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
  • 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
  • C03C25/26—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
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/285—Acrylic resins
• • 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
  • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/30—Polyolefins
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/321—Starch; Starch derivatives
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/323—Polyesters, e.g. alkyd resins
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/325—Polycarbonates
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/326—Polyureas; Polyurethanes
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/36—Epoxy resins
• • 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
  • 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
  • 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
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
  • C03B37/01—Manufacture of glass fibres or filaments
  • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
• • 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 a glass composition for glass fibers, a glass fiber composed of the glass composition for glass fibers, a glass fiber woven fabric containing the glass fibers, and a glass fiber reinforced resin composition containing the glass fibers.
• the glass fiber is prepared by melting a glass raw material prepared so as to be a glass composition for glass fiber having a desired composition in a glass melting furnace to obtain molten glass (a melt of a glass composition for glass fiber), and the molten glass. Is discharged from a container (bushing) having a nozzle plate on which several to several thousand nozzle tips are formed, and by winding at high speed, it is cooled while being stretched and solidified into a fibrous form (hereinafter, this operation is referred to as "this operation”. It is manufactured by "spinning").
• the bushing is formed of, for example, a precious metal such as platinum.
• glass fiber has been widely used in various applications for improving 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 notebook computers. Is increasing.
• glass absorbs energy as heat with respect to an alternating current, so when the resin molded product is used for a housing or a part 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 the dielectric loss tangent determined by the composition and structure of the glass, and is represented by the following formula (A).
• W kfv 2 ⁇ ⁇ 1/2 ⁇ tan ⁇ ⁇ ⁇ ⁇ (A)
• W is the dielectric loss energy
• k is a constant
• f is the frequency
• v 2 is the potential gradient
• ⁇ is the permittivity
• tan ⁇ is the dielectric loss tangent
• the housing of the electronic device in response to the increase in the frequency of AC current (f in the formula (A)) used for the housing or component of the electronic device, in order to reduce the dielectric loss energy, the housing of the electronic device Alternatively, glass fibers used in parts are required to have a lower dielectric constant and a lower dielectric loss tangent. In particular, since the influence on the equation (A) is larger than the dielectric constant multiplied by 1/2, a low dielectric loss tangent is required.
• the applicant has a low dielectric constant and a low dielectric tangent, and in order to enable efficient glass fiber formation, the generation of phase separation is suppressed, and the viscosity at a high temperature is increased.
• SiO 2 in the range of 52.0 to 59.5 mass% and the range of 17.5 to 25.5 mass% are in the range of 17.5 to 25.5 mass% with respect to the total amount of the glass composition for glass fiber.
• a glass composition for glass fibers containing MgO in the range and CaO in the range of 1.0 to 5.0% by mass, and F 2 and Cl 2 in the range of 0.1 to 3.0% by mass in total. See Patent Document 1).
• the phase separation is a phase separation phenomenon in which single-phase glass forms glass phases having different compositions due to heat or the like. When the phase split occurs, the chemical durability of the glass fiber decreases, and when the phase split occurs particularly significantly, it becomes difficult to make the molten glass into a fiber.
• the present inventors have studied diligently about the reason why the above-mentioned inconvenience occurs, and found that the cutting of the glass fiber during spinning is due to the generation of veins.
• the volume of the glass melting furnace is small according to the size of the bushing, and the temperature in the glass melting furnace and the glass raw material Volatile amount is relatively uniform.
• the volume of the glass melting furnace is large according to the size of the bushing, so that the inside of the glass melting furnace is large.
• Variations in temperature and volatilization of glass raw materials may occur, and due to these variations, the glass composition is biased.
• the dissimilar glass produced by this bias becomes streaky in the process of melting, and what appears as a difference in the refractive index in the glass is the vein.
• fibrillation occurs, when the molten glass is discharged from the bushing and stretched by winding at high speed, a viscosity difference is created due to the composition difference in the part where the fibrillation occurs, and this viscosity difference melts. It is presumed that cutting of glass fibers during spinning is likely to occur because the stretching of glass is inhibited.
• the present invention eliminates such inconveniences, and provides a glass composition for glass fibers, which has a low dielectric loss tangent, suppresses the generation of phase separation, reduces the viscosity at high temperature, and further reduces the occurrence of pulsation.
• the purpose is to provide.
• Another object of the present invention is to provide a glass fiber formed from the glass composition for glass fiber, a glass fiber woven fabric containing the glass fiber, and a glass fiber reinforced resin composition using the glass fiber. do.
• the glass composition for glass fiber of the present invention contains SiO 2 in a range of 52.0% by mass or more and 57.5% by mass or less with respect to the total amount of the glass composition for glass fiber.
• B 2 O 3 in the range of 5% by mass or more and 25.5% by mass or less
• Al 2 O 3 in the range of 8.0% by mass or more and 13.0% by mass or less
• 0% by mass or more and 2.0% by mass or less MgO in the range of 0% by mass or more and 6.0% by mass or less
• SrO in the range of 0.5% by mass or more and 6.5% by mass or less, and 0.1% by mass or more and 3.0% by mass.
• the ratio of the content rate (mass%) of Al 2 O 3 to the content rate (mass%) of B 2 O 3 is in the range of 0.35 to 0.54, including TiO 2 in the range of% or less.
• the content rate (mass%) SI of the SiO 2 the content rate (mass%) B of the B 2 O 3 , the content rate (mass%) M of the MgO, the content rate (mass%) C of the CaO, the above.
• the SrO content (mass%) SR and the TiO 2 content (mass%) T satisfy the following formula (1).
• the glass composition for glass fiber of the present invention SiO 2 , B 2 O 3 , Al 2 O 3 , MgO, CaO, SrO, and TiO 2 in the above range are contained, and B 2 O 3 is contained.
• a low dielectric loss tangent is provided, the generation of phase separation is suppressed, and the viscosity at high temperature is reduced. Further, the occurrence of pulse is reduced.
• having a low dielectric loss tangent means that the dielectric loss tangent is 0.0018 or less at a frequency of 10 GHz.
• the reduction of the viscosity at a high temperature means that the 1000-poise temperature (the temperature at which the viscosity of the molten glass becomes 1000-poise (100 Pa ⁇ s)) becomes 1375 ° C. or lower.
