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
• • 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
  • 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

Definitions

• the present invention relates to a glass fiber composition for producing glass fibers suitable as a reinforcing material for resins, as well as glass fibers made from the glass fiber composition and a method for producing the same.
• Glass fiber known as E-glass, is a long glass fiber used as part of the structural components of printed circuit boards and vehicles such as cars and airplanes.
• Long glass fiber is manufactured by continuous molding (spinning) using a molding device called a bushing.
• the bushing device has a roughly rectangular appearance and is equipped with multiple nozzles (or orifices), and molten glass flows continuously from the tip of the bushing nozzle and is rapidly cooled to become glass fiber.
• Control of the bubble layer is particularly important in the production of E-glass.
• the formation of the bubble layer on the glass melt is easily influenced by the oxidation-reduction state of the glass.
• Patent Document 1 in addition to inorganic nitrates, two types of oxidizing agents such as manganese, chromium, and cerium, which have an oxidation number of 2 or more, are added, and the ratio of the FeO amount to the total Fe amount is 0.4 or less, that is, melting is performed under oxidizing conditions, thereby ensuring good operation of the glass production equipment and the quality of the obtained glass fiber.
• an oxidizing agent is required, which leads to an increase in raw material costs.
• glass fibers are used as a reinforcing material for resins, it is important to make the shape of the glass fibers uniform in order to keep the amount of glass fibers in the resin constant and to make the mechanical strength of the composite material uniform.
• the shape of the glass fibers is affected by the rate of heat dissipation from the molten glass during spinning. If the molten glass is easily heat dissipated, it is easily solidified from the molten state and the shape is easily determined, so that a uniform fiber diameter can be obtained.
• Fe 2+ has a higher thermal conductivity than Fe 3+ , so when the ratio of the amount of FeO to the total amount of Fe is small, heat dissipation from the molten glass becomes insufficient, making it difficult to make the fiber shape uniform.
• the present invention aims to provide a glass composition that can suppress the formation of a bubble layer on the surface of the molten glass, increase the radiant heat transfer from the upper burner, improve melting efficiency, and is easy to form into a uniform fiber shape.
• the glass fiber composition of the present invention is characterized in that it contains, by mass%, SiO 2 as the main component, 0 to less than 10% B 2 O 3 , 20 to 30% MgO + CaO, and 600 ppm or less SO 3 , and the Fe 2+ /total Fe in the glass is 40% or more.
• SiO 2 as the main component
• the Fe 2+ /total Fe in the glass is 40% or more.
• the thermal conductivity of the glass raw material and glass is high, making it easier to absorb heat from the burner and electrodes in the melting furnace, and improving melting efficiency.
• the ratio of Fe2+ /total Fe is high, that is, when the glass is shifted to the reducing side, SO2 gas is easily generated and a bubble layer is easily formed on the molten glass, but in the composition of the present invention, the SO3 content is as low as possible to 600 ppm or less, so even when the ratio of Fe2+ /total Fe is high, SO2 gas is unlikely to be generated and a bubble layer is unlikely to be formed on the molten glass. As a result, heat from the upper burner is unlikely to be blocked, and energy efficiency can be improved.
• SiO2 as a main component means that the content of SiO2 is the highest among the components contained in the composition.
• x + y + means the content of each component.
• the composition for glass fiber of the present invention in the above [1] preferably contains, by mass%, 50 to 65% SiO 2 , 10 to 20% Al 2 O 3 , 0 to less than 10% B 2 O 3 , 20 to 30% MgO + CaO, 0.5% or less SrO + BaO, 1 to 200 ppm SO 3 , 0.8% or less F, and less than 0.1% P 2 O 5 , and the Fe 2+ /total Fe in the glass is 40% or more.
• the composition for glass fibers of the present invention preferably contains, by mass, 1% or less of TiO 2 , 2% or less of Li 2 O+Na 2 O+K 2 O, and 0 to 30 ppm of MoO 3 .
• the glass fiber composition of the present invention is characterized by comprising any one of the glass fiber compositions [1] to [3] above.
• the method for producing glass fibers of the present invention is a method for producing the glass fibers described in [4] above, characterized by comprising the steps of heating and melting glass raw materials prepared to have a predetermined composition in a melting furnace to obtain molten glass, and ejecting the molten glass from multiple bushing nozzles to form it into fibers.
