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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
  • H01M50/437—Glass
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/44—Fibrous material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to glass fibers suitable for use in power storage devices or filtering materials, specifically, as members for power storage devices such as separators and clad tubes, or as filtering materials in bag filters and the like.
• Lead-acid batteries which are typical secondary batteries, use lead dioxide for the positive electrode, lead for the negative electrode, and dilute sulfuric acid for the electrolyte.
• Sealed lead-acid batteries use a battery that prevents short circuits between the positive and negative electrodes.
• a separator is generally provided to hold the electrolyte.
• a nonwoven fabric made of short glass fibers having a diameter of several ⁇ m or less is known (Patent Document 1).
• clad lead-acid batteries are known to have a lead alloy core passed through a clad tube made of woven long glass fibers, and the clad tube prevents the active material from leaking into the electrolyte. Hold.
• a bag filter is a device that filters exhaust gas generated from powder-related equipment, incinerators, etc., and removes fine harmful substances such as dust and soot, and is composed of a filter material called a filter cloth.
• filter cloths those made of woven or nonwoven fabrics made of organic polymer fibers or glass fibers are known. Filter cloths for filtering exhaust gas from incinerators and the like are required to have excellent acid resistance.
• C glass composition is known as a glass with excellent acid resistance.
• the C glass composition contains about 4 to 6% by mass of diboron trioxide (B 2 O 3 ).
• B 2 O 3 easily scatters when glass raw materials are melted, and corrodes the walls of the melting furnace and the heat storage furnace. Therefore, a glass composition containing B 2 O 3 to the above-mentioned extent can affect the life of the equipment that manufactures it. Therefore, an object of the present invention is to provide a new glass fiber suitable for use in power storage devices and filter media, and also suitable for mass production.
• the present invention is a glass fiber for power storage devices or filter media, Displayed in mass%, 55 ⁇ SiO 2 ⁇ 75, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 15, 5 ⁇ CaO ⁇ 30, 0 ⁇ ( Li2O + Na2O + K2O ) ⁇ 20, A glass fiber comprising a glass composition containing the following components is provided.
• Another aspect of the present invention is a glass fiber for power storage devices or filter media, Displayed in mass%, 50 ⁇ SiO 2 ⁇ 75, 0 ⁇ B 2 O 3 ⁇ 2, 0.1 ⁇ (MgO+CaO) ⁇ 20, 9 ⁇ ( Li2O + Na2O + K2O ) ⁇ 20, 5 ⁇ ZrO 2 ⁇ 20,
• a glass fiber comprising a glass composition containing the following components is provided.
• a new glass fiber is provided that is suitable for use as a member for an electricity storage device or a filter material, and is also suitable for mass production.
• not substantially containing and not substantially containing mean that the content is less than 0.1% by mass, less than 0.05% by mass, less than 0.01% by mass, and even 0. This means less than 0.005% by weight, in particular less than 0.003% by weight, and in some cases less than 0.001% by weight.
• substantially means that the inclusion of trace amounts of impurities originating from glass raw materials, manufacturing equipment, molding equipment, etc. is allowed.
• Mainn component means a component having the highest content on a mass basis.
• T-Fe 2 O 3 means total iron oxide converted to diiron trioxide (Fe 2 O 3 ).
• Alkali metal oxide means lithium oxide (Li 2 O), sodium oxide (Na 2 O) and potassium oxide (K 2 O). The upper and lower limits of the content described below can be arbitrarily combined.
• Glass composition A An example of a glass composition (hereinafter referred to as glass composition A) is expressed in mass%, 55 ⁇ SiO 2 ⁇ 75, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 15, 5 ⁇ CaO ⁇ 30, 0 ⁇ ( Li2O + Na2O + K2O ) ⁇ 20, Contains the following ingredients.
• the content of silicon dioxide (SiO 2 ) in glass composition A may be 55% by mass or more and 72% by mass or less.
• the content of aluminum oxide (Al 2 O 3 ) may be 5% by mass or more and 14% by mass or less.
• the content of calcium oxide (CaO) may be 5% by mass or more and 30% by mass or less.
• the content of diboron trioxide (B 2 O 3 ) may be 0.1% by mass or more and less than 2% by mass.
• Glass composition A may be a composition that does not substantially contain B 2 O 3 .
• the total content of alkali metal oxides (Li 2 O+Na 2 O+K 2 O) may be 0.1% by mass or more and 20% by mass or less.
• Glass composition A may be a composition substantially free of alkali metal oxides. Glass composition A does not need to contain substantially any components other than the above-mentioned components.
• compositions A-1 to A-4 are illustrated as more specific glass compositions A.
• Composition A-1 contains the following components in mass %. 55 ⁇ SiO 2 ⁇ 67, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 15, 45 ⁇ (SiO 2 -Al 2 O 3 ) ⁇ 57, 0.1 ⁇ MgO ⁇ 10, 15 ⁇ CaO ⁇ 30, 0 ⁇ ( Li2O + Na2O + K2O ) ⁇ 12
• the glass composition having glass composition A-1 has excellent heat resistance, suppresses deformation when heated to high temperatures, and has excellent chemical durability.
• SiO2 is a component that forms the skeleton of glass and is the main component of composition A-1. Further, SiO 2 is a component that adjusts the devitrification temperature and viscosity during glass formation, and is a component that improves acid resistance.
• the content of SiO 2 is 55% by mass or more and 67% by mass or less, but the lower limit of the content of SiO 2 can be 56% by mass or more, 57% by mass or more, 58% by mass or more, 59% by mass or more. and may be greater than 60% by mass.
• the upper limit of the content of SiO 2 may be 64% by mass or less, or 63% by mass or less.
• B 2 O 3 is a component that forms the skeleton of glass. Moreover, B 2 O 3 is also a component that adjusts the devitrification temperature and viscosity during glass formation.
• the lower limit of the content of B 2 O 3 may be 0.1% by mass or more.
• the upper limit of the content of B 2 O 3 may be less than 2% by mass, 1.5% by mass or less, 1% by mass or less, or 0.5% by mass or less.
• the upper limit of the content of B 2 O 3 may be less than 0.1% by mass.
• Composition A-1 may be substantially free of B 2 O 3 .