• the SI, B, M, C, SR and T satisfy the following formula (2). 9.56 ⁇ 100 x (B / SI) 2 x ⁇ SR / (C + SR) ⁇ 2/3 x ⁇ T / (M + T) ⁇ 1/2 ⁇ 11.77 ... (2)
• the glass composition for glass fibers of the present invention more reliably has a low dielectric loss tangent and more reliably generates a phase separation. It is suppressed, the viscosity at high temperature is reduced more reliably, and the occurrence of fibrillation is more reliably reduced.
• the SI, B, M, C, SR and T satisfy the following formula (3).
• the glass composition for glass fibers of the present invention has a lower dielectric loss tangent and more reliably suppresses the occurrence of phase separation.
• the viscosity at high temperature is reduced more reliably, and the occurrence of pulsation is further reduced.
• having a lower dielectric loss tangent means that the dielectric loss tangent is 0.0017 or less at a frequency of 10 GHz.
• the SI, B, M, C, SR and T satisfy the following formula (4).
• the glass composition for glass fibers of the present invention more reliably has a lower dielectric loss tangent and more reliably phase separation. The occurrence is suppressed, the viscosity at high temperatures is further reduced, and the occurrence of pulsation is more reliably reduced.
• the fact that the viscosity at a high temperature is further reduced means that the 1000-poise temperature (the temperature at which the viscosity of the molten glass becomes 1000-poise (100 Pa ⁇ s)) is less than 1370 ° C.
• the SI, B, M, C, SR and T satisfy the following formula (5).
• the glass composition for glass fibers of the present embodiment more reliably has a lower dielectric loss tangent and more reliably phase separation. Is suppressed, the viscosity at high temperature is more surely reduced, and the occurrence of pulse is more surely reduced.
• the glass fiber of the present invention comprises the above-mentioned glass composition for glass fiber of the present invention.
• the glass fiber of the present invention melts, for example, the above-mentioned glass composition for glass fiber of the present invention, and discharges the obtained melt from a bushing having 1 to 8000 nozzle tips or a nozzle plate having holes formed therein. It can be obtained by winding it at a high speed, cooling it while stretching it, and solidifying it into a fibrous form. Therefore, the glass fiber of the present invention has the same glass composition as the above-mentioned glass composition for glass fiber of the present invention.
• the glass fiber woven fabric of the present invention contains the above-mentioned glass fiber of the present invention.
• the glass fiber reinforced resin composition of the present invention contains the above-mentioned glass fiber of the present invention.
• the glass fiber reinforced resin composition of the present invention is, for example, in a glass fiber reinforced resin composition containing a resin (thermoplastic resin or thermocurable resin), glass fiber, and other additives, in the total amount of the glass fiber reinforced resin composition. On the other hand, it contains 10 to 90% by mass of glass fiber.
• the glass composition for glass fiber of the present embodiment has SiO 2 in the range of 52.0% by mass or more and 57.5% by mass or less and 19.5% by mass or more and 25.5 by mass with respect to the total amount of the glass composition for glass fiber.
• B 2 O 3 in the range of 8.0% by mass or more, Al 2 O 3 in the range of 8.0% by mass or more and 13.0% by mass or less, MgO in the range of 0% by mass or more and 2.0% by mass or less, and 0 CaO in the range of mass% or more and 6.0% by mass or less, SrO in the range of 0.5% by mass or more and 6.5% by mass or less, and TiO 2 in the range of 0.1% by mass or more and 3.0% by mass or less.
• the ratio of the content of Al 2 O 3 (% by mass) to the content of B 2 O 3 (% by mass) is in the range of 0.35 to 0.54, and the content of SiO 2 is said to be (Mass%) SI, B 2 O 3 content (mass%) B, MgO content (mass%) M, CaO content (mass%) C, SrO content (mass%) ) SR and the content rate (mass%) T of the TiO 2 satisfy the above formula (1). Further, according to the glass composition for glass fiber, SiO 2 , B 2 O 3 , Al 2 O 3 , MgO, CaO, SrO, and TiO 2 in the above range are contained, and B 2 O 3 is contained.
• the glass composition for glass fibers of the present embodiment is a glass formed from the glass composition for glass fibers when the content of SiO 2 is less than 52.0% by mass with respect to the total amount of the glass composition for glass fibers.
• the mechanical strength of the fiber is greatly reduced, and the function of the glass fiber as a reinforcing material in the glass fiber reinforced resin composition is impaired.
• the glass fiber is liable to deteriorate when placed in an acidic environment.
• the content of SiO 2 is more than 57.5% by mass with respect to the total amount of the glass composition for glass fiber, the viscosity at a high temperature becomes high, so that the temperature at which the glass raw material is melted becomes high, and the manufacturing cost is increased. From the viewpoint, it becomes unsuitable for industrial glass fiber production using a glass melting furnace provided with a bushing that requires a nozzle plate having 100 or more nozzle tips formed therein.
• the content of SiO 2 with respect to the total amount of the glass composition for glass fibers is preferably 52.5% by mass or more and 55.5% by mass or less, preferably 53.1% by mass. It is more preferably 55.0% by mass or less, further preferably 53.3% by mass or more and 54.7% by mass or less, and particularly preferably 53.5% by mass or more and 54.3% by mass or less. It is preferably 53.6% by mass or more and 54.2% by mass or less.
• the content of B 2 O 3 is less than 19.5 wt%, the dielectric loss tangent of the glass composition for glass fiber It cannot be reduced sufficiently.
• the content of B 2 O 3 exceeds 25.5% by mass with respect to the total amount of the glass composition for glass fibers, the occurrence of phase separation cannot be sufficiently suppressed regardless of the content of other components.
• the content of B 2 O 3 with respect to the total amount of the glass composition for glass fibers is preferably 22.5% by mass or more and 24.8% by mass or less, preferably 22.8. It is more preferably 23.0% by mass or more and 24.7% by mass or less, further preferably 23.0% by mass or more and 24.6% by mass or less, and 23.1% by mass or more and 24.5% by mass or less. Is particularly preferable, and 23.2% by mass or more and 24.4% by mass or less are most preferable.
• the content of Al 2 O 3 when the content of Al 2 O 3 is less than 8.0% by mass with respect to the total amount of the glass composition for glass fibers, regardless of the content of other components, The occurrence of phase separation cannot be sufficiently suppressed. On the other hand, if the content of Al 2 O 3 exceeds 13.0% by mass with respect to the total amount of the glass composition for glass fibers, the dielectric loss tangent of the glass composition for glass fibers cannot be sufficiently reduced.
