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
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • 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
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
  • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

Definitions

• the present invention relates to glass fibers and glass compositions suitable for glass fibers.
• Patent Document 1 discloses a glass composition containing a large amount of rare earth oxides.
• the total content of Y 2 O 3 and La 2 O 3 in the glass composition of Patent Document 1 is in the range of 20 to 60 weight %.
• Patent Document 2 discloses a technique for improving the Young's modulus of a glass composition without requiring a large amount of rare earth oxides.
• the glass composition of Patent Document 2 contains 15 to 30% MgO expressed in mol % as a component for improving the Young's modulus.
• Patent Document 2 does not consider the acid resistance of the glass composition. Therefore, the object of the present invention is to provide a glass fiber having a high Young's modulus and excellent acid resistance, and a glass composition suitable for producing such a glass fiber.
• the inventors have conducted extensive research into the blending ratio of glass components and have completed a glass composition suitable for glass fibers that has an excellent balance between acid resistance and Young's modulus.
• the present invention relates to Expressed in mass %, SiO2 50-65% Al2O3 10-30 % MgO 10-20% CaO 0-7% TiO2 0-5% ZrO2 0-5% Including, The total content of SiO 2 , TiO 2 and ZrO 2 is 58% or more, The total content of TiO2 and ZrO2 is 0.1% or more, When the content of MgO is 10% or more and less than 16%, the glass composition for glass fiber contains 0.1% or more of ZrO2 .
• the present invention also provides a glass fiber comprising the glass composition for glass fiber according to the present invention.
• the present invention provides glass fibers that have an excellent balance between acid resistance and Young's modulus, and a glass composition for glass fibers that is suitable for such glass fibers.
• the contents of the components of the glass composition hereinafter are all shown in mass%, and mass% is basically expressed as "%".
• “substantially not contained” and “substantially not contained” mean that the content is less than 0.1 mass%, less than 0.05 mass%, less than 0.01 mass%, less than 0.005 mass%, even less than 0.003 mass%, and in some cases less than 0.001 mass%.
• “Substantially” is intended to allow the inclusion of trace amounts of impurities derived from glass raw materials, manufacturing equipment, etc.
• Alkali metal oxide means Li 2 O, Na 2 O, and K 2 O, and may be written as R 2 O.
• the upper and lower limits of the contents described below can be arbitrarily combined both when the upper and lower limits are individually described and when the upper and lower limits are described as ranges.
• SiO2 SiO 2 is a component that forms the skeleton of glass, adjusts the devitrification temperature and viscosity during glass formation, and improves acid resistance.
• the content of SiO 2 is, for example, 50 to 65%.
• the lower limit of the content of SiO 2 may be 55% or more, 57% or more, 57.5% or more, 58% or more, 59% or more, 59.6% or more, 59.8% or more, or even 60% or more.
• the upper limit of the content of SiO 2 may be 63% or less, 62.3% or less, 62% or less, 61.8%, 61.5% or less, or even 61% or less.
• the content of SiO 2 may be 55 to 62%, or even 57.5 to 61.5%.
• Al2O3 Al 2 O 3 is a component that adjusts the devitrification temperature and viscosity during glass formation and contributes to improving the water resistance of the glass.
• the content of Al 2 O 3 is, for example, 10 to 30%.
• the lower limit of the content of Al 2 O 3 may be, for example, 15% or more, 17% or more, 19% or more, 19.5% or more, 19.7% or more, or even 20% or more.
• the upper limit of the content of Al 2 O 3 may be 28% or less, 25% or less, 22% or less, 21% or less, 20.8% or less, or even 20.6% or less.
• the content of Al 2 O 3 may be 15 to 30%, or even 19.7 to 20.6%. However, as described later, when the content of MgO is in the range of less than 16%, the content of Al 2 O 3 may be 22 to 29%, or even 23.5 to 28%.
• B2O3 B 2 O 3 is an optional component that forms the skeleton of the glass and adjusts the devitrification temperature and viscosity during glass formation.
• the content of B 2 O 3 is, for example, 0 to 1.5%.
• the lower limit of the content of B 2 O 3 may be 0.02% or more.
• the upper limit of the content of B 2 O 3 may be 1.2% or less, 1% or less, 0.5% or less, 0.3% or less, 0.1% or less, or even 0.08% or less.
• B 2 O 3 may not be substantially contained.
