and SrO) with respect to the total amount of the glass fiber glass composition is reduced, and the content of SiO 2 and B 2 O 3 is reduced accordingly. It is conceivable to increase the content.
• the working temperature range represented by the difference between the 1000 poise temperature and the liquidus temperature is narrowed, and the glass fiber manufacturability is reduced, or the water resistance of the glass fiber is deteriorated, and precipitation on the surface of the glass fiber is caused by hydrolysis of the glass.
• the dielectric properties are deteriorated due to the foreign matter, and the strength of the glass fiber is greatly reduced.
• the present invention eliminates such inconveniences and provides a glass fiber with excellent water resistance and excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the high frequency range, which itself is sufficient. It is an object of the present invention to provide a glass composition for glass fibers that can have a temperature range.
• the glass composition for glass fiber of the present invention contains SiO 2 in the range of 59.00 to 65.00% by mass and B 2 O 3 in the range of 0.00 wt %, Al 2 O 3 in the range of 7.00-14.00 wt %, CaO in the range of 0-5.00 wt %, 0-4.00 wt % % range of MgO, 0-6.00 wt .
• the content of P 2 O 5 is less than 0.20% by mass
• the total content of Na 2 O, K 2 O and Li 2 O is less than 1.00% by mass
• the The ratio of the content (mass%) of TiO 2 to the total content (mass%) of CaO, MgO and SrO is in the range of 0.66 to 4.00
• the content (% by mass) SI and the content (% by mass) A of Al 2 O 3 satisfy the following formula (1). 1.00 ⁇ 1000 ⁇ A/SI 2 ⁇ 4.65 (1)
• the glass composition for glass fiber of the present invention contains SiO2 , B2O3 , Al2O3 , CaO, MgO, SrO, TiO2 , F2 and Cl2 , and P2O . 5 and Na 2 O, K 2 O and Li 2 O in the above ranges, and the ratio of the content (mass%) of TiO 2 to the total content (mass%) of CaO, MgO and SrO (TiO 2 / (CaO + MgO + SrO)) is in the range of 0.66 to 4.00, and the SiO 2 content (mass%) SI and the Al 2 O 3 content (mass%) A satisfy the formula (1) By satisfying it, a glass fiber with excellent water resistance and excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the high frequency range can be obtained, and itself can have a sufficient working temperature range. .
• the fact that the glass fiber obtained from the glass composition for glass fiber of the present invention has a low dielectric constant means that the dielectric constant is 4.2 or less at a measurement frequency of 10 GHz.
• Having a loss tangent means that the dielectric loss tangent is 0.0011 or less at a measurement frequency of 10 GHz.
• the glass fiber obtained from the glass composition for glass fiber of the present invention exhibits excellent water resistance when the mass reduction rate is 2.0% or less when evaluated by the following water resistance evaluation method. It means that almost no components of the glass fiber are eluted even in water.
• a glass batch obtained by mixing glass raw materials so that the glass composition after melting and solidification becomes a predetermined glass fiber glass composition is placed in a platinum crucible with a diameter of 80 mm and heated at 1550 ° C. 4 hours at 1650 ° C., 2 hours at 1650 ° C., the homogenous glass cullet obtained by removing it from the crucible is placed in a small cylindrical platinum bushing with one circular nozzle tip at the bottom of the container and heated to a predetermined temperature.
• the molten glass discharged from the nozzle tip is wound around a stainless steel collet at a predetermined speed to be cooled and solidified while being stretched to obtain a glass fiber having a circular cross section and a fiber diameter of 13 ⁇ m. .
• about 1 g of the obtained glass fiber (test glass fiber) is collected from the collet, dried at 120° C. for 1 hour, and the mass (mass before operation) is measured.
• the test glass fiber was placed in 100 ml of distilled water at 80° C. for 24 hours. It is dried at °C for 1 hour and the mass (mass after operation) is measured. Then, the mass reduction rate (100 ⁇ (1-(mass after operation/mass before operation))) is calculated from the mass before operation and the mass after operation.
• the glass composition for glass fiber of the present invention has a sufficient working temperature range means that the working temperature range is 20°C or higher.
• the upper limit of the working temperature range is not particularly limited, it is, for example, 500° C. or lower, preferably 450° C. or lower, more preferably 400° C. or lower.
• the glass composition for glass fiber of the present invention comprises the SiO 2 content (mass%) SI, the B 2 O 3 content (mass%) B, the Al 2 O 3 content (mass%) ) A, the CaO content (mass%) C, the MgO content (mass%) M, the SrO content (mass%) SR, the TiO 2 content (mass%) T, and
• the total content of F 2 and Cl 2 (% by mass) F preferably satisfies the following formula (2), more preferably satisfies the following formula (3), further preferably satisfies the following formula (4), especially Preferably, the following formula (4) is satisfied.
• the present invention provides a glass fiber comprising any one of the glass compositions for glass fibers, a glass fiber fabric comprising the glass fiber, or a glass fiber comprising the glass fiber.
• a glass fiber reinforced resin composition characterized by
• the glass fiber of the present invention can be obtained, for example, by melting the above-described glass composition for glass fiber of the present invention, and discharging the obtained melt from a bushing having a nozzle plate with 1 to 8000 nozzle tips or holes. , can be obtained by winding at a high speed, cooling while stretching, solidifying and forming into a fibrous form. Therefore, the glass fiber of the present invention has the same glass composition as the above-described glass composition for glass fiber of the present invention.
• the glass composition for glass fiber of the present embodiment contains SiO 2 in the range of 59.00 to 65.00 mass% and SiO 2 in the range of 16.00 to 26.00 mass% B 2 O 3 , Al 2 O 3 in the range of 7.00-14.00% by weight, CaO in the range of 0-5.00% by weight, MgO in the range of 0-4.00% by weight, SrO in the range of 0-6.00% by weight, TiO in the range of 0.10-5.00 % by weight, and F and Cl in the range of 0-2.00 % by weight in total ,
• the content of P 2 O 5 is less than 0.20% by mass, the total content of Na 2 O, K 2 O and Li 2 O is less than 1.00% by mass, and the total of CaO, MgO and SrO
• the ratio of the TiO 2 content (mass%) to the content (mass%) (TiO 2 /(CaO + MgO + SrO)) is in the range of 0.66 to 4.00, and the SiO 2 content (
• the glass composition for glass fiber of the present embodiment includes SiO2 , B2O3 , Al2O3 , CaO, MgO, SrO, TiO2 , F2 and Cl2 , and P2 .