• the glass raw material and/or the molten glass may be heated by electrodes installed in the melting furnace.
• the glass raw material and/or the molten glass may be heated by a burner installed in the melting furnace.
• the present invention makes it possible to suppress the formation of a bubble layer on the surface of the molten glass, thereby increasing the radiant heat transfer from the upper burner and improving melting efficiency, and also to provide a glass composition that is easy to form into a uniform fiber shape.
• the glass fiber composition of the present invention (hereinafter, also simply referred to as "glass composition”) is characterized in that it contains SiO2 as a main component, and contains, by mass%, 0 to less than 10% of B2O3 , 20 to 30% of MgO + CaO, and 600 ppm or less of SO3 , and the Fe2 + /total Fe in the glass is 40% or more.
• glass composition contains SiO2 as a main component, and contains, by mass%, 0 to less than 10% of B2O3 , 20 to 30% of MgO + CaO, and 600 ppm or less of SO3 , and the Fe2 + /total Fe in the glass is 40% or more.
• % refers to % by mass.
• SiO 2 is a component that forms the skeleton of the network structure in glass and improves the mechanical strength of glass.
• the glass composition of the present invention contains SiO 2 as a main component. If the content of SiO 2 is too low, it is difficult to obtain the desired mechanical strength when the glass fiber made of the glass composition of the present invention is mixed with a resin to form a composite material. On the other hand, if the content of SiO 2 is too high, the solubility of the raw material decreases, making it difficult to obtain a homogeneous glass. In addition, the spinning temperature tends to increase and the productivity tends to decrease. Therefore, the preferred lower limit range of SiO 2 is 50% or more, 51% or more, 52% or more, 53% or more, and most preferably 54% or more. The preferred upper limit range is 65% or less, 63% or less, 60% or less, 59% or less, 58% or less, and most preferably 57% or less.
• B2O3 is a component that forms the skeleton of glass like SiO2 , and at the same time , it is a component that reduces the viscosity of glass .
• the preferred lower limit range of B2O3 is 0% or more, 0.01% or more, 0.1% or more, 1% or more, 2% or more, 3% or more, 3.1% or more, 4% or more, 4.5% or more, and most preferably 4.7% or more.
• the preferred upper limit range of B2O3 is less than 10%, 9% or less, 8% or less, 7% or less, and most preferably less than 7%.
• MgO is a component that reduces the viscosity of glass.
• the preferred lower limit range of MgO is 0% or more, 0.5% or more, 0.8% or more, 1% or more, and most preferably 1.5% or more.
• the preferred upper limit range is 15% or less, 13% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2.8% or less, 2.7% or less, and especially 2.5% or less.
• CaO like MgO, is a component that reduces the viscosity of glass.
• the preferred lower limit range of CaO is 15% or more, 16% or more, 18% or more, 20% or more, 21% or more, and most preferably 22% or more.
• the preferred upper limit range is 30% or less, 29% or less, 28% or less, and most preferably 26% or less.
• the preferred upper limit range is 30% or less, 29% or less, 28% or less, 27% or less, and most preferably 26% or less.
• SO3 is a component that releases SO2 gas in a glass melt at 1400°C or higher, resulting in a clarification effect. If the content is too high, SO2 gas is released excessively from the glass melt, causing reboiling at the interface with the refractory material or platinum, which is a material of the melting equipment, forming a bubble layer on the glass melt, making it difficult for the radiant heat from the upper burner to be transmitted to the glass melt, which may cause a decrease in meltability. In addition, bubbles may be mixed into the glass, causing glass fiber breakage during spinning.
• the SO 3 content is preferably 600 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, 230 ppm, 200 ppm or less, 130 ppm or less, 120 ppm or less, 100 ppm or less, 90 ppm or less, 70 ppm or less, 60 ppm or less, 50 ppm or less, 40 ppm or less, and particularly 30 ppm or less.
• the lower limit of the SO 3 content is not particularly limited and is 0 ppm or more, but in order to obtain the desired clarification effect, it is preferably 1 ppm or more, 5 ppm or more, and particularly 7 ppm or more.
• the preferred lower limit of the value of Fe2 + /total Fe is 40% or more, 41% or more, 42% or more, 43% or more, 44% or more, 45% or more, 46% or more, 47% or more, 48% or more, 49% or more, 50% or more, 51% or more, 52% or more, 53% or more, 54% or more, 55% or more, 56% or more, 57% or more, 58% or more, 59% or more, particularly 60% or more.