• Al2O3 Al 2 O 3 is a component that forms the skeleton of glass. Furthermore, Al 2 O 3 is a component that adjusts the devitrification temperature and viscosity during glass formation, and is a component that improves the water resistance of the glass. On the other hand, excessive content of Al 2 O 3 lowers the acid resistance of the glass. When the Al 2 O 3 content is 5% by mass or more and 15% by mass or less, an increase in the devitrification temperature of the glass, which would make glass production difficult, is suppressed, and the acid resistance of the glass is increased. Furthermore, the melting point of the glass does not become excessively high, and the uniformity of melting the raw materials increases.
• the lower limit of the content of Al 2 O 3 may be 6% by mass or more, 7% by mass or more, 8% by mass or more, 8.5% by mass or more, 9% by mass or more, 9.5% by mass or more, 10% by mass % or more, 10.5% by mass or more, 11% by mass or more, and even 11.1% by mass or more.
• the upper limit of the content of Al 2 O 3 may be 14% by mass or less, 13% by mass or less, 12.5% by mass or less, less than 12% by mass, or even 11.9% by mass or less.
• the lower limit of the value obtained by subtracting the Al 2 O 3 content from the SiO 2 content (SiO 2 - Al 2 O 3 ) is 45% by mass or more, 47% by mass or more, It can be more than 48% by mass, more than 48.5% by mass, more than 49% by mass, and even more than 49.5% by mass.
• the upper limit of (SiO 2 -Al 2 O 3 ) may be 57% by mass or less, 56% by mass or less, 55% by mass or less, 54% by mass or less, 53% by mass or less, and even 52% by mass or less. It's possible.
• the lower limit may be 45% by mass or more, 46% by mass or more, 47% by mass or more, more than 48% by mass, 48.5% by mass or more, more than 49% by mass, and even 49.5% by mass or more. It's possible.
• the upper limit of (SiO 2 -B 2 O 3 -Al 2 O 3 ) may be 56% by mass or less, 55% by mass or less, 54% by mass or less, 53% by mass or less, 52% by mass or less, and even It may be 51% by mass or less.
• MgO, CaO MgO and CaO are components that adjust the devitrification temperature and viscosity during glass formation.
• the content of MgO is 1% by mass or more and 10% by mass or less, but the lower limit can be 1.5% by mass or more, 1.8% by mass or more, or even 2% by mass or more.
• the upper limit of the content of MgO may be 8% by mass or less, 6% by mass or less, 5% by mass or less, 4.5% by mass or less, or even 4% by mass or less.
• the devitrification temperature and the viscosity at the time of melting of the glass should be in a range suitable for manufacturing a glass composition while suppressing an excessive increase in the devitrification temperature. Can be done.
• the lower limit of the CaO content may be 16% by mass or more, 17% by mass or more, further 18% by mass or more, 19% by mass or more, and in some cases 20% by mass or more.
• the upper limit of the content of CaO may be 28% by mass or less, 27% by mass or less, 26% by mass or less, 25% by mass or less, or even 24% by mass or less.
• SrO strontium oxide
• SrO is a component that adjusts the devitrification temperature and viscosity during glass formation.
• excessive SrO content reduces the acid resistance of the glass.
• the lower limit of the SrO content may be 0.1% by mass or more.
• the upper limit of the content of SrO can be 15% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less , 2% by mass or less, 1.5% by mass or less, 1% by mass or less, and 0.5% by mass or less.
• the upper limit of the SrO content may be 0.1% by mass or less.
• Composition A-1 may be substantially free of SrO.
• the value of the total content of MgO, CaO and SrO (MgO+CaO+SrO) is important.
• the lower limit of (MgO + CaO + SrO) is preferably 15% by mass or more, 18% by mass or more, 20% by mass or more, 21% by mass or more, 22% by mass or more. , 23% by mass or more, 24% by mass or more, 25% by mass or more, 26% by mass or more, 27% by mass or more, and 28% by mass or more.
• the upper limit of (MgO+CaO+SrO) is preferably 40% by mass or less, more preferably 38% by mass or less, 36% by mass or less, 35% by mass or less, and 34% by mass or less.
• Composition A-1 may further contain barium oxide (BaO).
• BaO is a component that adjusts the devitrification temperature and viscosity during glass formation. On the other hand, excessive BaO content reduces the acid resistance of the glass.
• the upper limit of the BaO content may be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and even 0.1% by mass or less. % by mass or less.
• Composition A-1 may be substantially free of BaO.
• the value of the total content of MgO, CaO, SrO and BaO is important.
• the lower limit of (MgO+CaO+SrO+BaO) is preferably 15% by mass or more, 18% by mass or more, 20% by mass or more, 21% by mass or more, 22% by mass or more. , 23% by mass or more, 24% by mass or more, 25% by mass or more, 26% by mass or more, 27% by mass or more, and 28% by mass or more.
• the upper limit of (MgO+CaO+SrO+BaO) is preferably 40% by mass or less, more preferably 38% by mass or less, 36% by mass or less, 35% by mass or less, and 34% by mass or less.
• composition A-1 may further contain zinc oxide (ZnO). Furthermore, when included in composition A-1, ZnO is a component that adjusts the devitrification temperature and viscosity during glass formation. However, since ZnO is a relatively expensive raw material, if it is contained in a large amount, the raw material cost will increase. In composition A-1, the upper limit of the content of ZnO may be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, Furthermore, it may be 0.1% by mass or less. Composition A-1 may be substantially free of ZnO.
• Alkali metal oxides (Li 2 O, Na 2 O, K 2 O) are components that adjust the devitrification temperature and viscosity during glass formation.
• the value of the total content of alkali metal oxides (Li 2 O + Na 2 O + K 2 O) is 0% by mass or more and 12% by mass or less, the devitrification temperature and viscosity of the molten glass are reduced while suppressing an excessive increase in the devitrification temperature. can be in a range suitable for glass production. Further, while suppressing the increase in the melting point of the glass and achieving more uniform melting of the glass raw materials, high heat resistance of the glass can be ensured without excessively lowering the glass transition temperature.
• the lower limit of (Li 2 O+Na 2 O+K 2 O) may be greater than 0% by mass, or may be greater than or equal to 0.1% by mass.
• the upper limit of (Li 2 O+Na 2 O+K 2 O) may be 8% by mass or less, 6% by mass or less, 4% by mass or less, and even 2% by mass or less.