• O 5 and Na 2 O, K 2 O and Li 2 O in the above ranges, and the ratio of the content (mass%) of TiO 2 to the total content (mass%) of CaO, MgO and SrO (TiO 2 /(CaO+MgO+SrO)) is in the range of 0.66 to 4.00, and the SiO 2 content (% by mass) SI and the Al 2 O 3 content (% by mass) A are in the formula (1)
• the glass composition for glass fibers of the present embodiment has a SiO 2 content of less than 59.00% by mass with respect to the total amount of the glass composition for glass fibers, and the glass fiber obtained from the glass composition for glass fibers is The mechanical strength of the glass fiber is greatly reduced, and the function of the glass fiber as a reinforcing material in the glass fiber reinforced resin composition is impaired. In addition, the glass fibers tend to deteriorate when placed in an acidic environment. On the other hand, if the content of SiO 2 is more than 65.00% by mass with respect to the total amount of the glass composition for glass fiber, the viscosity at high temperatures increases, so the temperature for melting the glass raw material increases, and the manufacturing cost increases. From the point of view, it becomes unsuitable for industrial glass fiber production.
• the glass composition for glass fiber of the present embodiment preferably has a SiO 2 content of 59.20 to 64.50% by mass with respect to the total amount of the glass composition for glass fiber, and more preferably, 59.30 to 64.00% by mass, more preferably 59.40 to 63.50% by mass, particularly preferably 59.50 to 63.00% by mass, Particularly preferred is the range from 59.60 to 62.80% by weight, most preferred is the range from 60.10 to 62.60% by weight.
• the glass composition for glass fiber of the present embodiment is obtained from the glass composition for glass fiber when the content of B 2 O 3 is less than 16.00% by mass with respect to the total amount of the glass composition for glass fiber.
• the dielectric loss tangent of the glass fiber cannot be sufficiently reduced.
• the content of B 2 O 3 is more than 26.00% by mass with respect to the total amount of the glass composition for glass fiber, phase separation occurs in the glass fiber obtained from the glass composition for glass fiber.
• the chemical durability of the fiber may decrease.
• the content of B 2 O 3 is preferably in the range of 18.00 to 24.90% by mass, more preferably in the range of the total amount of the glass composition for glass fiber. is in the range of 19.00 to 24.50% by mass, more preferably in the range of 19.60 to 24.00% by mass, and particularly preferably in the range of 20.10 to 23.50% by mass. Yes, and most preferably in the range of 20.50 to 23.00% by mass.
• the glass composition for glass fiber of the present embodiment is obtained from the glass composition for glass fiber when the content of Al 2 O 3 is less than 7.00% by mass with respect to the total amount of the glass composition for glass fiber. Phase separation may occur in the glass fiber, and the chemical durability of the glass fiber may decrease. On the other hand, when the content of Al 2 O 3 is more than 14.00% by mass with respect to the total amount of the glass composition for glass fiber, the dielectric loss tangent of the glass fiber obtained from the glass composition for glass fiber is sufficiently reduced. I can't.
• the content of Al 2 O 3 is preferably in the range of 7.20 to 13.50% by mass with respect to the total amount of the glass composition for glass fiber, and more preferably. is in the range of 7.40 to 13.00% by mass, more preferably in the range of 7.60 to 12.50% by mass, particularly preferably in the range of 7.80 to 12.00% by mass , particularly preferably in the range of 8.00 to 11.80% by mass, most preferably in the range of 8.20 to 9.90% by mass.
• the glass composition for glass fiber of the present embodiment has a CaO content of more than 5.00% by mass with respect to the total amount of the glass composition for glass fiber, and the glass fiber obtained from the glass composition for glass fiber is Dielectric loss tangent cannot be sufficiently reduced.
• the glass composition for glass fiber of the present embodiment preferably has a CaO content in the range of 0.60 to 4.80% by mass, more preferably 1 .10 to 4.60% by mass, more preferably 1.60 to 4.40% by mass, particularly preferably 1.80 to 4.20% by mass. Preferably, it is in the range of 2.00-4.00% by mass, and most preferably in the range of 2.10-3.60% by mass.
• the content of MgO is more than 4.00% by mass with respect to the total amount of the glass composition for glass fibers
• striae are formed in the melt of the glass composition for glass fibers. may occur, the glass fiber may be easily broken during spinning, and the water resistance of the glass fiber obtained from the glass composition for glass fiber may deteriorate.
• the content of MgO is preferably in the range of less than 3.00% by mass, more preferably 2.00% by mass, based on the total amount of the glass composition for glass fiber. %, more preferably less than 1.50% by mass, particularly preferably less than 1.00% by mass, and most preferably less than 0.95% by mass. and most preferably in the range of less than 0.50% by mass.
• the glass composition for glass fiber of the present embodiment has a SrO content of more than 6.00% by mass with respect to the total amount of the glass composition for glass fiber, and the glass fiber obtained from the glass composition for glass fiber is The dielectric properties deteriorate and the target dielectric properties cannot be met.
• the glass composition for glass fiber of the present embodiment preferably has a SrO content of less than 4.00% by mass, more preferably 3.00% by mass, based on the total amount of the glass composition for glass fiber. %, more preferably less than 2.00% by mass, particularly preferably less than 1.00% by mass, and most preferably less than 0.50% by mass. and most preferably in the range of less than 0.45% by mass.
• the content of TiO 2 in the glass composition for glass fiber of the present embodiment is less than 0.10% by mass with respect to the total amount of the glass composition for glass fiber, the viscosity at high temperatures increases. The melting temperature becomes high, and from the viewpoint of production cost, it becomes unsuitable for industrial glass fiber production.
• the content of TiO 2 is more than 5.00% by mass with respect to the total amount of the glass composition for glass fiber, the dielectric loss tangent of the glass fiber obtained from the glass composition for glass fiber can be sufficiently reduced.
• the liquidus temperature of the glass composition for glass fibers is greatly increased, it becomes impossible to stably produce glass fibers.
• the content of TiO 2 is preferably in the range of 0.60 to 4.90% by mass with respect to the total amount of the glass composition for glass fiber, and more preferably, 1.60 to 4.70% by mass, more preferably 2.10 to 4.60% by mass, particularly preferably 2.50 to 4.50% by mass, Most preferably, it ranges from 2.80 to 4.40% by weight.
• the total content of F 2 and Cl 2 is more than 2.00% by mass with respect to the total amount of the glass composition for glass fiber. The chemical durability of the glass fiber obtained from is reduced.