• the upper limit of the value of Fe2+ /total Fe is not particularly limited and may be 100%, but if it is too high, the polyvalent oxide components in the glass are easily reduced and precipitate as metal particles, which may cause breakage of the glass fiber during spinning.
• the preferred upper limit is 99% or less, 95% or less, 90% or less, 88% or less, 87% or less, 86% or less, 85% or less, 84% or less, 83% or less, 82% or less, 81% or less, and particularly 80% or less.
• the adjustment of the redox can be performed by adding an oxidizing agent.
• the oxidizing agent means SO3 , NO3 , etc. SO3 also works as a clarifier, so the amount mentioned above is preferable.
• NO3 can be added as a nitrate. In that case, it is preferable to add 0 ppm or more, 100 ppm or more, 300 ppm or more, 500 ppm or more, 1000 ppm or more, 1500 ppm or more, or 2000 ppm or more in terms of NO3 to the raw material batch, and it is preferable to add 8000 ppm or less, 7000 ppm or less, or 6000 ppm or less. If there is too much NO3 , the ratio of Fe2+ /total Fe becomes too low, so that the fiber diameter may be difficult to stabilize.
• Al 2 O 3 is a component that forms the skeleton of glass, suppresses phase separation of glass, and stabilizes vitrification. It is also a component that improves the strength and chemical resistance of glass.
• the preferred lower limit of Al 2 O 3 is 10% or more, 11% or more, and most preferably 12% or more.
• the preferred upper limit is 20% or less, 19% or less, 18% or less, and most preferably 17% or less.
• BaO like MgO and CaO, is a component that reduces the viscosity of glass, but its effect in reducing the viscosity of glass is smaller than that of MgO and CaO, and its raw material cost is high. Therefore, the preferred upper limit range is 1% or less, 0.9% or less, 0.8% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, and especially 0.15% or less.
• the lower limit range for BaO is 0% or more, but in order to obtain the above effect, it may be 0.001% or more, 0.003% or more, and especially 0.005% or more.
• the preferred upper limit range of the SrO+BaO content is 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, and especially 0.15% or less.
• the preferred lower limit range of the SrO+BaO content is 0% or more, 0.001% or more, 0.003% or more, and especially 0.005% or more.
• the F is a component that has a clarifying effect. It also has the effect of lowering the viscosity of the molten glass. However, if the content is high, there is a risk of increasing the environmental load and corroding the melting equipment. Therefore, the preferred upper limit range is 0.8% or less, 0.5% or less, 0.3% or less, 0.2% or less, and particularly 0.1% or less.
• the lower limit range of the F content is not particularly limited and is 0% or more, but in order to obtain the above effect, it is preferable that it is 0.01% or more, 0.02% or more, and particularly 0.05% or more.
• P 2 O 5 is a component that promotes phase separation of glass and is likely to reduce water resistance. In addition, it is a component that is in low stock worldwide and is a concern for supply instability. Therefore, by reducing the P 2 O 5 content, the supply risk of raw materials can be reduced, and production efficiency can be maintained and products can be supplied stably.
• the preferred upper limit range of the P 2 O 5 content is less than 0.1%, 0.09% or less, 0.08% or less, and particularly 0.07% or less.
• TiO 2 is a component that reduces the viscosity of glass and improves water resistance. However, if the content is too high, the high-temperature viscosity of glass tends to increase, and the dissolution rate of the raw material tends to slow down. Therefore, the preferred upper limit range is 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.49% or less, 0.48% or less, 0.47% or less, 0.46% or less, 0.45% or less, 0.44% or less, 0.43% or less, 0.42% or less, 0.41% or less, and particularly 0.4% or less.
• the preferred lower limit range is not particularly limited and is 0% or more, but TiO 2 is a component that can be mixed as an impurity in the raw material, and the use of high-purity raw materials leads to an increase in raw material costs, so it may be more than 0%, 0.1% or more, or even 0.15% or more.
• Li 2 O is a component that reduces the viscosity of glass.
• the glass composition of the present invention when used as a reinforcement material for a printed wiring board, it is preferable that it is not substantially contained because it may reduce the electrical resistance of the glass.
• the preferred upper limit range of Li 2 O is 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, 0.1% or less, or even substantially not contained (specifically less than 0.1%).