• the value of (Li 2 O+Na 2 O+K 2 O) may be 0.1% by mass or less.
• Composition A-1 may be substantially free of alkali metal oxides.
• Each of Li 2 O, Na 2 O, and K 2 O is an optional component. In other words, the lower limit of the content of each of these components may be zero.
• the lower limit of the content of lithium oxide (Li 2 O) may be 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, and even 0.4% by mass or more.
• the upper limit of the content of Li 2 O may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, and even 1% by mass or less.
• the lower limit of the content of sodium oxide (Na 2 O) may be 0.1% by mass or more, or 0.2% by mass or more.
• the upper limit of the content of Na 2 O may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, or even 1% by mass or less.
• the lower limit of the potassium oxide (K 2 O) content may be 0.1% by mass or more, or 0.2% by mass or more.
• the upper limit of the content of K 2 O may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, or even 1% by mass or less.
• Composition A-1 may further contain titanium dioxide (TiO 2 ).
• TiO 2 is a component that improves the meltability and chemical durability of glass, and improves the ultraviolet absorption characteristics of glass. Furthermore, TiO 2 is a component that improves the acid resistance and water resistance of glass. However, since TiO 2 is a relatively expensive raw material, if it is contained in a large amount, the raw material cost will increase.
• the lower limit of the content of TiO 2 may be 0.1% by mass or more.
• the upper limit of the content of TiO 2 may be 10% by mass or less, 5% by mass or less, less than 2% by mass, 1% by mass or less, 0.5% by mass or less, 0.3% by mass or less, and even 0. It may be 2% by mass or less.
• Composition A-1 may be substantially free of TiO 2 .
• Composition A-1 may further contain zirconium oxide (ZrO 2 ).
• ZrO 2 is a component that adjusts the devitrification temperature and viscosity during glass formation. Furthermore, ZrO 2 is a component that improves the acid resistance and alkali resistance of glass.
• the upper limit of the content of ZrO 2 may be 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5 It may be less than 0.1% by mass, and even less than 0.1% by mass.
• Composition A-1 may be substantially free of ZrO 2 .
• Composition A-1 may further contain diiron trioxide (Fe 2 O 3 ).
• Iron (Fe) usually exists in the Fe 2+ or Fe 3+ state.
• Fe 3+ is a component that enhances the ultraviolet absorption properties of glass
• Fe 2+ is a component that enhances heat ray absorption properties of glass. Even if Fe is not intentionally included, it may be unavoidably mixed in with industrial raw materials. If the content of Fe is small, coloring of the glass can be prevented.
• the upper limit of the content of Fe expressed by T-Fe 2 O 3 may be 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3 mass% or less, 0.2 mass% or less, further 0.1 mass% or less, less than 0.1 mass%, 0.08 mass% or less, 0.05 mass% or less, 0.04 mass% or less , and even 0.03% by mass or less.
• the lower limit of the content of Fe expressed by T-Fe 2 O 3 may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, and further 0.2% by mass or more. Particularly in glass compositions with a low content of alkali metal oxides, trace amounts of iron oxide can contribute to promoting glass fining.
• Composition A-1 may further contain fluorine (F 2 ) and chlorine (Cl 2 ). Since F 2 easily volatizes, there is a possibility of it scattering during melting, and there is also the problem that it is difficult to control the content in the glass.
• the upper limit of the content of F2 can be 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.2% by mass or less, and even 0.1% by mass or less. It's possible.
• Composition A-1 may be substantially free of F 2 .
• Composition A-1 may be substantially free of Cl 2 .
• Composition A-1 may have a preferred composition described in mass % in the following paragraphs.
• composition containing the following components and substantially free of alkali metal oxides.
• composition containing the following components and substantially free of LI 2 O.
• composition containing the following ingredients.
• composition containing the following ingredients.
• composition containing the following ingredients.
• compositions excluding compositions where 0.1 ⁇ B 2 O 3 ⁇ 2), the composition does not substantially contain B 2 O 3 .
• compositions that does not substantially contain Li 2 O.
• Composition A-2 contains the following components in mass %. 65 ⁇ SiO2 ⁇ 75, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 15, 50 ⁇ (SiO 2 -Al 2 O 3 ) ⁇ 60, 0.1 ⁇ MgO ⁇ 10, 10 ⁇ CaO ⁇ 25, 0 ⁇ (Li 2 O+Na 2 O+K 2 O) ⁇ 4
• the glass fiber having the glass composition A-2 has excellent heat resistance, suppresses deformation when heated to high temperatures, and has excellent chemical durability, particularly acid resistance.
• SiO2 SiO 2 is also the main component in composition A-2.
• the content of SiO 2 is greater than 65% by mass and not more than 75% by mass, but the lower limit may be 66% by mass or more.
• the upper limit of the content of SiO 2 may be 72% by mass or less, 70% by mass or less, 69% by mass or less, 68% by mass or less, or even 67% by mass or less.
• composition A-2 the content of B 2 O 3 and Al 2 O 3 can have the same upper and lower limits as composition A-1.
• the lower limit of the value obtained by subtracting the Al 2 O 3 content from the SiO 2 content (SiO 2 -Al 2 O 3 ) is more than 50% by mass. It can be 51% by mass or more, 52% by mass or more, or even more than 53% by mass. Further, the upper limit of (SiO 2 -Al 2 O 3 ) may be 60% by mass or less, 59% by mass or less, 58% by mass or less, and even 57% by mass or less.
• the MgO content is 0.1% by mass or more and 10% by mass or less, but the lower limit is 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, and even It may be 2% by mass or more.
• the upper limit of the content of MgO may be 8% by mass or less, 6% by mass or less, 5% by mass or less, 4.5% by mass or less, or even 4% by mass or less.
• the CaO content is 10% by mass or more and 25% by mass or less.
• the lower limit of the CaO content may be 12% by mass or more, 13% by mass or more, 14% by mass or more, and even more than 15% by mass.
• the upper limit of the CaO content may be 23% by mass or less, 22% by mass or less, 21% by mass or less, or even 20% by mass or less.
• composition A-2 may further contain SrO.
• the upper limit of the content of SrO can be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less , and even 0.1% by mass or less.
• Composition A-2 may be substantially free of SrO.
• Composition A-2 may further contain BaO.
• the content of BaO may have the same upper and lower limits as in composition A-1.
• Composition A-2 may be substantially free of BaO.