• the total content of F 2 and Cl 2 is preferably in the range of 0.10 to 1.80% by mass with respect to the total amount of the glass composition for glass fiber. more preferably in the range of 0.30 to 1.60% by mass, still more preferably in the range of 0.50 to 1.50% by mass.
• the glass composition for glass fibers of the present embodiment has a P 2 O 5 content of more than 0.20% by mass and a SiO 2 content in the above-described range with respect to the total amount of the glass composition for glass fibers.
• the inclusion of P 2 O 5 does not contribute to the improvement of the dielectric properties of the glass fiber obtained from the glass composition for glass fiber, and on the other hand, the occurrence of phase separation of the glass fiber cannot be suppressed. , the chemical durability of the glass fiber deteriorates.
• the content of P 2 O 5 is preferably in the range of less than 0.10% by mass, more preferably 0 less than 0.05 mass %.
• the total content of Na 2 O, K 2 O and Li 2 O is more than 1.00% by mass with respect to the total amount of the glass composition for glass fiber. , the dielectric properties of the glass fiber obtained from the glass composition for glass fiber are greatly deteriorated, and the target dielectric properties cannot be satisfied.
• the total content of Na 2 O, K 2 O and Li 2 O is preferably less than 0.80% by mass with respect to the total amount of the glass composition for glass fiber. range, more preferably less than 0.50% by mass, more preferably less than 0.20% by mass, particularly preferably less than 0.10% by mass, and most preferably less than 0.10% by mass. It is preferably in the range of less than 0.05% by mass.
• the ratio of the content (mass%) of TiO 2 to the total content (mass%) of CaO, MgO and SrO is 0.66. If it is less than that, deterioration of the dielectric loss tangent due to the inclusion of alkaline earth metal oxides cannot be sufficiently suppressed, so the dielectric loss tangent of the glass fiber obtained from the glass composition for glass fiber cannot be sufficiently reduced. Moreover, the water resistance of the glass fiber may deteriorate. If it exceeds 4.00, the generation of striae in the glass cannot be suppressed, and the liquidus temperature greatly increases, making it impossible to stably produce glass fibers.
• the ratio of the content (mass%) of TiO 2 to the total content (mass%) of CaO, MgO and SrO is preferably , in the range of 0.67 to 2.15, more preferably in the range of 0.85 to 2.00, still more preferably in the range of 0.90 to 1.80, particularly preferably 0 0.95 to 1.70, most preferably 0.98 to 1.60.
• the ratio of the content rate (mass%) of TiO2 to the total content rate (mass%) of CaO, MgO and SrO is the The increase in the liquidus temperature of the glass composition for glass fibers due to the deterioration of the glass fiber production stability and the decrease in the dielectric loss tangent due to the increase in the liquidus temperature, and the inclusion of the alkaline earth metal oxide that is the network-modifying oxide. It is presumed that this expresses a balance between the improvement in glass fiber manufacturing stability and the deterioration in dielectric loss tangent and water resistance that accompany the decrease.
• the value of the formula (1) when the value of the formula (1) is less than 1.00, the water resistance of the glass fiber obtained from the glass composition for glass fiber is deteriorated, and It is not possible to suppress the increase in the glass fiber manufacturing cost due to the increased viscosity of the glass composition at high temperatures and the deterioration of the glass fiber manufacturability due to the increase in the number of fluffs generated during the glass fiber manufacturing process.
• the value of the formula (1) is more than 4.65, the glass fiber production stability deteriorates due to an increase in the liquidus temperature of the glass composition for glass fibers, and the glass composition for glass fibers Deterioration of the dielectric properties of the obtained glass fiber cannot be suppressed.
• the value of the formula (1) is preferably in the range of 1.50 to 4.50, more preferably in the range of 1.80 to 4.20. more preferably in the range of 2.00 to 4.00, particularly preferably in the range of 2.05 to 3.80, and most preferably in the range of 2.10 to 3.60 , most preferably in the range of 2.11 to 3.35.
• the higher the content A of Al 2 O 3 the lower the viscosity of the glass composition for glass fibers at high temperatures, which tends to lead to a reduction in glass fiber production costs.
• this value becomes too high, the generation of mullite crystals is accelerated, and the liquidus temperature of the glass composition for glass fibers increases, resulting in deterioration of the glass fiber production stability and the glass composition for glass fibers. There is a tendency that the deterioration of the dielectric properties of the resulting glass fiber cannot be suppressed.
• the lower this value the more the liquidus temperature of the glass composition for glass fibers is lowered, which tends to lead to the improvement in the stability of glass fiber production and the improvement in the dielectric properties of the glass composition for glass fibers.
• this value is too low, the water resistance of the glass fiber obtained from the glass composition for glass fiber is deteriorated, and along with the decrease in the strength of the glass fiber, fluff that hinders the production of glass fiber is generated. tends to be easier.
• the higher the content SI of SiO2 the better the dielectric properties of the glass fiber obtained from the glass composition for glass fiber, but the higher the viscosity of the glass composition for glass fiber at high temperatures, the higher the glass fiber production cost. tend to increase.
• the formula (1) expresses a balance between the overall glass fiber manufacturability of the glass composition for glass fibers and the dielectric properties obtained from the glass composition for glass fibers.
• the tendency to easily generate fluff is also an obstacle when glass fibers are processed into glass fiber products (eg, glass fiber fabrics, chopped strands, rovings).
• the glass composition for glass fiber of the present embodiment includes the SiO 2 content (mass%) SI, the B 2 O 3 content (mass%) B, the Al 2 O 3 content (mass %) A, the CaO content (mass%) C, the MgO content (mass%) M, the SrO content (mass%) SR, the TiO2 content (mass%) T, and , the total content of F 2 and Cl 2 (% by mass) F preferably satisfies the following formula (2), more preferably satisfies the following formula (3), more preferably satisfies the following formula (4), Particularly preferably, the following formula (5) is satisfied.
• the glass composition for glass fiber of the present embodiment has excellent water resistance and Glass fibers with excellent dielectric properties can be obtained and, as such, can be provided with a sufficient working temperature range.
• the glass composition for glass fiber of the present embodiment has excellent water resistance and high frequency A glass fiber with better dielectric properties in the region can be obtained and itself can have a sufficient working temperature range.
• that the glass fiber has better dielectric properties means that the dielectric constant at a measurement frequency of 10 GHz is 4.1 or less and the dielectric loss tangent is 0.0010 or less.