• K 2 O is a component that reduces the viscosity of glass, like Li 2 O and Na 2 O, but it may reduce the electrical resistance of glass, so it is preferable to reduce it as much as possible. Therefore, the preferred upper limit range is less than 1%, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, and most preferably 0.3% or less.
• K 2 O is often mixed in as an impurity in raw materials, and the use of high-purity raw materials leads to an increase in raw material costs. Therefore, the lower limit range may be 0% or more, 0.01% or more, and particularly 0.03% or more.
• alkali metal components and alkaline earth metal components are effective in reducing the viscosity of the glass melt, but they tend to reduce the electrical resistance of the glass and tend to precipitate crystals such as diopside and wollastonite, so they cannot be contained in large amounts. Therefore, in order to adjust the viscosity of the glass melt, it is effective to adjust the ratio of the total amount of components that tend to reduce the viscosity, such as alkali metal components (R 2 O), alkaline earth metal components (R'O), and B 2 O 3 , to the total amount of components that form the glass skeleton, such as SiO 2 and Al 2 O 3.
• the preferred upper limit range of the above value is 0.5 or less, 0.49 or less, 0.48 or less, particularly 0.47 or less.
• the preferred lower limit range is 0.34 or more, 0.35 or more, 0.36 or more, 0.37 or more, 0.38 or more, 0.39 or more, particularly 0.4 or more.
• ZrO2 is a component that improves the chemical durability of glass. However, if the content of ZrO2 is too high, the liquidus temperature will be high, devitrification will occur during spinning, and production efficiency may decrease. Therefore, the preferred upper limit range is 0.05% or less, 0.04% or less, or 0.03% or less.
• ZrO2 is a component that can be mixed into glass as an impurity of raw materials or by elution from refractories in melting equipment. The use of refractories sprayed with Pt or the like can suppress the mixing, but this leads to an increase in manufacturing costs. Therefore, the lower limit range of ZrO2 is 0% or more, but in view of the above points, it may be 0.01% or more.
• MoO3 is a component that easily reduces the Fe component in the glass. Therefore, the preferred lower limit range is 0.1 ppm or more, 0.5 ppm or more, 1 ppm or more, 1.5 ppm or more, 2 ppm or more, 5 ppm or more, or 6 ppm or more.
• the MoO3 content is too high, it may precipitate as Mo particles in the glass melt, causing glass fiber breakage during spinning. In particular, when the glass is shifted to the reduction side, this tendency becomes significant.
• the preferred upper limit range is 65 ppm or less, 63 ppm or less, 61 ppm or less, 50 ppm or less, 45 ppm or less, 40 ppm or less, 35 ppm or less, or 30 ppm or less.
• Cr 2 O 3 is a component that can be mixed in from the refractory material of the melting tank. Mixing can be suppressed by using a refractory material sprayed with Pt or the like, but this leads to an increase in manufacturing costs. Therefore, the preferred lower limit range of Cr 2 O 3 is 0% or more, 0.001% or more, 0.002% or more, or 0.003% or more. On the other hand, if the content of Cr 2 O 3 is high, it may precipitate as metal particles like MoO 3 , which may cause glass fiber breakage during spinning. This tendency is particularly noticeable when the glass is shifted to the reduction side. Therefore, the upper limit range is 0.02% or less, 0.015% or less, 0.013% or less, and particularly 0.011% or less.
• Pt and Rh are components that can be mixed in from bushing equipment. If the Pt or Rh content is high, they will precipitate as metal particles and may cause glass fiber breakage during spinning. Therefore, the preferred upper limits for the Pt and Rh content are 1 ppm or less, 0.7 ppm or less, 0.5 ppm or less, 0.3 ppm or less, and especially 0.1 ppm or less, respectively.
• SnO2 can be used as a clarifier. SnO2 releases oxygen gas at high temperatures of 1500°C or higher due to the change in valence of Sn associated with the temperature of the glass melt. Therefore, in order to obtain a sufficient clarification effect, SnO2 may be added in a range of 0.3% or less.
• the content of each is preferably 0.5% or less, 0.3% or less, 0.2% or less, 0.1% or less, and particularly less than 0.1%.
• the glass fiber of the present invention preferably contains, by mass%, 50-65% SiO 2 , 10-20% Al 2 O 3 , 0-10% or less B 2 O 3 , 20-30% MgO+CaO, 0.5% or less SrO+BaO, 1-200 ppm SO 3 , 0.8% or less F, and less than 0.1% P 2 O 5 , and the Fe 2+ /total Fe in the glass is 40% or more.