• composition A-2 may further contain ZnO.
• the ZnO content may have the same upper and lower limits as composition A-1.
• Composition A-2 may be substantially free of ZnO.
• composition A-2 the total content of alkali metal oxides (Li 2 O+Na 2 O+K 2 O) is 0% by mass or more and 4% by mass or less.
• the lower limit of (Li 2 O+Na 2 O+K 2 O) may be 0.1% by mass or more, 1% by mass or more, 1.5% by mass or more, or even 2% by mass or more.
• the upper limit of (Li 2 O+Na 2 O+K 2 O) may be 3.5% by mass or less, or 3% by mass or less.
• Composition A-2 may be substantially free of alkali metal oxides.
• Each of Li 2 O, Na 2 O, and K 2 O is an optional component. In other words, the lower limit of the content of each of these components may be zero.
• composition A-2 Li 2 O makes a particularly high contribution to the effect based on the alkali metal oxide described above.
• the lower limit of the content of Li 2 O in composition A-2 may be 0.1% by mass or more, 0.5% by mass or more, or even 1% by mass or more.
• the upper limit of the content of Li 2 O may be 4% by mass or less, 3% by mass or less, 2.5% by mass or less, or 2% by mass or less.
• composition A-2 the contents of Na 2 O and K 2 O can have the same upper and lower limits as composition A-1.
• Composition A-2 may further contain TiO 2 .
• the content of TiO 2 can have the same upper and lower limits as in composition A-1.
• Composition A-2 may be substantially free of TiO 2 .
• composition A-2 may further contain ZrO 2 .
• the content of ZrO 2 can have the same upper and lower limits as composition A-1.
• Composition A-2 may be substantially free of ZrO 2 .
• composition A-2 may further contain each of the above components.
• the preferred contents and other details of each of these components are the same as those for composition A-1, so their description will be omitted.
• Composition A-3 contains the following components expressed in mass %. 55 ⁇ SiO 2 ⁇ 67, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 15, 47 ⁇ (SiO 2 -Al 2 O 3 ) ⁇ 60, 0.1 ⁇ MgO ⁇ 10, 10 ⁇ CaO ⁇ 25, 4 ⁇ ( Li2O + Na2O + K2O ) ⁇ 9
• the glass fiber having the glass composition A-3 has excellent heat resistance, suppresses deformation when heated to high temperatures, and has excellent chemical durability, particularly acid resistance.
• composition A-3 Each component in glass composition A-3 will be explained below. However, regarding the role of each component, descriptions that overlap with the glass composition A-1 or A-2 will be omitted.
• SiO2 SiO 2 is also the main component in composition A-3. In composition A-3, the content of SiO 2 can have the same upper and lower limits as composition A-1.
• composition A-3 the contents of B 2 O 3 and Al 2 O 3 can have the same upper and lower limits as composition A-1.
• the lower limit of the value obtained by subtracting the content of Al 2 O 3 from the content of SiO 2 (SiO 2 -Al 2 O 3 ) is 47% by mass or more, It can be more than 49% by weight, more than 50% by weight, more than 51% by weight, more than 52% by weight, and even more than 53% by weight.
• the upper limit of (SiO 2 -Al 2 O 3 ) may be 60% by mass or less, 59% by mass or less, 58% by mass or less, and even 57% by mass or less.
• composition A-3 the MgO content can have the same upper and lower limits as composition A-1.
• the content of CaO is 10% by mass or more and 25% by mass or less.
• the lower limit of the CaO content may be 12% by mass or more, 13% by mass or more, 14% by mass or more, and even more than 15% by mass.
• the upper limit of the content of CaO may be 23% by mass or less, 21% by mass or less, 20% by mass or less, 19% by mass or less, or even 18% by mass or less.
• the sum of the contents of MgO and CaO can be set to 11% by mass or more and 35% by mass or less.
• the total content of alkali metal oxides and the total content of MgO and CaO are in appropriate ranges, so that the devitrification temperature of the glass can be suppressed while suppressing an excessive rise in the devitrification temperature.
• the temperature and viscosity at the time of melting can be set within a range suitable for producing a glass composition. Moreover, high acid resistance of the glass can be ensured.
• the lower limit of (MgO+CaO) may be 13% by mass or more, more than 14% by mass, 15% by mass or more, 16% by mass or more, and even more than 17% by mass.
• the upper limit of (MgO+CaO) may be 30% by mass or less, 28% by mass or less, 26% by mass or less, 25% by mass or less, or even 24% by mass or less.
• composition A-3 may further contain SrO.
• the SrO content can have the same upper and lower limits as composition A-2.
• Composition A-3 may be substantially free of SrO.
• Composition A-3 may further contain BaO.
• the content of BaO may have the same upper and lower limits as in composition A-1.
• Composition A-3 may be substantially free of BaO.
• composition A-3 may further contain ZnO.
• the ZnO content can have the same upper and lower limits as composition A-1.
• Composition A-3 may be substantially free of ZnO.
• the total content of alkali metal oxides is greater than 4% by mass and less than 9% by mass.
• the lower limit of (Li 2 O+Na 2 O+K 2 O) may be 4.5% by mass or more, or 5% by mass or more.
• the upper limit of (Li 2 O+Na 2 O+K 2 O) may be 8.5% by mass or less, 8% by mass or less, 7.5% by mass or less, and further 7% by mass or less.
• Each of Li 2 O, Na 2 O, and K 2 O is an optional component. In other words, the lower limit of the content of these components may be 0 as long as the total content of alkali metal oxides exceeds 4% by mass.
• composition A-3 Li 2 O makes a particularly high contribution to the effect based on the alkali metal oxide described above.
• the lower limit of the Li 2 O content in composition A-3 may be 0.1% by mass or more, 0.5% by mass or more, or even 1% by mass or more.
• the upper limit of the content of Li 2 O may be 3% by mass or less, or 2% by mass or less.
• the lower limit of the content of Na 2 O may be 0.1% by mass or more, 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass. In addition to the above, the content may be 2% by mass or more.
• the upper limit of the content of Na 2 O may be 8% by mass or less, 7% by mass or less, and further 6% by mass or less.
• the lower limit of the content of K 2 O may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more.
• the upper limit of the content of K 2 O may be 3% by mass or less, less than 2% by mass, and even less than 1% by mass.