• the glass composition for glass fiber of the present embodiment has excellent water resistance and high frequency A glass fiber with better dielectric properties in the region can be obtained and itself can have an excellent working temperature range of 120° C. and above.
• the glass composition for glass fiber of the present embodiment has excellent water resistance and high frequency Glass fibers can be obtained with very good dielectric properties in the region, which themselves can have a better working temperature range of 200° C. and above.
• the fact that the glass fiber has excellent dielectric properties means that the dielectric constant at a measurement frequency of 10 GHz is 4.0 or less and the dielectric loss tangent is less than 0.0010.
• the ratio of the content of MgO (% by mass) to the total content of CaO and SrO (% by mass) is, for example, 0.60. less than the range, the viscosity of the glass composition for glass fibers is reduced at high temperature while suppressing the occurrence of phase separation of the glass fibers obtained from the glass composition for glass fibers promoted by MgO, and By lowering the liquidus temperature of the glass composition for glass fiber, it is possible to contribute to the overall improvement of the glass fiber manufacturability of the glass composition for glass fiber.
• the ratio of the content of MgO (% by mass) to the total content of CaO and SrO (% by mass) is preferably less than 0.40. More preferably less than 0.30, more preferably less than 0.20, particularly preferably less than 0.10, most preferably 0. 05 or less.
• the ratio (TiO 2 /Al 2 O 3 ) of the content of TiO 2 (% by mass) to the content of Al 2 O 3 (% by mass) is, for example, When the range is 0.24 to 0.72, the dielectric loss tangent due to the inclusion of TiO 2 is suppressed while suppressing the increase in the liquidus temperature of the glass composition for glass fiber accompanying the crystal growth promoted by TiO 2 . and the effect of improving the water resistance due to the inclusion of Al 2 O 3 .
• the ratio of the TiO 2 content (mass%) to the Al 2 O 3 content (mass%) (TiO 2 /Al 2 O 3 ) is preferably 0. 0.28 to 0.56, more preferably 0.29 to 0.50, still more preferably 0.30 to 0.45, most preferably 0.35 ⁇ 0.44.
• the B, A, C, M, SR, T, F and the P 2 O 5 content (% by mass) P satisfy the following formula (6)
• a glass fiber having excellent water resistance and excellent dielectric properties in the high frequency range can be obtained, and itself can be provided with a sufficient working temperature range.
• B, A, C, M, SR, T, F and P preferably satisfy the following formula (7), more preferably the following formula (8) is satisfied, and particularly preferably the following formula (9) is satisfied.
• the glass composition for glass fiber of the present embodiment has excellent water resistance and higher Glass fibers with excellent dielectric properties can be obtained and, as such, can be provided with a sufficient working temperature range.
• the glass composition for glass fiber of the present embodiment has excellent water resistance and A glass fiber can be obtained with better dielectric properties at 120° C. and itself with an excellent working temperature range of 120° C. and above.
• the glass composition for glass fiber of the present embodiment has excellent water resistance and It is possible to obtain glass fibers with very good dielectric properties at 200° C. and themselves with a better working temperature range of 200° C. and above.
• the glass composition for glass fibers of the present embodiment may contain ZnO in the range of 0 to 3.00% by mass with respect to the total amount of the glass composition for glass fibers.
• ZnO in the range of 0 to 3.00% by mass
• the content of ZnO is more than 3.00% by mass, devitrification is likely to occur, and stable glass fiber production cannot be achieved.
• the content of ZnO with respect to the total amount of the glass composition for glass fiber is preferably 2.50% by mass or less, more preferably 1.50% by mass. % or less, more preferably 0.50 mass % or less.
• the glass composition for glass fiber of the present embodiment may contain MnO 2 in a range of 0 to 3.00% by mass with respect to the total amount of the glass composition for glass fiber.
• MnO 2 if the content of MnO 2 exceeds 3.00% by mass, the dielectric properties deteriorate and desired dielectric properties cannot be obtained.
• the content of MnO 2 with respect to the total amount of the glass composition for glass fibers is preferably 2.50% by mass or less, more preferably 1.50% by mass. % or less, more preferably 0.50 mass % or less.
• the glass composition for glass fiber of the present embodiment may contain Fe 2 O 3 in a range of 0% by mass or more and 1.00% by mass or less with respect to the total amount of the glass composition for glass fiber.
• the content of Fe 2 O 3 is 0.10% by mass or more and 0.10% by mass or more, from the viewpoint of suppressing air bubbles contained in the glass fiber. A range of 60% by mass or less is effective.
• the glass composition for glass fiber of the present embodiment may contain SnO 2 in the range of 0% by mass or more and 1.00% by mass or less with respect to the total amount of the glass composition for glass fiber.
• the content of SnO 2 should be 0.10% by mass or more and 0.60% by mass or less from the viewpoint of suppressing air bubbles contained in the glass fiber. is effective.
• the glass composition for glass fibers of the present embodiment may contain ZrO 2 as long as the content of ZrO 2 is less than 0.50% by mass with respect to the total amount of the glass composition for glass fibers. If the content of ZrO 2 is 0.50% by mass or more relative to the total amount of the glass composition for glass fiber, devitrification is likely to occur, making stable glass fiber production impossible.
• the content of ZrO2 is preferably in the range of less than 0.45% by mass, more preferably , in the range of less than 0.40% by mass, more preferably in the range of less than 0.20% by mass, particularly preferably in the range of less than 0.10% by mass, most preferably in the range of less than 0.05% by mass % range.
• the glass composition for glass fiber of the present embodiment may contain Cr 2 O 3 as long as the content of Cr 2 O 3 is less than 0.05% by mass with respect to the total amount of the glass composition for glass fiber. good. If the content of Cr 2 O 3 is 0.05% by mass or more relative to the total amount of the glass composition for glass fiber, devitrification is likely to occur, making stable glass fiber production impossible.
• the glass composition for glass fiber of the present embodiment contains Ba, Co, Ni, Cu, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb as impurities originating from the raw materials. may contain less than 1.00% by mass of the total amount of the oxides of the glass composition for glass fiber.
• the glass composition for glass fiber of the present embodiment contains BaO, CeO 2 , Y 2 O 3 , La 2 O 3 , Bi 2 O 3 , Gd 2 O 3 , Pr 2 O 3 and Sc 2 O 3 as impurities.
• the content is each independently preferably less than 0.40% by mass, more preferably less than 0.20% by mass, still more preferably 0.10 % by weight, particularly preferably below 0.05% by weight, most preferably below 0.01% by weight.