• MgO is a component that contributes to improving Young's modulus and affects devitrification temperature, viscosity, etc.
• the content of MgO is, for example, 10 to 20%.
• the lower limit of the content of MgO may be 12% or more, 14% or more, 16% or more, 16.5% or more, 16.6% or more, 16.8% or more, or even 17% or more.
• the upper limit of the content of MgO may be 19% or less, 18% or less, 17.8% or less, 17.7% or less, or even 17.6% or less.
• the content of MgO may be 12 to 20%, or even 14 to 19%. If the content of MgO is less than 16%, the addition of ZrO2 is recommended.
• CaO CaO is an optional component that adjusts the devitrification temperature and viscosity during glass formation.
• the CaO content is, for example, 0 to 7%.
• the lower limit of the CaO content may be 0.1% or more, 0.3% or more, 0.5% or more, or even 0.7% or more.
• the upper limit of the CaO content may be 5% or less, 3% or less, 2% or less, 1.5% or less, 1.4% or less, 1.3% or less, 1.2% or less, or even 1% or less.
• Alkali metal oxide (R 2 O) is an optional component that adjusts the devitrification temperature and viscosity during glass formation.
• the total content of alkali metal oxides, specifically [Li 2 O] + [Na 2 O] + [K 2 O], is, for example, 0 to 3%.
• the lower limit of the content of alkali metal oxides may be 0.05% or more, 0.1% or more, 0.2% or more, or even 0.3% or more.
• the upper limit of the content of R 2 O may be 2% or less, 1.5% or less, 1.2% or less, 1.0% or less, 0.9% or less, or even 0.8% or less. If the content of R 2 O is high, the Young's modulus may not increase sufficiently.
• the content of Li 2 O is, for example, 0 to 1.5%.
• the lower limit of the content of Li 2 O is 0.1% or more, 0.2% or more, 0.3% or more, and may further be 0.4% or more.
• the upper limit of the content of Li 2 O may be 1% or less, 0.8% or less, 0.6% or less, and further 0.5% or less.
• a preferred example of the content of Li 2 O is 0.1 to 0.8%.
• Li 2 O is more advantageous than Na 2 O and K 2 O in terms of adjusting the properties such as the devitrification temperature while suppressing the effect of lowering the Young's modulus.
• the content of Li 2 O may be higher than the content of Na 2 O, may be higher than the content of K 2 O, or may be higher than the sum of the content of Na 2 O and the content of K 2 O. However, Li 2 O may not be substantially contained.
• the content of Na 2 O is, for example, 0 to 1%.
• the upper limit of the content of Na 2 O may be 0.5% or less, 0.2% or less, 0.18% or less, 0.15% or less, 0.13% or less, 0.1% or less, or even 0.08% or less.
• Na 2 O may not be substantially contained.
• the content of K 2 O is, for example, 0 to 0.5%.
• the upper limit of the content of K 2 O may be 0.3% or less, 0.1% or less, 0.08% or less, or even 0.06% or less, or even 0.04% or less.
• K 2 O may not be substantially contained.
• the sum of the Na 2 O content and the K 2 O content may be in the range of 0 to 1%, 0 to 0.5%, or even 0 to 0.3%.
• TiO2 and ZrO2 are optional components that can contribute to improving acid resistance. However, it is desirable to add at least one selected from TiO 2 and ZrO 2.
• ZrO 2 has been found to be a component that can supplement the effect of improving Young's modulus by MgO.
• the lower limit of the total content of TiO 2 and ZrO 2 may be 0.1% or more, 0.3% or more, 0.5% or more, 0.8% or more, 1% or more, or even 1.5% or more.
• the upper limit of the total content of TiO 2 and ZrO 2 may be 5% or less, 4% or less, 3.5% or less, 3% or less, or even 2.5% or less. In this embodiment, for example, the total content of TiO 2 and ZrO 2 may be in the range of 0.5 to 5%, 0.8 to 4%, or 1 to 3.5%.
• TiO2 and ZrO2 are added in the range of, for example, 0 to 5%.
• the TiO2 content and ZrO2 content may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, or even 1.2% or more.
• the TiO2 content and ZrO2 content may be 4% or less, 3% or less, 2.5% or less, or even 2% or less. However, TiO2 or ZrO2 may not be substantially contained.