• Composition A-3 may further contain TiO 2 .
• the content of TiO 2 can have the same upper and lower limits as in composition A-1.
• Composition A-3 may be substantially free of TiO 2 .
• composition A-3 may further contain ZrO 2 .
• the content of ZrO 2 can have the same upper and lower limits as composition A-1.
• Composition A-3 may be substantially free of ZrO 2 .
• composition A-3 may further contain each of the above components.
• the preferred contents and other details of each of these components are the same as those for composition A-1, so their description will be omitted.
• Composition A-4 contains the following components expressed in mass %. 55 ⁇ SiO 2 ⁇ 67, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 15, 47 ⁇ (SiO 2 -Al 2 O 3 ) ⁇ 60, 5 ⁇ CaO ⁇ 20, 6 ⁇ Na 2 O ⁇ 20, 9 ⁇ ( Li2O + Na2O + K2O ) ⁇ 20
• the glass composition having glass composition A-4 further has excellent heat resistance and chemical durability.
• composition A-4 Each component in glass composition A-4 will be explained below. However, regarding the role of each component, descriptions that overlap with the glass compositions A-1 to A-3 will be omitted.
• SiO2 SiO 2 is also the main component in composition A-4. In composition A-4, the content of SiO 2 can have the same upper and lower limits as composition A-3.
• composition A-4 the contents of B 2 O 3 and Al 2 O 3 can have the same upper and lower limits as composition A-1.
• composition A-4 from the viewpoint of improving the acid resistance of the glass, the value obtained by subtracting the content of Al 2 O 3 from the content of SiO 2 (SiO 2 -Al 2 O 3 ) is the same as that of composition A-3. It can have an upper limit and a lower limit.
• composition A-4 may further contain MgO.
• MgO MgO, CaO
• the lower limit of the content of MgO may be 0% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, or even 2% by mass or more.
• the upper limit of the MgO content may be 10% by mass or less, 8% by mass or less, 6% by mass or less, 5% by mass or less, 4.5% by mass or less, or even 4% by mass or less.
• the content of CaO is 5% by mass or more and 20% by mass or less.
• the lower limit of the content of CaO may be 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, or even 10% by mass or more.
• the upper limit of the content of CaO may be 18% by mass or less, 17% by mass or less, 16% by mass or less, and even 15% by mass or less.
• composition A-4 when the ease of molding of the glass composition is important, the sum of the contents of MgO and CaO (MgO+CaO) can be set to 5% by mass or more and 30% by mass or less.
• the sum of the content of alkali metal oxides and the sum of the contents of MgO and CaO is in an appropriate range, so that the devitrification temperature of the glass can be suppressed while suppressing an excessive rise in the devitrification temperature.
• the temperature and viscosity at the time of melting can be set within a range suitable for producing a glass composition. Moreover, high acid resistance of the glass can be ensured.
• the lower limit of (MgO+CaO) may be 6% by mass or more, 8% by mass or more, 9% by mass or more, 10% by mass or more, 11% by mass or more, 12% by mass or more, and even 13% by mass or more.
• the upper limit of (MgO+CaO) may be 26% by mass or less, 23% by mass or less, 22% by mass or less, 21% by mass or less, 20% by mass or less, 19% by mass or less, or even 18% by mass or less.
• composition A-4 may further contain SrO.
• the SrO content can have the same upper and lower limits as composition A-2.
• Composition A-4 may be substantially free of SrO.
• Composition A-4 may further contain BaO.
• the BaO content may have the same upper and lower limits as composition A-1.
• Composition A-4 may be substantially free of BaO.
• composition A-4 may further contain ZnO.
• the ZnO content can have the same upper and lower limits as composition A-1.
• Composition A-4 may be substantially free of ZnO.
• the total content of alkali metal oxides (Li 2 O, Na 2 O, K 2 O) is 9% by mass or more and 20% by mass or less.
• the lower limit of (Li 2 O+Na 2 O+K 2 O) may be 9.5% by mass or more, or may be 10% by mass or more.
• the upper limit of (Li 2 O + Na 2 O + K 2 O) can be 18% by mass or less, 16% by mass or less, less than 15% by mass, 14% by mass or less, 13% by mass or less, 12.5% by mass or less, 12% by mass % or less.
• Each of Li 2 O and K 2 O is an optional component. In other words, the lower limit of the content of these components may be 0 as long as the total content of alkali metal oxides is 9% by mass or more.
• Li 2 O makes a particularly high contribution to the effect based on the alkali metal oxide described above.
• the inclusion of Li 2 O can lower the working temperature of the glass substrate when forming the glass composition, and when the working temperature is lowered, the glass composition becomes easier to form, and its productivity improves.
• excessive inclusion of Li 2 O lowers the glass transition temperature and reduces the heat resistance of the glass.
• the lower limit of the content of Li 2 O in composition A-4 may be 0% by mass or more, 0.1% by mass or more, 0.5% by mass or more, or even 1% by mass or more.
• the upper limit of the content of Li 2 O may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or even less than 2% by mass.
• the content of Na 2 O is 6% by mass or more and 20% by mass or less. When the content of Na 2 O is within these ranges, the effect based on the alkali metal oxide described above becomes more reliable.
• the lower limit of the content of Na 2 O may be 7% by mass or more, and further may be 8% by mass or more.
• the upper limit of the content of Na 2 O may be 17% by mass or less, 16% by mass or less, 15% by mass or less, 14% by mass or less, 13% by mass or less, or even 12% by mass or less.
• the lower limit of the content of K 2 O may be 0.1% by mass or more, and more preferably 0.5% by mass or more.
• the upper limit of the content of K 2 O may be 5% by mass or less, 3% by mass or less, 2% by mass or less, less than 2% by mass, or even 1% by mass or less.
• Composition A-4 may further contain TiO 2 .
• the content of TiO 2 can have the same upper and lower limits as in composition A-1.
• Composition A-4 may be substantially free of TiO 2 .
• composition A-4 may further contain ZrO 2 .
• the content of ZrO 2 can have the same upper and lower limits as composition A-1.
• Composition A-4 may be substantially free of ZrO 2 .
• composition A-4 may further contain each of the above components.
• the preferred contents and other details of each of these components are the same as those for composition A-1, so their description will be omitted.