• the generation of a bubble layer on the surface of the molten glass can be suppressed, and the glass can easily absorb heat from the combustion atmosphere and the electrodes, thereby improving the melting efficiency.
• the spinning temperature of the glass fiber of the present invention is preferably 1300° C. or less, 1280° C. or less, 1250° C. or less, 1240° C. or less, particularly 1220° C. or less.
• the spinning temperature is the temperature at which the viscosity of the glass composition becomes 10 3 dPa ⁇ s.
• the liquidus temperature T L is high, stable production becomes difficult, so the liquidus temperature is preferably 1200° C. or less, 1190° C. or less, 1180° C. or less, 1150° C. or less, particularly preferably 1100° C. or less.
• the dielectric constant of the glass composition of the present invention at 25°C and 1 MHz is preferably 8 or less, and particularly 7.5 or less.
• the dielectric tangent at 25°C and 1 MHz is preferably less than 0.003, and particularly 0.002 or less.
• Young's modulus is a property that affects the mechanical strength of a composite material of glass fiber and resin. If the Young's modulus is too low, it is difficult to obtain a composite material with sufficient mechanical strength. Therefore, the preferred lower limit range of the Young's modulus of the glass composition is 80 GPa or more, 83 GPa or more, 85 GPa or more, and particularly 86 GPa or more. There is no particular upper limit for the Young's modulus, but in reality it is 200 GPa or less.
• the glass fiber composition of the present invention preferably has a mass reduction rate of 50% or less, 49% or less, 48% or less, 47% or less, and particularly 45% or less when glass classified into particle sizes of 300 to 500 ⁇ m and having a mass corresponding to the specific gravity is immersed in 100 ml of a 10% by volume aqueous HCl solution at 80°C for 90 hours. If the mass reduction rate is too high, it becomes difficult to use the composition in applications requiring acid resistance.
• the glass fiber composition of the present invention preferably has a mass loss rate of 5% or less, 4.8% or less, 4.6% or less, 4.4% or less, 4.2% or less, 4% or less, 3.8% or less, 3.6% or less, 3.4% or less, 3.2% or less, and particularly 3% or less when glass classified into particle sizes of 300 to 500 ⁇ m and having a specific gravity is immersed in 100 ml of a 10% by mass aqueous NaOH solution at 80°C for 90 hours. If the mass loss rate is too high, it becomes difficult to use the composition in applications requiring alkali resistance.
• the total amount of Li ions, Na ions, and K ions eluted from the glass in terms of oxide is preferably 0.03 mg or less, 0.029 mg or less, 0.028 mg or less, 0.027 mg or less, 0.026 mg or less, 0.025 mg or less, 0.024 mg or less, 0.023 mg or less, 0.022 mg or less, 0.021 mg or less, and particularly preferably 0.020 mg or less.
• the glass fiber composition and glass fiber manufacturing method of the present invention will be described below. Note that in the following explanation, the direct melt method (DM method) and the indirect molding method (MM method: marble melt method) are described as examples, but the present invention is not limited to the following, and other methods can also be used.
• DM method direct melt method
• MM method marble melt method
• a raw material batch is mixed to obtain the glass composition described above.
• Cullet may be used as part or all of the glass raw materials. The reasons for limiting the content of each component have already been described, and will not be explained here.
• the prepared raw material batch is put into a melting furnace, melted, and homogenized.
• the melting temperature is preferably about 1400 to 1600°C.
• the raw material batch is heated and melted by a burner or electrodes arranged in the melting furnace.
• the glass composition of the present invention is unlikely to form a bubble layer on the molten glass during melting, so that the radiant heat from the burner is unlikely to be blocked.
• the value of Fe 2+ /total Fe is high, the thermal conductivity is excellent and the heat from the electrodes is easily transferred into the molten glass. Therefore, whether a burner or an electrode is used as the heat source, the melting efficiency is excellent. Note that a burner and an electrode may be used in combination as the heat source.
• the molten glass obtained is continuously drawn from the bushing and formed into fibers to obtain glass fibers (DM method).
• the molten glass obtained is first formed into marbles, and then remelted.
• the molten glass is continuously drawn from the bushing and formed into fibers to obtain glass fibers (MM method).