• the content of each component described above can be measured using an ICP emission spectrometer for Li, which is a light element, and the other elements have a wavelength of Measurements can be made using a dispersive X-ray fluorescence spectrometer.
• glass batch mixed and prepared glass raw materials
• glass fiber when organic matter is attached to the surface of glass fiber, or glass fiber is mainly in organic matter (resin) If it is contained as a reinforcing material, for example, it is heated in a muffle furnace at 300 to 650 ° C. for about 0.5 to 24 hours to remove organic matter before use) is placed in a platinum crucible and electrically In the furnace, the glass batch is held at 1550° C. for 4 hours and 1650° C. for 2 hours to melt while stirring, and the glass fiber is held at 1550° C. for 6 hours and melted while stirring. to obtain a homogeneous molten glass.
• a muffle furnace at 300 to 650 ° C. for about 0.5 to 24 hours to remove organic matter before use
• the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then pulverized into powder to obtain glass powder.
• the obtained glass powder is thermally decomposed with an acid, and then quantitatively analyzed using an ICP emission spectrometer.
• Other elements are quantitatively analyzed using a wavelength dispersive X-ray fluorescence spectrometer after molding the glass powder into a disc shape with a press.
• quantitative analysis using a wavelength dispersive X-ray fluorescence spectrometer can be performed by preparing a calibration curve sample based on the results measured by the fundamental parameter method and analyzing by the calibration curve method.
• the content of each component in the calibration curve sample can be quantitatively analyzed by an ICP emission spectrometer.
• the glass composition for glass fiber of the present embodiment can be obtained by melting a glass raw material (glass batch) prepared so as to have the above composition after melting and solidifying, and then cooling and solidifying.
• the glass raw material prepared as described above is supplied to a glass melting furnace, and the temperature is 1000 poise temperature or higher. temperature range, specifically in the range 1400°C to 1700°C. Then, the molten glass melted at the above temperature is discharged from 1 to 8000 nozzle tips or holes controlled to a predetermined temperature, and is wound at high speed to be stretched and cooled, thereby solidifying the glass fiber. is formed.
• the single glass fiber (glass filament) discharged from one nozzle tip or hole and cooled and solidified usually has a perfect circular cross-sectional shape and a diameter of 3.0 to 35.0 ⁇ m.
• the glass filaments preferably have a diameter of 3.0-6.0 ⁇ m, more preferably in the range of 3.0-4.5 ⁇ m.
• a non-circular shape for example, elliptical or oval
• a glass filament having a cross-sectional shape is obtained.
• the ratio of the long axis to the short axis of the cross-sectional shape is, for example, in the range of 2.0 to 10.0, and the cross-sectional area is true.
• the fiber diameter when converted to yen is in the range of 3.0 to 35.0 ⁇ m.
• the glass fiber of the present embodiment usually takes the form of a glass fiber bundle (glass strand) in which 10 to 8000 glass filaments are bundled, and has a weight in the range of 1 to 10000 tex (g/km).
• the glass filaments discharged from a plurality of nozzle tips or holes may be bundled into one glass fiber bundle or bundled into a plurality of glass fiber bundles.
• the glass fiber of the present embodiment is obtained by further processing the glass strand in various ways, such as yarns, woven fabrics, knitted fabrics, nonwoven fabrics (including chopped strand mats and multiaxial nonwoven fabrics), chopped strands, rovings, and powders.
• yarns such as yarns, woven fabrics, knitted fabrics, nonwoven fabrics (including chopped strand mats and multiaxial nonwoven fabrics), chopped strands, rovings, and powders.
• the glass fiber of the present embodiment improves the bundling property of the glass filament, improves the adhesion between the glass fiber and the resin, improves the uniform dispersion of the glass fiber in the mixture of the glass fiber and the resin or the inorganic material, and the like.
• the surface may be coated with an organic material.
• organic substances include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (especially carboxylic acid-modified polypropylene), (poly)carboxylic acid (especially maleic acid) and unsaturated monomers.
• a copolymer etc. can be mentioned.
• the glass fiber of the present embodiment may be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, and the like.
• the glass fiber of the present embodiment may be coated with a treatment composition that does not contain the above resin but contains a silane coupling agent, a surfactant, and the like.
• a resin composition or treatment composition is used in an amount of 0.03 to 2.0% by mass based on the mass of the glass fiber of the present embodiment that is not coated with the resin composition or treatment composition. proportion to cover the fiberglass.
• the coating of the glass fiber with an organic substance can be performed, for example, by applying a resin solution or a resin composition solution to the glass fiber using a known method such as a roller applicator in the glass fiber manufacturing process, and then applying the resin solution or the resin composition solution to the glass fiber. It can be carried out by drying the glass fibers to which the composition solution has been applied.
• the glass fiber of the present embodiment in the form of a woven fabric can be immersed in a treatment composition solution, and then the glass fiber to which the treatment composition has been applied can be dried.
• silane coupling agents include aminosilane, chlorosilane, epoxysilane, mercaptosilane, vinylsilane, and (meth)acrylsilane.
• Aminosilanes include ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)-N′- ⁇ -(aminoethyl)- ⁇ - Aminopropyltrimethoxysilane, ⁇ -anilinopropyltrimethoxysilane and the like can be mentioned.
• chlorosilane examples include ⁇ -chloropropyltrimethoxysilane and the like.
• epoxysilanes examples include ( ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and the like.
• Mercaptosilane includes ⁇ -mercaptotrimethoxysilane and the like.
• vinylsilane examples include vinyltrimethoxysilane and N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane.
• (Meth)acrylsilane includes ⁇ -methacryloxypropyltrimethoxysilane and the like.
• the silane coupling agents may be used alone, or two or more of them may be used in combination.
• 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, polyethyleneimine, poly Alkylpolyamine alkylamide derivatives, fatty acid amides, quaternary ammonium salts can be mentioned.
• animal oils examples include beef tallow.
• vegetable oils examples include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.
• Animal waxes include beeswax and lanolin.
• Examples of vegetable waxes include candelilla wax and carnauba wax.
• mineral wax examples include paraffin wax and montan wax.
• Condensates of higher saturated fatty acids and higher saturated alcohols include stearates such as lauryl stearate.
• fatty acid amides include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine and fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid.
• quaternary ammonium salts include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.
• the lubricants may be used alone, or two or more of them may be used in combination.
• surfactants examples include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
• the surfactants may be used alone, or two or more of them may be used in combination.