• Glass composition B In addition, another example of the glass composition (hereinafter referred to as glass composition B) is expressed in mass%, 50 ⁇ SiO 2 ⁇ 75, 0 ⁇ B 2 O 3 ⁇ 2, 0.1 ⁇ (MgO+CaO) ⁇ 20, 9 ⁇ ( Li2O + Na2O + K2O ) ⁇ 20, 5 ⁇ ZrO 2 ⁇ 20, Contains the following ingredients.
• Glass composition B does not need to contain substantially any components other than the above-mentioned components. Moreover, the glass composition B can be a glass fiber with high chemical durability.
• SiO2 is a component that forms the skeleton of glass and is the main component of composition B. Further, SiO 2 is a component that adjusts the devitrification temperature and viscosity during glass formation. A component that improves water resistance and acid resistance.
• the content of SiO 2 is 50% by mass or more and 75% by mass or less, but the lower limit of the content of SiO 2 can be 52% by mass or more, 54% by mass or more, 56% by mass or more, 58% by mass or more. , 60% by mass or more, 62% by mass or more, 63% by mass or more, 64% by mass or more, more than 65% by mass, or even more than 66% by mass.
• the upper limit of the content of SiO 2 may be 74% by mass or less, 73% by mass or less, 71% by mass or less, or even 70% by mass or less.
• Composition B may further contain B 2 O 3 .
• B 2 O 3 is a component that forms the skeleton of glass.
• B 2 O 3 is also a component that adjusts the devitrification temperature and viscosity during glass formation.
• excessive content of B 2 O 3 lowers the acid resistance of the glass.
• the upper limit of the content of B 2 O 3 may be less than 2% by mass, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and even less than 0.1% by mass.
• Composition B may be substantially free of B 2 O 3 .
• Composition B may further contain Al 2 O 3 .
• Al 2 O 3 is a component that forms the skeleton of glass.
• Al 2 O 3 is a component that adjusts the devitrification temperature and viscosity during glass formation, and is a component that improves the water resistance of the glass.
• excessive content of Al 2 O 3 lowers the acid resistance of the glass.
• the upper limit of the content of Al 2 O 3 may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or even 1.5% by mass or less.
• composition B when ease of forming the glass and acid resistance are important, the sum of the contents of B 2 O 3 and Al 2 O 3 (B 2 O 3 +Al 2 O 3 ) may be important.
• composition B (B 2 O 3 +Al 2 O 3 ) may be 5% by mass or less.
• an increase in the devitrification temperature of the glass, which would make it difficult to manufacture the glass, is suppressed, and the acid resistance of the glass is increased.
• the melting point of the glass does not become excessively high, and the uniformity of melting the raw materials increases.
• the upper limit of (B 2 O 3 +Al 2 O 3 ) may be 4% by mass or less, 3% by mass or less, 2% by mass or less, or even 1.5% by mass or less.
• Composition B may further contain MgO.
• MgO is a component that adjusts the devitrification temperature and viscosity during glass formation.
• MgO is also a component that adjusts the acid resistance and water resistance of the glass composition.
• the lower limit of the MgO content may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, or even more than 2% by mass.
• the upper limit of the content of MgO may be 15% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, or even 5% by mass or less.
• Composition B may further contain CaO.
• CaO is a component that adjusts the devitrification temperature and viscosity during glass formation.
• CaO is also a component that adjusts the acid resistance and water resistance of the glass composition.
• the lower limit of the CaO content may be 0.1% by mass or more, 1% by mass or more, 2% by mass or more, or even more than 3% by mass.
• the upper limit of the CaO content may be 15% by mass or less, 12% by mass or less, 10% by mass or less, or even 8% by mass or less.
• composition B when the value of the sum of the contents of MgO and CaO (MgO+CaO) is 0.1% by mass or more and 20% by mass or less, the devitrification temperature and viscosity of the molten glass can be controlled while suppressing an excessive increase in the devitrification temperature. , the range suitable for glass production. Further, within this range, it is also possible to improve the chemical durability of the glass.
• the lower limit of (MgO+CaO) may be 2% by mass or more, 4% by mass or more, 6% by mass or more, 8% by mass or more, or even 9% by mass or more.
• the upper limit of (MgO+CaO) may be 20% by mass or less, 18% by mass or less, 16% by mass or less, less than 14% by mass, or even 13% by mass or less.
• each of MgO and CaO is an optional component.
• the lower limit of the content of these components may be 0 as long as the total content is 0.1% by mass or more.
• Composition B may further contain SrO.
• SrO is a component that adjusts the devitrification temperature and viscosity during glass formation.
• excessive SrO content reduces the acid resistance of the glass.
• the upper limit of the SrO content can be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and even 0.1% by mass or less. % by mass or less.
• Composition B may be substantially free of SrO.
• Composition B may further contain BaO.
• BaO is a component that adjusts the devitrification temperature and viscosity during glass formation.
• excessive BaO content reduces the acid resistance of the glass.
• the upper limit of the BaO content may be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and even 0.1% by mass or less. % by mass or less.
• Composition B may be substantially free of BaO.
• ZnO Composition B may further contain ZnO.
• ZnO is a component that adjusts the devitrification temperature and viscosity during glass formation.
• ZnO is easily volatilized and may scatter during melting, excessive ZnO content causes significant fluctuations in the glass component ratio due to volatilization, making it difficult to manage the glass composition.
• ZnO is a relatively expensive raw material, if it is contained in a large amount, the raw material cost will increase.
• the upper limit of the content of ZnO may be 10% by mass or less, 5% by mass or less, less than 3% by mass, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, Furthermore, it may be 0.1% by mass or less.
• Alkali metal oxides (Li 2 O, Na 2 O, K 2 O) are components in composition B that adjust the devitrification temperature and viscosity during glass formation. Further, the alkali metal oxides (Li 2 O, Na 2 O, K 2 O) are also components that adjust the acid resistance and water resistance of the glass.
• the lower limit of the content of Li 2 O may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, or 1.5% by mass or more.
• the upper limit of the content of Li 2 O may be 5% by mass or less, 4% by mass or less, 3.5% by mass or less, or even 3% by mass or less.
• the lower limit of the content of Na 2 O may be 0.1% by mass or more, 1% by mass or more, or 3% by mass or more.
• the content of Na 2 O may be 6% by mass or more and 20% by mass or less.