• the content of Al 2 O 3 with respect to the total amount of the glass composition for glass fibers is preferably 11.1% by mass or more and 12.9% by mass or less. It is more preferably 4% by mass or more and 12.8% by mass or less, further preferably 11.6% by mass or more and 12.7% by mass or less, and 11.9% by mass or more and 12.6% by mass or less. It is particularly preferable, and it is most preferable that it is 12.0% by mass or more and 12.5% by mass or less.
• the veins are irrelevant regardless of the contents of other components. Occurrence cannot be reduced sufficiently.
• the content of MgO with respect to the total amount of the glass composition for glass fibers is preferably 0% by mass or more and 1.4% by mass or less, and 0% by mass or more and 1.1% by mass. % Or less, more preferably 0% by mass or more and 0.9% by mass, particularly preferably 0% by mass or more and 0.7% by mass or less, and 0% by mass or more and 0.5% by mass. Most preferably, it is% or less.
• the glass for glass fibers of the present embodiment when the CaO content is more than 6.0% by mass with respect to the total amount of the glass composition for glass fibers, the glass for glass fibers is suppressed while suppressing the occurrence of phase separation.
• the dielectric tangent of the composition cannot be sufficiently reduced.
• the content of CaO with respect to the total amount of the glass composition for glass fibers is preferably 1.5% by mass or more and 5.5% by mass or less, preferably 2.0% by mass. It is more preferably 5.3% by mass or less, more preferably 2.5% by mass or more and 5.2% by mass or less, and particularly preferably 2.8% by mass or more and 5.1% by mass or less. It is particularly preferable that it is 3.0% by mass or more and 5.0% by mass or less, and most preferably 3.0% by mass or more and 4.9% by mass or less.
• the glass composition for glass fibers of the present embodiment has a glass composition for glass fibers when the content of SrO is less than 0.5% by mass or more than 6.5% by mass with respect to the total amount of the glass composition for glass fibers.
• the dielectric tangent of the glass cannot be sufficiently reduced.
• the content of SrO with respect to the total amount of the glass composition for glass fibers is preferably 1.5% by mass or more and 6.0% by mass or less, preferably 2.0% by mass or more. It is more preferably 5.5% by mass or less, further preferably 2.2% by mass or more and 5.3% by mass or less, and particularly preferably 2.3% by mass or more and 5.2% by mass or less. , 2.5% by mass or more and 4.7% by mass or less is particularly preferable, and 2.8% by mass or more and 4.5% by mass or less is most preferable.
• the content of TiO 2 is less than 0.1% by mass with respect to the total amount of the glass composition for glass fiber, the viscosity at high temperature becomes high, so that the glass raw material is used.
• the melting temperature becomes high, and from the viewpoint of manufacturing cost, it becomes unsuitable for industrial glass fiber manufacturing using a glass melting furnace equipped with a bushing that requires a nozzle plate having 100 or more nozzle tips formed therein.
• the content of TiO 2 is more than 3.0% by mass with respect to the total amount of the glass composition for glass fibers, the dielectric loss tangent of the glass composition for glass fibers cannot be sufficiently reduced.
• the content of TiO 2 with respect to the total amount of the glass composition for glass fibers is preferably 0.2% by mass or more and 2.8% by mass or less, preferably 0.2% by mass. It is more preferably 2.7% by mass or less, more preferably 0.3% by mass or more and 2.6% by mass or less, and particularly preferably 0.4% by mass or more and 2.5% by mass or less. It is preferably 0.5% by mass or more and 2.0% by mass or less.
• the glass composition for glass fibers of the present embodiment may contain F 2 and Cl 2 in a total amount of 0.1% by mass or more and 2.0% by mass or less with respect to the total amount of the glass composition for glass fibers.
• F 2 and Cl 2 in this range in the glass composition for glass fibers of the present embodiment, it contributes to the reduction of viscosity at high temperature.
• F 2 and Cl 2 are contained in an amount of more than 2.0% by mass in total, the chemical durability of the glass composition for glass fibers may be deteriorated.
• glass composition for glass fiber of the present embodiment includes an F 2 and Cl 2
• the total content of F 2 and Cl 2 to the glass fiber glass the total amount of the composition is 0.2 mass% or more and 1.8 or mass% It is preferably 0.5% by mass or more and 1.5% by mass or less, more preferably 0.6% by mass or more and 1.4% by mass or less, and 0.7% by mass or less. It is particularly preferably 1.3% by mass or more, 0.8% by mass or more and 1.2% by mass or less, and 0.8% by mass or more and 1.0% by mass or less. Most preferred.
• glass fiber glass composition of this embodiment comprises a F 2
• the content of F 2 for the glass composition for glass fiber total amount is preferably 0.2 mass% to 1.8 mass%, It is more preferably 0.5% by mass or more and 1.5% by mass or less, further preferably 0.6% by mass or more and 1.4% by mass or less, and 0.7% by mass or more and 1.3% by mass or less. Is particularly preferable, 0.8% by mass or more and 1.2% by mass or less is particularly preferable, and 0.8% by mass or more and 1.0% by mass or less is most preferable.
• Glass composition for glass fiber of the present embodiment when containing F 2 to 0.4 mass%, it may be free of Cl 2 substantially (i.e., the content of Cl 2 is 0.01 May be less than%).
• the glass composition for glass fibers of the present embodiment may contain ZnO in the range of 0 to 3.0% by mass with respect to the total amount of the glass composition for glass fibers.
• ZnO in the range of 0 to 3.0% by mass
• the glass composition for glass fibers of the present embodiment contains ZnO, if the ZnO content is more than 3.0% by mass, devitrified substances are likely to occur, and stable glass fiber production cannot be performed.
• the content of ZnO with respect to the total amount of the glass composition for glass fibers is preferably 2.5% by mass or less, preferably 1.5% by mass or less. More preferably, it is more preferably 0.5% by mass or less.
• the glass composition for glass fibers of the present embodiment may contain Fe 2 O 3 in the range of 0% by mass or more and 1.0% by mass or less with respect to the total amount of the glass composition for glass fibers. If glass composition for glass fiber of the present embodiment includes Fe 2 O 3, from the viewpoint of suppressing bubbles contained in the glass fiber, the content of Fe 2 O 3 0.1 wt% 0. It is effective to set the range to 6% by mass or less.