• Nonionic surfactants include ethylene oxide propylene oxide alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene-block copolymers, alkylpolyoxyethylene-polyoxypropylene-block copolymer ethers, polyoxyethylene fatty acid esters.
• polyoxyethylene fatty acid monoester polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester ethylene oxide adduct, polyoxyethylene castor oil ether, hydrogenated castor oil ethylene oxide adduct, alkylamine ethylene oxide adduct , fatty acid amide ethylene oxide adduct, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyhydric alcohol alkyl ether, fatty acid alkanolamide, acetylene glycol, acetylene alcohol , ethylene oxide adducts of acetylene glycol, and ethylene oxide adducts of acetylene alcohol.
• cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethylsulfate, higher alkylamine salts (acetate, hydrochloride, etc.), ethylene oxide adducts to higher alkylamines, higher Condensates of fatty acids and polyalkylenepolyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridinium salts can be mentioned.
• anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, ⁇ -olefin sulfates, alkylbenzenesulfonates, ⁇ -olefinsulfonates, reactions of fatty acid halides with N-methyltaurine. products, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphates of higher alcohol ethylene oxide adducts.
• Amphoteric surfactants include amino acid-type amphoteric surfactants such as alkylaminopropionic acid alkali metal salts, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.
• the glass fiber fabric of this embodiment contains the glass fiber of this embodiment described above.
• the glass fiber fabric of the present embodiment can be obtained by weaving the glass fiber of the present embodiment described above as at least part of the warp or weft using a loom known per se.
• the loom include jet looms such as air jet or water jet looms, shuttle looms, and rapier looms.
• the weaving method using the loom include plain weave, satin weave, Nanako weave, and twill weave, and plain weave is preferable from the viewpoint of manufacturing efficiency.
• the glass fiber fabric of the present embodiment preferably uses the glass fibers of the present embodiment described above as the warp and the weft.
• the glass fiber of the present embodiment described above is composed of 35 to 400 glass filaments with a filament diameter of 3.0 to 9.0 ⁇ m, which are bundled at 0 to 1.0 turns/25 mm. It preferably has a twist and a mass of 0.9 to 69.0 tex (g/km).
• the warp weaving density is preferably 40 to 120/25 mm, and the weft weaving density is preferably 40 to 120. It is preferably book/25 mm.
• the glass fiber fabric of the present embodiment may be subjected to deoiling treatment, surface treatment, and fiber opening treatment.
• the glass fiber fabric is placed in a heating furnace with an atmospheric temperature of 350°C to 400°C for 40 to 80 hours to thermally decompose the organic matter adhering to the glass fiber.
• 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 then the temperature is 80 to 180 ° C. In the range of 1 to 30 minutes, a treatment of drying by heating can be mentioned.
• fiber opening for example, while applying a tension of 30 to 200 N to the warps of the glass fiber fabric, fiber opening is performed by water pressure, high frequency vibration using liquid as a medium, and pressure of fluid having surface pressure. Examples include a process of widening the width of the warp and weft by performing fiber opening by pressurization with a fiber and a roll.
• the glass fiber fabric of the present embodiment preferably has a mass per unit area in the range of 7.0 to 190.0 g/m 2 and preferably has a thickness in the range of 8.0 to 200.0 ⁇ m. .
• the width of the warp of the glass fiber fabric of the present embodiment is preferably 110 to 600 ⁇ m, and the width of the weft is preferably 110 to 600 ⁇ m.
• 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.
• the surface treatment layer has a mass in the range of, for example, 0.03 to 1.50% by mass with respect to the total amount of the glass fiber fabric including the surface treatment layer. can be provided.
• the glass fiber reinforced resin composition of this embodiment contains the glass fiber of this embodiment described above.
• the glass fiber reinforced resin composition of the present embodiment is a glass fiber reinforced resin composition containing a resin (thermoplastic resin or thermosetting resin), glass fibers, and other additives, in which the glass fiber reinforced resin It contains 10 to 90% by mass of glass fiber relative to the total amount of the composition.
• the glass fiber reinforced resin composition of the present embodiment contains 90 to 10% by mass of resin and 0 to 40% by mass of other additives with respect to the total amount of the glass fiber reinforced resin composition.
• thermoplastic resin polyethylene, polypropylene, polystyrene, styrene/maleic anhydride resin, styrene/maleimide resin, polyacrylonitrile, acrylonitrile/styrene (AS) resin, acrylonitrile/butadiene/styrene (ABS) resin, chlorine 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, polyarylene sulfide
• polyethylene examples include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.
• HDPE high-density polyethylene
• LDPE low-density polyethylene
• LLDPE linear low-density polyethylene
• ultra-high molecular weight polyethylene examples include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.
• polypropylene examples include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.
• polystyrene examples include general-purpose polystyrene (GPPS), which is atactic polystyrene having an atactic structure, high-impact polystyrene (HIPS) obtained by adding a rubber component to GPPS, syndiotactic polystyrene having a syndiotactic structure, and the like.
• GPPS general-purpose polystyrene
• HIPS high-impact polystyrene
• methacrylic resin a polymer obtained by homopolymerizing one of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl ester, or two or more of them. can be mentioned.
• polyvinyl chloride a vinyl chloride homopolymer polymerized by a conventionally known emulsion polymerization method, suspension polymerization method, microsuspension polymerization method, bulk polymerization method, or the like, or copolymerizable with a vinyl chloride monomer
• a copolymer with a monomer, or a graft copolymer obtained by graft-polymerizing a vinyl chloride monomer to a polymer can be mentioned.
• Polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), polypentamethylene adipamide polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), poly decamethylene sebacamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polyundecaneamide (nylon 11), polyundecanamide (nylon 116), polydodecanamide (nylon 12), polyxylene Adipamide (Nylon XD6), Polyxylene Sebacamide (Nylon XD10), Polymetaxylylene Adipamide (Nylon MXD6), Polyparaxylylene Adipamide (Nylon PXD6), Polytetramethylene
• Polyacetals include homopolymers containing oxymethylene units as main repeating units, and copolymers containing oxyalkylene units consisting mainly of oxymethylene units and having 2 to 8 adjacent carbon atoms in the main chain. etc. can be mentioned.
• polyethylene terephthalate examples include polymers obtained by polycondensation of terephthalic acid or its derivatives and ethylene glycol.
• polybutylene terephthalate examples include polymers obtained by polycondensation of terephthalic acid or its derivatives and 1,4-butanediol.