• a sizing agent that imparts the desired properties may be applied to the surface of the glass fiber.
• sizing agents include polyurethane resins, epoxy resins, acid copolymers, modified polypropylene resins, polyester resins, antistatic agents, surfactants, antioxidants, coupling agents, lubricants, etc., obtained by mixing one or more of these agents.
• Examples of coupling agents that can be used for surface treatment of glass fibers include ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane hydrochloride, ⁇ -chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, and vinyltriethoxysilane. It is preferable to select an appropriate one from these depending on the type of resin to be composited
• the glass fiber of the present invention is suitable for use as chopped strands for resin reinforcement, and may also be processed into any glass fiber product, such as glass cloth, glass filler, glass paper, nonwoven fabric, continuous strand mat, glass roving, milled fiber, etc.
• the glass fiber of the present invention can be used in a mixture with other fibers as long as the purpose of the present invention is not hindered.
• Such fibers include glass fibers such as S-glass fibers, and fibers other than glass fibers such as carbon fibers and metal fibers.
• Tables 1 to 4 show Examples 1 to 17 and Comparative Example 1.
• Example 10 to 13 and Comparative Example 1 the oxidation-reduction state of the glass was changed by blending raw materials with different COD (chemical oxygen demand) or nitrate raw materials in the glass composition of Example 1, or by adjusting the SO3 content.
• COD chemical oxygen demand
• the dielectric constant ⁇ and dielectric tangent tan ⁇ at a frequency of 1 MHz were measured using plate-shaped samples processed to dimensions of 50 mm x 50 mm x 2 mmt from the glass samples obtained using the above method. Both main surfaces of the sample were lapped and polished using a polishing solution containing No. 1200 alumina powder. The measurements were performed at room temperature using a 1 MHz resonator and an impedance analyzer.
• Young's modulus was measured using a sample piece made by processing the glass obtained by the above method into a plate shape of 40 mm x 20 mm x 2 mm. Both main surfaces of this sample piece were polished with a polishing solution containing No. 1200 alumina powder. This sample piece was precision annealed prior to measurement to remove distortion. For the measurement, a thin gold film of 1500 ⁇ or more was formed on the sample piece by vapor deposition. The measurement was performed using a free resonance type elastic modulus measuring device (JE-RT3, manufactured by Nippon Technoplus).
• Acid resistance was measured as follows. First, the glass sample obtained above was crushed to obtain glass powder with a particle size of 300 to 500 ⁇ m, and the mass (m1) of the specific gravity of the glass powder was precisely weighed and placed in a resin container. Next, 100 ml of a 10% by volume hydrochloric acid solution obtained by diluting 35% by mass hydrochloric acid with ion-exchanged water was placed in the container, and the container was shaken for 90 hours in a water bath at 80 ° C. The shaking speed was 50 rpm. Then, the container was removed and cooled with water for 30 minutes.
• the glass powder in the container was removed into a glass filter (manufactured by SHIBATA, pore size 10 to 16 ⁇ m) while filtering with a suction filtration device.
• the mass (m2) of the glass funnel used here was measured in advance.
• the container was washed with ion-exchanged water so that no glass powder remained in the container.
• the funnel containing the glass powder was placed in a dryer at 120 ° C and kept until the powder was dried.
• the funnel containing the glass powder was then transferred to a desiccator and cooled to room temperature. After confirming that the funnel had returned to room temperature, the combined mass (m3) of the glass powder and the funnel was measured.
• the alkali resistance was measured as follows. First, the glass sample obtained above was crushed to obtain glass powder with a particle size of 300 to 500 ⁇ m, and the mass (m1) of the specific gravity of the glass powder was precisely weighed and placed in a resin container. Next, 100 ml of a 10% by mass aqueous sodium hydroxide solution prepared using sodium hydroxide reagent and ion-exchanged water was placed in the container, and the container was shaken for 90 hours in a water bath at 80 °C. The shaking speed was 50 rpm. Then, the container was removed and cooled with water for 30 minutes.
• the glass powder in the container was removed into a glass filter (manufactured by SHIBATA, pore size 10 to 16 ⁇ m) while filtering with a suction filtration device.
• the mass (m2) of the glass funnel used here was measured in advance.
• the container was washed with ion-exchanged water so that no glass powder remained in the container.
• the funnel containing the glass powder was placed in a dryer at 120 °C and held until the powder was dried.