• the glass composition for glass fibers of the present embodiment may contain SnO 2 in the range of 0% by mass or more and 1.0% by mass or less with respect to the total amount of the glass composition for glass fibers. If glass fiber glass composition of this embodiment comprises SnO 2, from the viewpoint of suppressing bubbles contained in the glass fiber, the content of SnO 2 or less 0.6% 0.1 wt% It is effective to set it in the range of.
• the total content of Na 2 O, K 2 O and Li 2 O is less than 1.0% by mass with respect to the total amount of the glass composition for glass fibers, and If the content of each component is less than 0.4% by mass, Na 2 O, K 2 O or Li 2 O may be contained.
• the total content of Na 2 O, K 2 O and Li 2 O is 1.0% by mass or more, or the content of each component is 0.4% by mass or more, based on the total amount of the glass composition for glass fibers. , The dielectric constant and the dielectric loss tangent of the glass composition for glass fibers are significantly deteriorated.
• the content of ZrO 2 is less than 0.4% by mass with respect to the total amount of the glass composition for glass fibers, ZrO 2 may be contained. If the content of ZrO 2 is 0.4% by mass or more with respect to the total amount of the glass composition for glass fibers, devitrified substances are likely to be generated, and stable glass fiber production cannot be performed.
• 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 fibers, Cr 2 O 3 may be contained. If the content of Cr 2 O 3 is 0.05% by mass or more with respect to the total amount of the glass composition for glass fibers, devitrified substances are likely to be generated, and stable glass fiber production cannot be performed.
• the glass composition for glass fibers of the present embodiment contains a total of oxides of Ba, P, Mn, Co, Ni, Cu, Mo, W, Ce, Y, and La as impurities derived from the raw materials for glass fibers. It may be contained in an amount of less than 1.0% by mass based on the total amount of the glass composition.
• glass composition for glass fiber of the present embodiment as impurities, BaO, P 2 O 5, CeO 2, Y 2 O 3, or if it contains La 2 O 3, in each of its content independently 0.40 It is preferably less than mass%, more preferably less than 0.20% by mass, further preferably less than 0.10% by mass, particularly preferably less than 0.05% by mass, and 0. Most preferably, it is less than 01% by mass.
• the glass composition for glass fiber of the present embodiment contains Bi 2 O 3 , Gd 2 O 3 , Pr 2 O 3 , Sc 2 O 3 , or Yb 2 O 3 as impurities caused by the raw materials.
• the contents thereof are independently preferably less than 0.10% by mass, more preferably less than 0.05% by mass, and even more preferably less than 0.01% by mass.
• the total content of SiO 2 , B 2 O 3 , Al 2 O 3 , MgO, CaO, SrO and TiO 2 is 97.0% by mass or more, and 97. It is preferably 5% by mass or more, more preferably 98.0% by mass or more, further preferably 98.5% by mass or more, particularly preferably 98.8% by mass or more, and 99. Most preferably, it is 0.0% by mass.
• the B ratio of the content of 2 O 3 content of Al 2 O 3 with respect to (mass%) (mass%) (Al 2 O 3 / B 2 O 3) is , 0.35 to 0.54.
• the range of the content of B 2 O 3 and the content of Al 2 O 3 is within the above range and Al 2 O 3 / B 2 O 3 is less than 0.35, the occurrence of phase separation is sufficient. Cannot be suppressed.
• the content of B 2 O 3 and the content of Al 2 O 3 are in the above range and Al 2 O 3 / B 2 O 3 is more than 0.54, the dielectric loss tangent is sufficient. It cannot be reduced or the occurrence of pulse cannot be sufficiently reduced.
• the B ratio of the content of 2 O 3 content of Al 2 O 3 with respect to (mass%) (mass%) (Al 2 O 3 / B 2 O 3) is , 0.49 to 0.53, more preferably 0.50 to 0.53, and even more preferably 0.50 to 0.52.
• the CaO content (mass%) C, the SrO content (mass%) SR, and the TiO 2 content (mass%) T satisfy the following formula (1).
• the glass composition for glass fibers of the present embodiment has a low dielectric loss tangent, the generation of phase separation is suppressed, and the temperature is high. Viscosity in the glass is reduced, and the occurrence of fibrillation is further reduced.
• the SI, B, M, C, SR and T satisfy the following formula (2).
• the glass composition for glass fibers of the present embodiment more reliably has a low dielectric loss tangent and more phase separation occurs. It is reliably suppressed, the viscosity at high temperatures is more reliably reduced, and the occurrence of fibrillation is more reliably reduced.
• the glass composition for glass fiber of the present embodiment has a mass of 53.1 with respect to the total amount of the glass composition for glass fiber.
• SiO 2 in the range of% or more and 55.0% by mass or less
• B 2 O 3 in the range of 22.5% by mass or more and 24.8% by mass or less, and 11.1% by mass or more and 12.9% by mass or less in the range.
• Al 2 O 3 , MgO in the range of 0% by mass or more and 1.4% by mass or less
• CaO in the range of 1.5% by mass or more and 5.5% by mass or less, and 1.5% by mass or more and 6.0.
• the (mass%) ratio (Al 2 O 3 / B 2 O 3 ) is preferably in the range of 0.49 to 0.53.
• the SI, B, M, C, SR and T satisfy the following formula (3).
• the glass composition for glass fibers of the present embodiment has a lower dielectric loss tangent and more reliably generates phase separation. It is suppressed, the viscosity at high temperature is reduced more reliably, and the occurrence of fibrillation is further reduced.
• the glass composition for glass fiber of the present embodiment has a mass of 53.1 with respect to the total amount of the glass composition for glass fiber.
• SiO 2 in the range of% or more and 55.0% by mass or less
• B 2 O 3 in the range of 22.5% by mass or more and 24.8% by mass or less, and 11.1% by mass or more and 12.9% by mass or less in the range.
• Al 2 O 3 of, MgO in the range of 0% by mass or more and 1.4% by mass or less
• CaO in the range of 2.5% by mass or more and 5.5% by mass or less, and 2.5% by mass or more and 4.7.
• the (mass%) ratio (Al 2 O 3 / B 2 O 3 ) is preferably in the range of 0.50 to 0.53.
• the SI, B, M, C, SR and T satisfy the following formula (4).
• the glass composition for glass fibers of the present embodiment more reliably has a lower dielectric loss tangent and more reliably phase separation. Is suppressed, the viscosity at high temperature is further reduced, and the occurrence of pulsation is more reliably reduced.