• polytrimethylene terephthalate examples include polymers obtained by polycondensation of terephthalic acid or its derivatives and 1,3-propanediol.
• polycarbonates examples include polymers obtained by a transesterification method in which a dihydroxydiaryl compound and a carbonate ester such as diphenyl carbonate are reacted in a molten state, or polymers obtained by a phosgene method in which a dihydroxyaryl compound and phosgene are reacted. be able to.
• polyarylene sulfide examples include linear polyphenylene sulfide, crosslinked polyphenylene sulfide whose molecular weight is increased by performing a curing reaction after polymerization, 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-phenylene ether), poly(2-chloro-1,4-pheny
• Modified polyphenylene ethers include polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, poly(2,6-dimethyl-1,4-phenylene) ether and styrene/butadiene copolymers.
• 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 Polymer alloy with polyamide, polymer alloy with poly(2,6-dimethyl-1,4-phenylene) ether and styrene/butadiene/acrylonitrile copolymer, amino group, epoxy group, carboxy groups, styryl groups, etc., and polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxy groups, styryl groups, methacrylic groups, etc. are introduced into the polymer chain side chains of the above polyphenylene ethers. .
• polyaryletherketone examples include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), and the like.
• liquid crystal polymer As the liquid crystal polymer (LCP), one or more structures selected from aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, etc., which are thermotropic liquid crystal polyesters Examples include (co)polymers composed of units.
• Fluorine resins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluoroethylene propylene resin (FEP), fluoroethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyfluoride Examples include vinylidene (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene/chlorotrifluoroethylene resin (ECTFE), and the like.
• PTFE polytetrafluoroethylene
• PFA perfluoroalkoxy resin
• FEP fluoroethylene propylene resin
• ETFE fluoroethylene tetrafluoroethylene resin
• PVF polyvinyl fluoride
• PVDF vinylidene
• PCTFE polychlorotrifluoroethylene
• ECTFE ethylene/chlorotrifluoroethylene resin
• ionomer (IO) resins include copolymers of olefins or styrene and unsaturated carboxylic acids, in which some of the carboxyl groups are 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 L-isomer, poly-D-lactic acid, which is a homopolymer of D-isomer, and stereocomplex-type polylactic acid, which is a mixture thereof.
• Cellulose resins include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.
• thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic resins (PF), urethane resins (PU), polyisocyanates, polyisocyanurates, Polyimide (PI), urea (UF) resin, silicone (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleidotriazine (BT) resin, diallyl phthalate resin (PDAP), etc. can be mentioned.
• unsaturated polyester resins include resins obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol.
• vinyl ester resins include bis-based vinyl ester resins and novolak-based 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-phenylenediisoprediene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexidiene bisphenol type epoxy resin), phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol group ethane type novolak type epoxy resin, novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure, biphenyl type epoxy resin, xylylene type epoxy resin and phenyl aralkyl epoxy resins, naphthylene ether epoxy resins, naphthol epoxy resins, naphthalene diol epoxy resins, bifunctional to tetrafunctional epoxy naphthalene
• Melamine resins include polymers formed by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.
• Phenolic resins include novolac-type phenolic resins such as phenol novolak resins, cresol novolac resins, and bisphenol A-type novolak resins, resol-type phenol resins such as methylol-type resol resins and dimethylene ether-type resol resins, or arylalkylene-type phenol resins. and the like, and one of them or a combination of two or more of them can be mentioned.
• Urea resins include resins obtained by condensation of urea and formaldehyde.
• thermoplastic resin or thermosetting resin may be used alone or in combination of two or more.
• the glass fiber reinforced resin composition of the present embodiment is used for applications requiring low dielectric properties
• examples of the resin include epoxy resin, modified polyphenylene ether, polybutylene terephthalate, polypropylene, fluororesin, liquid crystal polymer (LCP ) is preferred.
• additives include reinforcing fibers other than glass fibers (e.g., carbon fibers, metal fibers), fillers other than glass fibers (e.g., glass powder, talc, mica), flame retardants, ultraviolet absorbers, and heat stabilizers. agents, antioxidants, antistatic agents, fluidity improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments and the like.
• 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 it.
• the glass fiber reinforced resin composition of the present embodiment can be produced by injection molding, injection compression molding, two-color molding, blow molding, foam molding (including supercritical fluid), insert molding, and in-mold coating molding. , extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, blow molding, stamping molding, infusion, hand lay-up, spray-up, resin transfer molding , a sheet molding compound method, a bulk molding compound method, a pultrusion method, a filament winding method, or the like, to obtain various glass fiber reinforced resin molded articles.
• a glass fiber reinforced resin molded product can also be obtained by curing the prepreg.
• molded products include, for example, electronic device housings, electronic parts, vehicle exterior members, vehicle interior members, vehicle engine peripheral members, muffler-related members, and high-pressure tanks.
• a printed wiring board can be mentioned as an electronic component.
• Vehicle exterior parts include bumpers, fenders, bonnets, air dams, and wheel covers.
• Vehicle interior materials include door trims and ceiling materials.
• Vehicle engine peripherals include oil pans, engine covers, intake manifolds, exhaust manifolds, and the like.
• muffler-related members examples include muffling members.
• the glass fiber of the present embodiment can also 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 the present embodiment.
• gypsum in particular, gypsum board with a thickness of 4 to 60 mm
• the glass fiber having the glass composition in the above range is 0.1 to 4.0 with respect to the total mass of gypsum. It can be contained in the range of % by mass.
• glass raw materials were mixed so that the glass composition after melting and solidification would be each composition of Examples 1 to 4 shown in Table 1 and Comparative Examples 1 to 10 shown in Tables 2 and 3, A glass batch was obtained.
• the glass batches corresponding to the glass compositions for glass fibers of Examples 1 to 4 or Comparative Examples 1 to 10 are placed in a platinum crucible with a diameter of 80 mm, melted at 1550 ° C. for 4 hours and 1650 ° C. for 2 hours, and the crucible to obtain homogeneous glass bulk and glass cullet. Then, the obtained glass bulk and glass cullet were annealed at 620° C. for 8 hours to obtain test pieces. The obtained test pieces were evaluated for dielectric constant and dielectric loss tangent by the methods described below. Also, using the glass cullet obtained in the process of preparing the test piece, the water resistance was evaluated by the method shown below.
• the working temperature range was calculated by the method shown below.
• the results of Examples 1 to 4 are shown in Table 1
• the results of Comparative Examples 1 to 5 are shown in Table 2
• the results of Comparative Examples 6 to 10 are shown in Table 3, respectively.