• ZnO ZnO is an optional component that may be added. ZnO is added in the range of, for example, 0 to 3%, or further 0 to 1.5%. The upper limit of the ZnO content may be 1.4% or less, 1% or less, or further 0.5% or less. ZnO may not be substantially contained.
• F2 is also an optional component that may be added for clarification, etc.
• F2 is added in the range of, for example, 0 to 0.5%, and further 0 to 0.1%.
• the upper limit of the F2 content may be 0.08% or less.
• F2 may not be substantially contained.
• SiO2 + TiO2 + ZrO2 The total content of SiO 2 , TiO 2 and ZrO 2 (SiO 2 + TiO 2 + ZrO 2 ) is, for example, 58% or more.
• the total content of SiO 2 , TiO 2 and ZrO 2 may be 58.5% or more, 59% or more, 59.5% or more, 60% or more, 60.5% or more, or even 61% or more.
• a glass composition having a high (SiO 2 + TiO 2 + ZrO 2 ) is suitable for achieving excellent acid resistance.
• the upper limit of (SiO 2 + TiO 2 + ZrO 2 ) is not particularly limited, but is, for example, 63.5% or less, 63% or less, or even 62.5% or less.
• SiO2 + Al2O3 + MgO The total content of SiO2 , Al2O3 , and MgO ( SiO2 + Al2O3 +MgO) may be 95% or more, 96% or more, 97% or more, or even 97.5% or more. ( SiO2 + Al2O3 +MgO) may be, for example , 99% or less , or even 98.5% or less.
• the addition of CaO and alkali metal oxides (R 2 O) is suitable for adjusting the devitrification temperature of the glass composition.
• the sum of the CaO content and the R 2 O content (CaO+R 2 O) may be 0 to 2.5%.
• the lower limit of (CaO+R 2 O) may be 0.05% or more, 0.1% or more, 0.3% or more, 0.5% or more, 0.7% or more, or even 1% or more.
• the upper limit of (CaO+R 2 O) may be, for example, 2.3% or less, 2.2% or less, 2% or less, or even 1.8% or less.
• the glass composition may contain components other than those described above. Examples of other components that the glass composition may contain include Fe2O3 , Y2O3 , La2O3 , SrO , BaO, Cl2 , SnO2 , CeO2 , P2O5 , and SO3 .
• Fe2O3 is added in the range of, for example , 0 to 1%.
• the upper limit of the content of Fe2O3 may be 0.5%, 0.3% or less, 0.2% or less, 0.15% or less, or even 0.1% or less.
• Fe2O3 may not be substantially contained. Note that iron oxide is also present in the glass composition as a part of FeO , but the content is shown in terms of Fe2O3 according to conventional practice.
• Y 2 O 3 and La 2 O 3 are optional components that contribute to improving the Young's modulus. However, the raw materials of these components are relatively expensive.
• the total content of Y 2 O 3 and La 2 O 3 is, for example, 0 to 5%.
• the upper limit of the total content of Y 2 O 3 and La 2 O 3 may be 3% or less, 2% or less, 1% or less, or even 0.5% or less.
• Y 2 O 3 may not be substantially contained.
• La 2 O 3 may not be substantially contained either.
• each of SrO, BaO, Cl2 , SnO2 , CeO2 , P2O5 , and SO3 is, for example, 0 to 0.5 %.
• the upper limit of the content of each of these components may be 0.3% or less, 0.2% or less, or even 0.1% or less. Each of these components may not be substantially contained.
• composition example A containing 16% or more MgO
• the glass composition of the present embodiment may contain the following components. SiO2 50-65% B2O3 0-1.5 % Al2O3 10-25 % MgO 16-20% CaO 0-7% Li2O 0-1.0% Na2O 0-0.2% K2O 0-0.1% TiO2 0-5% ZrO2 0-5% Including, The total content of SiO 2 , TiO 2 and ZrO 2 is 58% or more, The total content of TiO2 and ZrO2 is 0.1% or more.
• the glass composition of the present embodiment may contain the following components. SiO2 50-65% B2O3 0-1.5 % Al2O3 10-30 % MgO 10-16% (except 16%) CaO 0-7% Li2O 0-1.0% Na2O 0-0.2% K2O 0-0.1% TiO2 0-5% ZrO2 0.1 to 5% Including, The total content of SiO 2 , TiO 2 and ZrO 2 is 58% or more.