• the glass composition for glass fiber of the present embodiment has a mass of 53.1 with respect to the total amount of the glass composition for glass fiber.
• SiO 2 in the range of% or more and 54.3% by mass or less
• B 2 O 3 in the range of 23.1% by mass or more and 24.5% by mass or less
• the range of 11.6% by mass or more and 12.7% by mass or less Al 2 O 3 of, MgO in the range of 0% by mass or more and 1.1% by mass or less
• CaO in the range of 2.5% by mass or more and 5.5% by mass or less, and 2.5% by mass or more and 4.7.
• the (mass%) ratio (Al 2 O 3 / B 2 O 3 ) is preferably in the range of 0.50 to 0.53.
• the SI, B, M, C, SR and T satisfy the following formula (5).
• the glass composition for glass fibers of the present embodiment more reliably has a lower dielectric loss tangent and more reliably phase separation. Is suppressed, the viscosity at high temperature is more surely reduced, and the occurrence of pulse is more surely reduced.
• the glass composition for glass fiber of the present embodiment has a mass of 53.1 with respect to the total amount of the glass composition for glass fiber.
• SiO 2 in the range of% or more and 54.2% by mass or less
• B 2 O 3 in the range of 23.1% by mass or more and 24.4% by mass or less, and 11.6% by mass or more and 12.5% by mass or less.
• Al 2 O 3 of, MgO in the range of 0% by mass or more and 1.1% by mass or less
• CaO in the range of 2.5% by mass or more and 5.0% by mass or less, and 3.0% by mass or more and 4.7.
• the (mass%) ratio (Al 2 O 3 / B 2 O 3 ) is preferably in the range of 0.50 to 0.52.
• the content of each component described above is measured by using an ICP emission spectroscopic analyzer for Li, which is a light element, and wavelength dispersive fluorescence X for other elements. This can be done using a line analyzer.
• a glass batch (mixed and prepared by mixing glass raw materials) or glass fiber (when an organic substance is attached to the surface of the glass fiber, or the glass fiber is mainly contained in the organic substance (resin)). If it is contained as a reinforcing material, for example, it is used after removing organic substances by heating it in a muffle furnace at 300 to 650 ° C for about 0.5 to 24 hours). In a furnace, a homogeneous molten glass is obtained by holding the glass batch at a temperature of 1550 ° C. and glass fibers at a temperature of 1400 ° C. for 6 hours and melting the glass while stirring.
• the obtained molten glass is poured onto a carbon plate to prepare a glass cullet, which is then pulverized and pulverized to obtain a glass powder.
• Li which is a light element, is quantitatively analyzed using an ICP emission spectrophotometer after heat-decomposing the glass powder with an acid.
• Other elements are quantitatively analyzed using a wavelength dispersive fluorescent X-ray analyzer after the glass powder is formed into a disk shape with a press machine. The content and total amount of each component can be calculated by converting these quantitative analysis results into oxides, and the content rate of each component described above can be obtained from these numerical values.
• the glass composition for glass fibers of the present embodiment can be obtained by melting a glass raw material (glass batch) prepared to have the above-mentioned composition after melting and solidifying, and then cooling and solidifying.
• the 1000-poise temperature is in the range of 1330 to 1400 ° C, preferably in the range of 1340 to 1390 ° C, and more preferably in the range of 1345 to 1380 ° C. More preferably, it is in the range of 1350 to 1375 ° C.
• the liquidus temperature (the temperature at which crystal precipitation first occurs when the temperature of the molten glass is lowered) is in the range of 1050 to 1240 ° C., preferably.
• the temperature range (working temperature range) between the 1000 poison temperature and the liquid phase temperature is 200 ° C. or higher, preferably 200 to 400 ° C. , More preferably in the range of 210 to 360 ° C.
• the glass raw material prepared as described above is supplied to the glass melting furnace, and the temperature is 1000 poise temperature or higher. It melts in the range, specifically in the range of 1450 to 1550 ° C. Then, the molten glass melted to the above temperature is discharged from 100 to 8000 nozzle tips or holes controlled to a predetermined temperature, and the glass fiber is cooled and solidified while being stretched by winding at high speed. Is formed.
• the glass single 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 filament preferably has a diameter of 3.0 to 6.0 ⁇ m, more preferably a diameter in the range of 3.0 to 4.5 ⁇ m.
• the nozzle tip has a non-circular shape and has a protrusion or a notch for rapidly cooling the molten glass
• the nozzle tip has a non-circular shape (for example, elliptical shape or oval shape) by controlling the temperature condition.
• a glass filament having a cross-sectional shape can be obtained.
• 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, and the cross-sectional area is true.
• the fiber diameter (converted fiber diameter) when converted to a circle is in the range of 3.0 to 35.0 ⁇ m.
• the glass fiber of the present embodiment usually has the shape 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 the plurality of nozzle tips or holes may be focused on one glass fiber bundle or may be focused on 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 yarn, woven fabric, knitted fabric, non-woven fabric (including chopped strand mat and multiaxial non-woven fabric), chopped strand, roving, powder and the like. It can take various forms.
• the glass fiber of the present embodiment improves the focusing property of the glass filament, improves the adhesiveness between the glass fiber and the resin, improves the uniform dispersibility 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 substance.
• organic substances include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (particularly carboxylic acid-modified polypropylene), (poly) carboxylic acid (particularly maleic acid), and unsaturated monomers. Examples thereof include copolymers.
• 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 in addition to these resins.
• the glass fiber of the present embodiment may be coated with a treatment agent composition containing a silane coupling agent, a surfactant and the like without containing the above resin.
• a resin composition or a treatment agent composition is 0.03 to 2.0% by mass based on the mass of the glass fiber of the present embodiment in a state where the resin composition or the treatment agent composition is not coated. Coat the glass fiber in proportion.
• a resin solution or a resin composition solution is applied to the glass fiber by using a known method such as a roller type applicator, and then the resin solution or the resin is applied. This can be done by drying the glass fibers to which the composition solution has been applied. Further, the glass fiber of the present embodiment in the form of a woven fabric can be immersed in the treatment agent composition solution, and then the glass fiber to which the treatment agent composition is applied is dried.