• the devitrification temperature and viscosity of the molten glass can be controlled to be within a range suitable for glass production while suppressing an excessive increase in the devitrification temperature. Further, while suppressing the increase in the melting point of the glass and achieving more uniform melting of the glass raw materials, high heat resistance of the glass can be ensured without excessively lowering the glass transition temperature. Furthermore, within this range, it is also possible to improve the chemical durability of the glass.
• the lower limit of Na 2 O may be 7% by mass or more, 7.5% by mass or more, or even 8% by mass or more.
• the upper limit of Na 2 O may be 18% by weight or less, 16% by weight or less, 15% by weight or less, 14% by weight or less, less than 13% by weight, or even less than 12% by weight.
• the lower limit of the content of K 2 O may be 0.1% by mass or more, and may be greater than 0.5% by mass.
• the upper limit of the content of K 2 O may be 10% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, and even 2% by mass or less.
• composition B when the total content of alkali metal oxides (Li 2 O + Na 2 O + K 2 O) is 9% by mass or more and 20% by mass or less, the devitrification temperature is suppressed and the molten glass is not devitrified excessively.
• the transmission temperature and viscosity can be set in a range suitable for glass production. Further, while suppressing the increase in the melting point of the glass and achieving more uniform melting of the glass raw materials, high heat resistance of the glass can be ensured without excessively lowering the glass transition temperature. Furthermore, within this range, it is also possible to improve the chemical durability of the glass.
• the lower limit of (Li 2 O+Na 2 O+K 2 O) may be 9.5% by mass or more, or may be 10% by mass or more.
• the upper limit of (Li 2 O + Na 2 O + K 2 O) may be 18% by mass or less, 16% by mass or less, 15% by mass or less, 14% by mass or less, 13% by mass or less, or even 12% by mass or less.
• Each of Li 2 O, Na 2 O and K 2 O is an optional component.
• the lower limit of the content of each of these components may be 0 as long as the total content of alkali metal oxides is 9% by mass or more.
• composition B may further contain TiO2 .
• TiO 2 is a component that improves the meltability and chemical durability of glass. However, since TiO 2 is a relatively expensive raw material, if it is contained in a large amount, the raw material cost will increase.
• the upper limit of the content of TiO 2 may be 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.3% by mass or less, and even 0.2% by mass or less. It's possible.
• Composition B may be substantially free of TiO2 .
• ZrO2 is a component that adjusts the devitrification temperature and viscosity during glass formation.
• ZrO 2 is also a component that adjusts the acid resistance and water resistance of the glass composition.
• the content of ZrO 2 in composition B is 5% by mass or more and 20% by mass or less, an increase in the devitrification temperature of the glass, which would make it difficult to manufacture the glass, is suppressed, and the water resistance and acid resistance of the glass are increased.
• ZrO 2 is a relatively expensive raw material, if it is contained in a large amount, the raw material cost will increase.
• the lower limit of the content of ZrO 2 is greater than 5% by mass, and may be 5.5% by mass or more, 6% by mass or more, 6.5% by mass or more, or even 7% by mass or more.
• the upper limit of the content of ZrO 2 can be 18% by mass or less, 15% by mass or less, 12% by mass or less, less than 10% by mass, 9.5% by mass or less, 9% by mass or less, 8.5% by mass or less , or even 8% by mass or less.
• Fe Iron (Fe) contained in the glass composition usually exists in the form of Fe 2+ or Fe 3+ .
• Fe 3+ is a component that enhances the ultraviolet absorption properties of the glass composition
• Fe 2+ is a component that enhances the heat ray absorption properties of the glass composition. Even if Fe is not intentionally included, it may be unavoidably mixed in with industrial raw materials. If the content of Fe is small, coloring of the glass composition can be prevented.
• the upper limit of the content of Fe expressed by T-Fe 2 O 3 may be 5% by mass or less, 2% by mass or less, less than 1% by mass, 0.5% by mass or less, 0.4% by mass or less, 0.3 mass% or less, 0.2 mass% or less, further 0.1 mass% or less, less than 0.1 mass%, 0.08 mass% or less, 0.05 mass% or less, 0.04 mass% or less , and even 0.03% by mass or less.
• the lower limit of the content of Fe expressed by T-Fe 2 O 3 may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, and further 0.2% by mass or more. Particularly in glass compositions with a low content of alkali metal oxides, trace amounts of iron oxide can contribute to promoting glass fining.
• Composition B may further contain fluorine (F 2 ) and chlorine (Cl 2 ). Since F 2 easily volatizes, there is a possibility of it scattering during melting, and there is also the problem that it is difficult to control the content in the glass.
• the upper limit of the content of F2 can be 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.2% by mass or less, and even 0.1% by mass or less. It's possible.
• F 2 may be substantially absent.
• Cl 2 Since Cl 2 easily volatizes, there is a possibility of it scattering during melting, and there is also the problem that it is difficult to control the content in the glass.
• the upper limit of the content of Cl 2 may be 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.2% by mass or less, and even 0.1% by mass or less. It's possible. Cl 2 may be substantially free.
• Glass composition A and glass composition B may further contain the following components as long as the effects of the present invention can be obtained.
• Glass composition A and glass composition B include P 2 O 5 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , CeO 2 , Pr 2 O 3 , Nd 2 O 3 , Pm 2 O as other components.
• the total allowable content of these components may be 5% by weight or less, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, or even less than 0.1% by weight. .
• the other components mentioned above may not be substantially contained.
• oxides of litanoid La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
• La europoride
• Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy Ho, Er, Tm, Yb, Lu
• Glass composition A and glass composition B each contain at least one kind selected from SO 3 , Br 2 , I 2 , SnO 2 , As 2 O 3 and Sb 2 O 3 as an additive in an amount of 0% by mass or more and 1% by mass. It can be contained in a content of % by mass or less.
• the permissible content of these components can be less than 0.5% by weight, less than 0.2% by weight, or even less than 0.1% by weight for each.
• the total allowable content of these components may be 1% by weight or less, less than 0.5% by weight, less than 0.2% by weight, or even less than 0.1% by weight.
• the other components mentioned above may not be substantially contained.
• Glass composition A and glass composition B each contain H 2 O, OH, H 2 , CO 2 , CO, He, Ne, Ar, and N 2 at a content of 0% by mass or more and 0.1% by mass or less. sell.