• the content of each component may be appropriately adjusted by referring to the above-mentioned ranges.
• the content of Al 2 O 3 may be adjusted to be slightly higher, for example, 22 to 29%, or further 23.5 to 28%.
• the glass composition of the present embodiment may contain the following components. SiO2 55-65% B2O3 0-1.5 % Al2O3 10-28 % MgO 10-20% CaO 0-7% Li2O 0-1.0% Na2O 0-0.2% K2O 0-0.1% TiO2 0-5% ZrO2 1.2-5% Including, The total content of SiO 2 , TiO 2 and ZrO 2 is 60.4% or more.
• the content of ZrO 2 in Composition Examples A to C may be 1.5 to 3%.
• the Young's modulus of the glass composition of the present embodiment is, for example, 98 GPa or more.
• the lower limit of the Young's modulus can be 99 GPa or more, 99.5 GPa or more, or in some cases, 100 GPa or more.
• the upper limit of the Young's modulus is not particularly limited, but may be, for example, 115 GPa or less, or even 110 GPa or less.
• the acid resistance can be evaluated by the mass reduction rate ⁇ W (%) obtained by the test described in the Examples section.
• the ⁇ W of the glass composition of this embodiment is, for example, 0.3 mass% or less.
• the upper limit of ⁇ W can be 0.25 mass% or less, or further 0.1 mass% or less.
• the glass composition of the present embodiment is suitable for producing glass fibers.
• the glass fibers may be long glass fibers or short glass fibers.
• the glass fibers may be in at least one form selected from the group consisting of, for example, strands, rovings, yarns, cloths, chopped strands, glass wool, and milled fibers.
• the cloths are, for example, roving cloths and yarn cloths.
• the glass compositions of the above forms can also be used as glass molded products other than glass fibers.
• a glass molded product is particulate glass. Particulate glass can be broken into small pieces to the extent that the external shape of glass fibers is lost, or can be produced using a nozzle according to the desired shape, similar to glass fibers.
• the glass compositions of the above forms are also suitable for producing particulate glass while avoiding devitrification.
• the particulate glass includes the glass composition of the above forms, or is composed of the glass composition of the above forms.
• the particulate glass may correspond to at least one selected from the group consisting of glass flakes, glass powder, glass beads, and fine flakes.
• Particulate glass can be used for FRP, i.e., for reinforcing reinforced bodies such as resins.
• the above-mentioned glass composition can also be understood as a glass composition for glass fiber or particulate glass.
• Each glass fiber provided by the present invention can be used in the same applications as conventional glass fibers.
• One embodiment of the present invention provides a glass fiber nonwoven fabric containing glass fibers.
• Another embodiment of the present invention provides a rubber reinforcing cord containing strands of bundled glass fibers.
• the glass fibers can also be used in other applications.
• Other applications include reinforcing a reinforced object, typically a resin.
• a single glass fiber having a diameter of 15 ⁇ m was cut to a length of 20 mm, and an amount in grams equal to the specific gravity of the glass was taken. This glass fiber was immersed in 80 mL of an aqueous sulfuric acid solution having a specific gravity of 1.2 at 99° C. for 60 minutes to determine the mass reduction rate, which was defined as ⁇ W.
• Mass reduction rate (%) ⁇ (Wa ⁇ Wb)/Wa ⁇ 100
• ⁇ W is the mass reduction rate when the glass composition, whose mass is in grams equal to the specific gravity of the glass composition, is immersed in 80 mL of sulfuric acid solution having a specific gravity of 1.2 and a temperature of 99° C. for 60 minutes.
• the glass fiber according to technology 11 having a form corresponding to at least one selected from the group consisting of strands, rovings, yarns, cloths, chopped strands, glass wool, and milled fibers.

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• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Glass Compositions (AREA)

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Citations (8)

• 2022
  • 2022-11-16 JP JP2022183742A patent/JP2024072725A/ja active Pending
• 2023
  • 2023-11-08 CN CN202380075122.4A patent/CN120051446A/zh active Pending
  • 2023-11-08 EP EP23891444.4A patent/EP4620932A1/en active Pending
  • 2023-11-08 WO PCT/JP2023/040292 patent/WO2024106292A1/ja not_active Ceased
  • 2023-11-13 TW TW112143636A patent/TW202432488A/zh unknown

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