• silane coupling agent aminosilane ( ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) -N'- ⁇ -(Aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ -anilinopropyltrimethoxysilane, etc.), Chlorsilane ( ⁇ -chloropropyltrimethoxysilane, etc.), Epoxysilane ( ⁇ - (3,4-epoxycyclohexyl)) Ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, etc.), mercaptosilane ( ⁇ -mercaptotrimethoxysilane, etc.), vinylsilane (vinyltrimethoxysilane, N- ⁇
• modified silicone oil As lubricants, modified silicone oil, animal oil (beef fat, etc.) and its hydrogen additive, vegetable oil (soy acid, palm oil, rapeseed oil, palm oil, castor oil, etc.) and this hydrogen additive, animal wax (myristic acid, lanolin) Etc.), vegetable wax (candelilla wax, carnauba wax, etc.), mineral wax (paraffin wax, montan wax, etc.), condensate of higher saturated fatty acid and higher saturated alcohol (stearic acid ester such as lauric stearate, etc.), Polyethyleneimine, polyalkylpolyamine Alkyl amide derivatives, fatty acid amides (eg, dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid) Etc.), quaternary ammonium salts (alkyltri
• surfactant examples include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
• the surfactant may be used alone or in combination of two or more.
• Nonionic surfactants include ethylene oxide propylene oxide alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene-block copolymer, alkylpolyoxyethylene-polyoxypropylene-block copolymer ether, and polyoxyethylene fatty acid ester.
• Polyoxyethylene fatty acid monoester Polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester ethylene oxide adduct, polyoxyethylene caster oil ether, hardened 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 , Ethethylene oxide adduct of acetylene glycol and ethylene oxide adduct of acetylene alcohol.
• Cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (acetate, hydrochloride, etc.), ethylene oxide adducts to higher alkylamines, higher grades.
• alkylamine salts acetate, hydrochloride, etc.
• Examples thereof include a condensate of a fatty acid and a polyalkylene polyamine, a salt of an ester of a higher fatty acid and an alkanolamine, a salt of a higher fatty acid amide, an imidazoline-type cationic surfactant, and an alkylpyridinium salt.
• anionic surfactants higher alcohol sulfate ester salt, higher alkyl ether sulfate ester salt, ⁇ -olefin sulfate ester salt, alkylbenzene sulfonate, ⁇ -olefin sulfonate, fatty acid halide and reaction with N-methyltaurine.
• Products include sulfosuccinic acid dialkyl ester salts, higher alcohol phosphate ester salts, and phosphate ester salts of higher alcohol ethylene oxide adducts.
• amphoteric tensides examples include amino acid amphoteric tensides such as alkylaminopropionic acid alkali metal salts, betaine amphoteric tensides such as alkyldimethylbetaine, and imidazoline amphoteric tensides.
• the glass fiber woven fabric of the present embodiment includes the above-mentioned glass fiber of the present embodiment.
• the glass fiber woven fabric of the present embodiment can be obtained by weaving the above-mentioned glass fibers of the present embodiment as at least a part of warp or weft by a loom known per se.
• the loom include jet looms such as air jets and water jets, shuttle looms, rapier looms and the like.
• the weaving method by the loom for example, plain weave, satin weave, Nanako weave, twill weave and the like can be mentioned, and plain weave is preferable from the viewpoint of production efficiency.
• the glass fiber woven fabric of the present embodiment it is preferable to use the above-mentioned glass fibers of the present embodiment as warp threads and weft threads.
• glass fiber woven fabric of the present embodiment in the above-mentioned glass fiber of the present embodiment, 35 to 400 glass filaments having a filament diameter of 3.0 to 9.0 ⁇ m are focused and 0 to 1.0 times / 25 mm. It is preferably twisted and has a mass of 0.9 to 69.0 tex (g / 1000 m).
• the warp weaving density is preferably 40 to 120 threads / 25 mm, and the weft weaving density is 40 to 120. This is preferably 25 mm.
• the glass fiber woven fabric of the present embodiment may be subjected to deoiling treatment, surface treatment, and opening treatment after being woven.
• Examples of the deoiling treatment include a treatment in which the glass fiber woven fabric is placed in a heating furnace having an atmospheric temperature of 350 ° C. to 400 ° C. for 40 to 80 hours to heat-decompose the organic matter adhering to the glass fiber.
• the glass fiber woven fabric is immersed in the silane coupling agent or a solution containing the silane coupling agent and the surfactant, excess water is squeezed, and then the temperature is 80 to 180 ° C. In the range, a treatment of heating and drying for 1 to 30 minutes can be mentioned.
• the fiber opening treatment for example, while applying a tension of 30 to 200 N to the warp of the glass fiber fabric, the fiber is opened by water flow pressure, the fiber is opened by high frequency vibration using a liquid as a medium, and the fiber is opened by the pressure of a fluid having surface pressure. Examples thereof include a process of widening the width of the warp and weft by opening the fiber by applying pressure with a fiber or a roll.
• the glass fiber woven fabric of the present embodiment preferably has a thickness in the range of 7.0 to 190.0 g / m 2 and a thickness in the range of 8.0 to 200.0 ⁇ m.
• the yarn width of the warp yarn of the glass fiber woven fabric of the present embodiment is preferably 110 to 600 ⁇ m, and the yarn width of the weft yarn is preferably 110 to 600 ⁇ m.
• the glass fiber woven fabric of the present embodiment may include the silane coupling agent or a surface treatment layer containing the silane coupling agent and the surfactant.
• the surface-treated layer is in the range of, for example, 0.03 to 1.50 mass% with respect to the total amount of the glass fiber woven fabric including the surface-treated layer. Can have mass.
• the glass fiber reinforced resin composition of the present embodiment contains the above-mentioned glass fiber of the present embodiment.
• the glass fiber reinforced resin composition of the present embodiment is a glass fiber reinforced resin in a glass fiber reinforced resin composition containing a resin (thermoplastic resin or thermocurable resin), glass fiber, and other additives. It contains 10 to 90% by mass of glass fiber based on the total amount of the composition. Further, the glass fiber reinforced resin composition of the present embodiment contains 90 to 10% by mass of the resin and other additives in the range of 0 to 40% by mass with respect to the total amount of the glass fiber reinforced resin composition.
• thermoplastic resin examples include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, and chlorine.
• polyethylene examples include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high-density polyethylene.
• HDPE high-density polyethylene
• LDPE low-density polyethylene
• LLDPE linear low-density polyethylene
• ultra-high-density polyethylene examples include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high-density polyethylene.
• polypropylene examples include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.
• polystyrene examples include general-purpose polystyrene (GPPS) which is an atactic polystyrene having an atactic structure, impact-resistant polystyrene (HIPS) in which a rubber component is added to GPPS, and syndiotactic polystyrene having a syndiotactic structure.