• the funnel containing the glass powder was then transferred to a desiccator and cooled to room temperature. After confirming that the funnel had returned to room temperature, the combined mass (m3) of the glass powder and the funnel was measured.
• the presence or absence of a bubble layer on the surface of the molten glass was confirmed as follows. First, a predetermined amount of a variety of glass raw materials, including natural and chemical raw materials, was weighed out to a total of 100 g, and the glass composition obtained after melting was adjusted to the glass composition shown in Table 2. The obtained raw materials were placed in a 1.1 liter resin container and mixed for 15 minutes with a turbulent mixer to obtain a raw material batch. Next, the obtained raw material batch was placed in a triangular crucible made of platinum-gold alloy, and then melted in an indirect heating electric furnace in an air atmosphere. The temperature conditions were 1250°C, left to stand for 40 minutes, then heated to 1500°C over 40 minutes, and left to stand at 1500°C for 40 minutes.
• the triangular crucible containing the molten glass was removed from the electric furnace and allowed to cool to solidify the molten glass.
• the bottom and sides of the triangular crucible were carefully immersed in a bucket of water, taking care not to let water get into the crucible, and the glass was removed by utilizing the difference in thermal expansion coefficient between the crucible and the glass.
• the removed glass was immediately moved into an annealer that had been heated to 720°C and slowly cooled.
• the slowly cooled glass was left to stand at 720°C for 30 minutes, then cooled to 400°C at a cooling rate of -3°C/min, and then cooled to room temperature at a cooling rate of -10°C/min.
• the glass sample cooled to room temperature was observed from above to check for the presence or absence of a bubble layer on the sample surface.
• the COD and Fe2 + /total Fe values in the raw materials were measured by chemical analysis.
• the COD was analyzed in accordance with JIS K 0102 Industrial Wastewater Test Method 20. Oxygen consumption by potassium dichromate (COD Cr).
• the Fe 2+ /total Fe in the glass was measured as follows. First, the Fe 2+ amount was analyzed as follows. The glass sample obtained by the above method was pulverized to obtain glass powder, and 0.5 g of the glass powder was weighed, placed in a Teflon container, and moistened with deoxygenated water. Next, 15 ml of (1+1) sulfuric acid was added while introducing nitrogen gas through a tube, and deoxygenated water was added to obtain a 50 ml aqueous solution. Next, the Teflon container was heated in a water bath at 100°C for 10 minutes while flowing nitrogen gas.
• the nitrogen gas introduction tube was removed, 7 ml of hydrofluoric acid was added, and the mixture was stirred every 10 minutes while flowing nitrogen gas through the tube again, and heated for 30 minutes.
• the nitrogen gas introduction tube was removed again, and 6 g of boric acid was added, and the mixture was heated for 10 minutes while flowing nitrogen gas again.
• the Teflon container was cooled in water while flowing nitrogen gas. The tube was removed, and deoxygenated water was added to make the total amount 150 ml.
• 0.5 ml of O-phenanthroline indicator was added, and the solution was titrated with an N/200 aqueous cerium sulfate solution, and the point at which the solution changed from red to pale blue was read.
• the total Fe content was analyzed as follows. After the glass sample was pulverized to obtain glass powder, 0.3 g of the glass powder was weighed on a plate made of a platinum-rhodium alloy and moistened with pure water. 3 ml of SSG (1+1) sulfuric acid, 1 ml of SSG nitric acid, and 20 ml of hydrofluoric acid were added, and the glass powder was decomposed and dried by heating with an electric heater. Next, 12.5 ml of a mixed aqueous solution of pure water and SSG hydrochloric acid was added to the obtained solid, and the mixture was heated and dissolved with an electric heater and then allowed to cool.
• the solid was filtered with a 5C filter paper and the volume was adjusted to a constant volume in a 250 ml measuring flask.
• the Fe concentration in the sample solution was measured using an ICP-AES (inductively coupled plasma atomic emission spectrometry) device.
• the concentrations of the comparative standard solutions were 0, 0.5, 1.0, 2.0, and 5.0 ( ⁇ g/ml).
• the measurement wavelength was Fe: 238.277 nm.
• (1+1) means a solution obtained by diluting the stock solution of each acid solution with water at a ratio of 1:1.
• SSG means super-special grade reagent.
• the Fe2 + /total Fe value was calculated using the amount of Fe2 + and the amount of total Fe measured as described above.

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