• the glass cullet obtained as described above is placed in a small cylindrical platinum bushing having one circular nozzle tip at the bottom of the container, heated to a predetermined temperature and melted, and then discharged from the nozzle tip.
• the glass was wound around a stainless steel collet at a predetermined speed and then cooled and solidified while being stretched to obtain a glass fiber having a perfectly circular cross section and a fiber diameter of 13 ⁇ m.
• About 1 g of the obtained glass fiber (test glass fiber) was collected from the collet, dried at 120° C. for 1 hour, and the mass (mass before operation) was measured.
• the test glass fibers were then placed in 100 ml of distilled water at 80° C. for 24 hours. After that, the test glass fiber was placed on a wire mesh having an opening of about 150 ⁇ m, washed with distilled water, dried at 120° C. for 1 hour, and the mass (mass after operation) was measured.
• the mass reduction rate (100 x (1-(mass after operation/mass before operation)) was calculated from the mass before operation and the mass after operation. If the mass reduction rate is 2.0% or less and almost no glass fiber components are eluted in water, it is regarded as OK. I made a thing NG.
• the test piece was polished to prepare a polished test piece of 80 mm ⁇ 3 mm (thickness 1 mm). Next, the obtained polished test piece was dried completely and then stored in a room at 23° C. and humidity of 60% for 24 hours. Then, the dielectric constant (dielectric constant Dk ) and dielectric loss tangent (dissipation factor Df) were measured.
• the glass cullet is pulverized, and 40 g of glass particles with a particle size of 0.5 to 1.5 mm are placed in a platinum boat of 180 x 20 x 15 mm, and placed in a tubular electric furnace with a temperature gradient of 1000 to 1400°C for 8 hours. After heating as described above, it was taken out from the tubular electric furnace and observed with a polarizing microscope to identify the position where glass-derived crystals (devitrification) began to precipitate. The temperature in the tubular electric furnace was actually measured using a B thermocouple, and the temperature at the position where the crystals began to precipitate was obtained and taken as the liquidus temperature.
• the working temperature range was calculated from the difference between the 1000 poise temperature and the liquidus temperature.
• SiO 2 in the range of 59.00 to 65.00% by mass
• B 2 O 3 in the range of 16.00 to 26.00% by mass
• 0-5.00% by weight of CaO 0-4.00% by weight of MgO
• 0-6.00% by weight of SrO in the range of 0.10 to 5.00 wt .
• TiO is less than 0.20% by mass, the total content of Na 2 O, K 2 O and Li 2 O is less than 1.00% by mass, and the total content (% by mass) of CaO, MgO and SrO 2 (TiO 2 /(CaO+MgO+SrO)) is in the range of 0.66 to 4.00, and the SiO 2 content (mass%) SI and the Al 2 O 3 content
• the rate (% by mass) A satisfies the formula (1), excellent water resistance and a dielectric constant of 4.2 in a high frequency range at a measurement frequency of 10 GHz were obtained. It is clear from the following that a glass fiber with excellent dielectric properties such as a dielectric loss tangent of 0.0011 or less can be obtained, and itself can be provided with a sufficient working temperature range of 26° C. or higher.
• the content of SiO2 is less than 59.00% by mass
• the content of B2O3 is more than 26.00 % by mass
• the content of Al2O3 is According to the glass composition for glass fibers of Comparative Example 1, in which the content of TiO 2 is less than 7.00% by mass and the content of TiO 2 is less than 0.10% by mass, glass fibers having sufficient water resistance can be obtained. It is clear that you cannot.
• the content of SiO2 is less than 59.00% by mass
• the content of B2O3 is more than 26.00 % by mass
• the content of Al2O3 is 7.00% by mass, based on the total amount of the glass composition for glass fiber. It is clear that even in the glass composition for glass fiber of Comparative Example 2, which has a content of less than 00% by mass, a glass fiber having sufficient water resistance cannot be obtained.
• the content of SiO2 is less than 59.00% by mass
• the content of B2O3 is more than 26.00 % by mass
• the content of Al2O3 is 7.00% by mass, based on the total amount of the glass composition for glass fiber. It is clear that even in the glass composition for glass fiber of Comparative Example 3, which has a content of less than 00% by mass, a glass fiber having sufficient water resistance cannot be obtained.
• the content of SiO2 is less than 59.00% by mass
• the content of B2O3 is more than 26.00 % by mass
• the content of Al2O3 is 7.00% by mass, based on the total amount of the glass composition for glass fiber.
• 00% by mass and the content of TiO 2 is more than 5.00% by mass, glass fibers with sufficient water resistance cannot be obtained in the glass composition for glass fibers of Comparative Example 4. , it is clear that crystallization occurs.
• the glass for glass fiber of Comparative Example 5 which has a SiO 2 content of less than 59.00% by mass and a B 2 O 3 content of more than 26.00% by mass with respect to the total amount of the glass composition for glass fiber It is clear that it is not possible to obtain glass fibers with sufficient water resistance even in the composition.
• the content of SiO 2 is less than 59.00% by mass and the content of Al 2 O 3 is more than 14.00% by mass with respect to the total amount of the glass composition for glass fiber, and the formula (1 ) is more than 4.65, it is clear that in the glass composition for glass fiber of Comparative Example 6, a glass fiber having sufficient water resistance cannot be obtained, and phase separation occurs. .
• the glass for glass fiber of Comparative Example 7 which has a SiO 2 content of less than 59.00% by mass and a B 2 O 3 content of more than 26.00% by mass with respect to the total amount of the glass composition for glass fiber It is clear that it is not possible to obtain glass fibers with sufficient water resistance even in the composition.
• the content of Al 2 O 3 is more than 14.00% by mass with respect to the total amount of the glass composition for glass fiber, and according to the glass composition for glass fiber of Comparative Example 8, it does not have a sufficient working temperature range. , it is clear that it is not possible to obtain glass fibers with a sufficiently low dielectric loss tangent in the high frequency range of the measurement frequency of 10 GHz.
• the ratio of the content (% by mass) of TiO 2 to the total content (% by mass) of CaO, MgO and SrO with respect to the total amount of the glass composition for glass fiber is less than 0.66. According to the glass composition for glass fiber of Comparative Example 10, it is clear that a glass fiber having sufficient water resistance and a sufficiently low dielectric loss tangent in the high frequency region of the measurement frequency of 10 GHz cannot be obtained.

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