• GPPS general-purpose polystyrene
• HIPS impact-resistant polystyrene
• syndiotactic polystyrene having a syndiotactic structure examples include general-purpose polystyrene (GPPS) which is an atactic polystyrene having an atactic structure, impact-resistant polystyrene (HIPS) in which a rubber component is added to GPPS, and syndiotactic polystyrene having a syndiotactic structure.
• GPPS general-purpose polystyrene
• HIPS impact-resistant polystyrene
• methacrylic acid a polymer obtained by homopolymerizing one of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and vinyl fatty acid ester, or two or more thereof.
• examples thereof include a polymer obtained by copolymerizing the above.
• the polyvinyl chloride can be copolymerized with a vinyl chloride homopolymer polymerized by a conventionally known method such as an emulsion polymerization method, a suspension polymerization method, a microsuspension polymerization method, a massive polymerization method, or a vinyl chloride monomer.
• a conventionally known method such as an emulsion polymerization method, a suspension polymerization method, a microsuspension polymerization method, a massive polymerization method, or a vinyl chloride monomer.
• a copolymer with a monomer a graft copolymer obtained by graft-polymerizing a vinyl chloride monomer on the polymer, and the like.
• polycaproamide nylon 6
• polyhexamethylene adipamide nylon 66
• polytetramethylene adipamide nylon 46
• polytetramethylene sebacamide nylon 410
• polypentamethylene adipa Mido nylon 56
• polypentamethylene sebacamide 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
• polyundecamethylene adipamide nylon 116
• polydodecaneamide Nylon 12
• polyxylene Adipamide nylon XD6
• polyxylene sebacamide nylon XD10
• polymethoxylylen adipamide nylon MXD6
• polyparaxylylene adipamide polyparaxylylene adipamide
• the polyacetal includes a homopolymer having an oxymethylene unit as a main repeating unit and a copolymer containing an oxyalkylene unit having 2 to 8 adjacent carbon atoms in the main chain, which is mainly composed of an oxymethylene unit. And so on.
• polyethylene terephthalate examples include a polymer obtained by polycondensing ethylene glycol with terephthalic acid or a derivative thereof.
• polybutylene terephthalate examples include polymers obtained by polycondensing 1,4-butanediol with terephthalic acid or a derivative thereof.
• polytrimethylene terephthalate examples include polymers obtained by polycondensing 1,3-propanediol with terephthalic acid or a derivative thereof.
• polycarbonate examples include a polymer obtained by an ester exchange method in which a dihydroxydiaryl compound and a carbonic acid ester such as diphenyl carbonate are reacted in a molten state, or a polymer obtained by a phosgene method in which a dihydroxyaryl compound and a phosgene are reacted. Be done.
• polyphenylene sulfide examples include linear polyphenylene sulfide, crosslinked polyphenylene sulfide that has been polymerized by performing a curing reaction after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.
• polyphenylene ether examples include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1,4-phenylene ether), and 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-chlor
• Modified polyphenylene ethers include polymer alloys of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, and poly (2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene copolymers.
• polyaryletherketone examples include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).
• the liquid crystal polymer (LCP) has 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 thereof include (co) polymers composed of units.
• fluororesin examples include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylenepropylene resin (FEP), fluorinated ethylenetetrafluoroethylene resin (ETFE), polyvinylfluorolide (PVF), and polyvinylidene fluoride.
• PTFE polytetrafluoroethylene
• PFA perfluoroalkoxy resin
• FEP fluorinated ethylenepropylene resin
• ETFE fluorinated ethylenetetrafluoroethylene resin
• PVDF vinylidene
• PCTFE polychlorotrifluoroethylene
• ECTFE ethylene / chlorotrifluoroethylene resin
• ionomer (IO) resin examples include a copolymer of olefin or styrene and an unsaturated carboxylic acid, which is obtained by neutralizing a part of the carboxyl group with a metal ion.
• olefin / vinyl alcohol resin examples include ethylene / vinyl alcohol copolymer, propylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer saponified product, and propylene / vinyl acetate copolymer saponified product.
• cyclic olefin resin examples include monocyclics such as cyclohexene, polycyclics such as tetracyclopentadiene, and polymers of cyclic olefin monomers.
• polylactic acid examples include poly-L-lactic acid, which is an L-form homopolymer, poly-D-lactic acid, which is a D-form homopolymer, and stereocomplex-type polylactic acid, which is a mixture thereof.
• cellulose resin examples include methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate and the like.
• thermosetting resin examples include unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenol resin (PF), urethane resin (PU), polyisocyanate, and polyisocyanurate.
• PI polygonic
• UF urea
• SI silicone
• FR furan
• BR benzoguanamine
• alkyd resin xylene resin
• BT bismaride triazine
• PDAP diallyl phthalate resin
• examples of the unsaturated polyester resin include a resin obtained by subjecting an aliphatic unsaturated dicarboxylic acid to an aliphatic diol in an esterification reaction.
• vinyl ester resin examples include bis-based vinyl ester resin and novolac-based vinyl ester resin.
• epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and bisphenol M type epoxy resin (4,5'-(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'-cyclohexidiene bisphenol) Type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, novolac type epoxy resin having a fused ring aromatic hydrocarbon structure, biphenyl type epoxy resin, xylylene type epoxy resin Aralkill type epoxy resin such as phenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetra
• melamine resin examples include a polymer composed of a polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.
• phenol resin examples include novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, and bisphenol A-type novolak resin, resol-type phenol resins such as methylol-type resol resin and dimethylene ether-type resol resin, or arylalkylene-type phenol resins. Etc., and one of them, or a combination of two or more of them can be mentioned.
• urea resin examples include resins obtained by condensation of urea and formaldehyde.
• thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more.
• the resins include epoxy resin, modified polyphenylene ether, polybutylene terephthalate, polypropylene, fluororesin, and liquid crystal polymer (LCP). ) Is preferable.
• the other additives include reinforcing fibers other than glass fibers (for example, carbon fibers and metal fibers), fillers other than glass fibers (for example, glass powder, talc, mica), flame retardants, ultraviolet absorbers, and heat stabilizers.
• reinforcing fibers other than glass fibers for example, carbon fibers and metal fibers
• fillers other than glass fibers for example, glass powder, talc, mica
• flame retardants ultraviolet absorbers
• heat stabilizers examples thereof include 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 in which the glass fiber woven fabric of the present embodiment is impregnated with the resin by a method known per se and semi-cured.
• the glass fiber reinforced resin composition of the present embodiment includes an injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method, a foam molding method (including a supercritical fluid), an insert molding method, and an in-mold coating molding method.
• Sheet molding compound method, bulk molding compound method, plutruding method, filament winding method and other known molding methods can be used to obtain various glass fiber reinforced resin molded products. Further, by curing the prepreg, a glass fiber reinforced resin molded product can also be obtained.
• molded products include, for example, electronic device housings, electronic parts (printed wiring boards), vehicle exterior members (bumpers, fenders, bonnets, air dams, wheel covers, etc.), vehicle interior members (door trims, ceiling materials, etc.). Etc.), vehicle engine peripheral members (oil pan, engine cover, intake manifold, exhaust manifold, etc.), muffler-related members (silencer, etc.), high-pressure tank, etc.
• the glass fiber of the present embodiment can be suitably used as a reinforcing material for an inorganic material such as gypsum or cement in addition to the glass fiber reinforced resin composition of the present embodiment.
• an inorganic material such as gypsum or cement
• the glass fiber having the above range is 0.1 to 4.0% by mass based on the total mass of gypsum. Can be included in the range.
• glass raw materials were mixed so that the glass composition after melting and solidification had the respective compositions of Examples 1 to 5 and Comparative Examples 1 to 5 shown in Table 1 to obtain a glass batch.
• a glass batch corresponding to the glass composition for glass fibers of Examples 1 to 5 or Comparative Examples 1 to 5 was melted at 1550 ° C. for 6 hours to obtain a homogeneous glass cullet. Then, it was placed in a platinum crucible having a diameter of 80 mm and melted at 1500 ° C. for 4 hours, and the crucible was taken out to obtain a glass bulk. Then, the obtained glass bulk was annealed at 580 ° C. for 8 hours to obtain a test piece. The dielectric loss tangent and phase separation characteristics of the obtained test piece were measured or evaluated by the methods shown below. In addition, a 1000-poise temperature was measured using a glass cullet obtained in the process of preparing the test piece.
• the glass batch or the glass cullet corresponding to the glass composition for glass fibers of Examples 1 to 5 or Comparative Examples 1 to 5 was melted in a glass melting furnace at 1550 ° C., and the obtained melt was 200.
• Glass beads were obtained by discharging from a bushing having a nozzle plate on which individual nozzle tips were formed, cooling and solidifying. The obtained glass beads were slowly cooled at 580 ° C. for 8 hours, and the pulse characteristics were evaluated by the method shown below using at least 40 slowly cooled glass beads.
• the test piece was polished to prepare a polishing test piece of 80 mm ⁇ 3 mm (thickness 1 mm). Then, the obtained polishing test piece was stored in a room at 23 ° C. and a humidity of 60% for 24 hours after being completely dried. Next, the obtained polishing test piece was subjected to dielectric loss tangent (dissipation factor Df) at 10 GHz using JIS C 2565: 1992, a cavity resonator method dielectric constant measuring device ADMS01Oc1 (trade name) manufactured by AET Co., Ltd. ) was measured.
• dielectric loss tangent dissipation factor Df
• SiO 2 in the range of 52.0% by mass or more and 57.5% by mass or less with respect to the total amount of the glass composition for glass fibers shown in Examples 1 to 5 and 19.5.
• B 2 O 3 in the range of mass% or more and 25.5 mass% or less, Al 2 O 3 in the range of 8.0 mass% or more and 13.0 mass% or less, and 0 mass% or more and 2.0 mass% or less.
• MgO in the range
• CaO in the range of 0% by mass or more and 6.0% by mass or less
• SrO in the range of 0.5% by mass or more and 6.5% by mass or less, and 0.1% by mass or more and 3.0% by mass or less.
• the ratio (Al 2 O 3 / B 2 O 3 ) of the content rate (mass%) of Al 2 O 3 to the content rate (mass%) of B 2 O 3 including TiO 2 in the following range is 0. It is in the range of .35 to 0.54, the content rate (mass%) SI of the SiO 2 , the content rate (mass%) B of the B 2 O 3 , the content rate (mass%) M of the MgO, and the CaO.
• Content rate (mass%) C, content rate (mass%) SR of SrO, and content rate (mass%) T of TiO 2 satisfy the following formula (1), the glass composition for glass fibers of the present invention.
• the object has a low dielectric tangent (dielectric tangent of 0.0018 or less), phase separation is suppressed, viscosity at high temperature is reduced (with 1000 poison temperature of 1375 ° C or less), and the pulse The outbreak was reduced.
• the glass batch was melted at 1550 ° C., and the obtained melt was discharged from a bushing having a nozzle plate having 200 nozzle tips formed, and wound at a predetermined speed to be cooled and solidified while being stretched.
• a sizing agent was applied to the obtained 200 glass filaments with an applicator to assemble them, and the glass filaments were wound around a collet to obtain a glass fiber bundle. When a series of operations (spinning) was continued for 6 hours, no cutting of the glass fiber occurred.
• Comparative Example 6 Glass raw materials were mixed so that the glass composition after melting and solidification had the same composition as that of Comparative Example 5, and a glass batch was obtained. Next, the glass batch was melted at 1550 ° C., and the obtained melt was discharged from a bushing having a nozzle plate having 200 nozzle tips formed, and wound at a predetermined speed to be cooled and solidified while being stretched. , A glass fiber (glass filament) having a perfect circular cross section and a fiber diameter of 5 ⁇ m was formed. A sizing agent was applied to the obtained 200 glass filaments with an applicator to assemble them, and the glass filaments were wound around a collet to obtain a glass fiber bundle. When a series of operations (spinning) was continued for 6 hours, glass fiber cutting occurred 15 times.
• the glass composition for glass fibers of the present invention can produce glass fibers and glass fiber bundles by suppressing their cutting. Further, it was confirmed that the glass composition for glass fiber of the present invention sufficiently satisfies this level when it can withstand industrial production if the number of times of cutting the glass fiber when spinning is continued for 6 hours is 7 times or less. Was done. In the case of industrially producing glass fibers, the number of times the glass fibers are cut when spinning is continued for 6 hours is preferably 5 times or less, more preferably 3 times or less, and further preferably 1 time or less.

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• 2020
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