• the permissible content of these components can be less than 0.05% by weight, less than 0.03% by weight, or even less than 0.01% by weight for each.
• the total allowable content of these components can be 0.1% by weight or less, less than 0.05% by weight, less than 0.03% by weight, and even less than 0.01% by weight.
• the other components mentioned above may not be substantially contained.
• Glass composition A and glass composition B may contain trace amounts of noble metal elements.
• noble metal elements such as Pt, Rh, Au, and Os can be included at a content of 0% by mass or more and 0.1% by mass or less, respectively.
• the permissible content of these components may be less than 0.1% by weight each, less than 0.05% by weight, less than 0.03% by weight, or even less than 0.01% by weight.
• the total allowable content of these components can be 0.1% by weight or less, less than 0.05% by weight, less than 0.03% by weight, and even less than 0.01% by weight.
• the other components mentioned above may not be substantially contained.
• Glass composition A and glass composition B may be compositions that do not substantially contain CuO. Moreover, the glass composition A and the glass composition B may be compositions that do not substantially contain CoO. Furthermore, glass composition A and glass composition B may be compositions that do not substantially contain PbO. Moreover, the glass composition A and the glass composition B may be compositions that do not substantially contain NiO.
• the characteristics that the glass composition of this embodiment can have will be explained below.
• the temperature at which the viscosity of the molten glass becomes 1000 dPa ⁇ sec (1000 poise) is called the working temperature of the glass, and is the most suitable temperature for forming the glass.
• the working temperature is 1100° C. or higher, variations in glass fiber diameter can be reduced. If the working temperature is 1300° C. or lower, the fuel cost for melting glass can be reduced, the glass manufacturing equipment will be less susceptible to corrosion due to heat, and the life of the equipment will be extended.
• the lower limit of the working temperature may be 1100°C or higher, 1120°C or higher, 1140°C or higher, 1150°C or higher, 1160°C or higher, 1170°C or higher, 1180°C or higher, or even 1200°C or higher.
• the upper limit of the working temperature may be 1300°C or less, 1280°C or less, 1270°C or less, 1260°C or less, or even 1250°C or less.
• ⁇ T may be 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 40°C or higher, or even 50°C or higher.
• ⁇ T may be 200° C. or less, the glass composition can be easily adjusted.
• ⁇ T may be 200°C or less, 180°C or less, or even 160°C or less.
• glass fibers are produced by pulling out a molten glass base through a nozzle of a bushing provided at the bottom of a kiln tank, continuously winding it up with a winder, and spinning it into a fiber.
• the glass composition must have excellent meltability and good formability, appropriate temperature-viscosity characteristics, and a devitrification temperature lower than the working temperature. is required.
• the devitrification temperature is the temperature at which crystals are generated in the molten glass base and begin to grow.
• Acid resistance, electrolyte resistance, and water resistance are suitable as indicators of chemical durability for use in power storage devices such as secondary batteries. Acid resistance and water resistance are appropriate indicators of chemical durability in filter media applications.
• the mass reduction rate ⁇ W 1 described later is employed, and the smaller this ⁇ W 1 is, the higher the acid resistance is.
• ⁇ W 1 is preferably 5.0% by mass or less.
• ⁇ W 1 of the glass composition of the present embodiment may be 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 2.0% by mass or less, 1.5% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0
• the content may be .5% by weight or less, 0.4% by weight or less, 0.3% by weight or less, or 0.2% by weight or less.
• the ⁇ W 1 that can be achieved by this embodiment is, for example, 0.01 to 5.0% by mass.
• ⁇ W 2 As an index of electrolytic solution resistance, the mass reduction rate ⁇ W 2 described later is employed, and the smaller this ⁇ W 2 is, the higher the electrolytic solution resistance is.
• ⁇ W 2 is preferably 0.12% by mass or less.
• ⁇ W 2 of the glass composition of the present embodiment may be 0.12% by mass or less, 0.11% by mass or less, 0.10% by mass or less, 0.09% by mass or less, 0.08% by mass or less, Most preferably, it is 0.07% by mass or less.
• ⁇ W 3 As an index of water resistance, the mass reduction rate ⁇ W 3 described later is employed, and the smaller the mass reduction rate ⁇ W 3 is, the higher the water resistance is.
• ⁇ W 3 is preferably less than 0.50% by mass.
• ⁇ W 3 of the glass composition of the present embodiment may be less than 0.50 mass%, 0.45 mass% or less, 0.40 mass% or less, 0.35 mass% or less, 0.30 mass% or less, It may be 0.25% by mass or less, and 0.20% by mass or less.
• the ⁇ W 3 that can be realized by this embodiment is, for example, 0.01% by mass or more and less than 0.50% by mass.
• the glass fiber of this embodiment is made of the glass composition described above.
• the glass fibers of this embodiment may be long glass fibers or short glass fibers.
• Long glass fibers are produced by flowing a viscosity-controlled glass melt through a nozzle and winding it up with a winder. This continuous fiber is cut to an appropriate length at the time of use.
• Short glass fibers are manufactured by blowing away glass melt using high-pressure air, centrifugal force, or the like. Short glass fibers are sometimes called glass wool because they have a cotton-like morphology.
• the average fiber diameter of the glass fibers is, for example, 0.1 to 50 ⁇ m.
• the average fiber diameter of the glass fibers may be 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.3 ⁇ m or more, 0.4 ⁇ m or more, and even 0.5 ⁇ m or more, 50 ⁇ m or less, 40 ⁇ m or less, It may be 30 ⁇ m or less, or 25 ⁇ m or less.
• the average fiber diameter may be 1 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 4 ⁇ m or more, or even 5 ⁇ m or more.
• the average fiber diameter may be 10 ⁇ m or less, 5 ⁇ m or less, 4 ⁇ m or less, 3 ⁇ m or less, 2 ⁇ m or less, or even 1 ⁇ m or less.
• the member for an electricity storage device of this embodiment includes the glass fiber described above.
• the electricity storage device member is, for example, a separator or a clad tube. These members can be manufactured using known manufacturing methods.
• the separator is, for example, a sheet formed by wet-forming glass fiber.
• the clad tube can be obtained, for example, by knitting glass fibers into a tube shape, then baking and hardening the tube, and filling the inside with an active material.
• the active material is, for example, lead powder.
• the filter medium of this embodiment includes the glass fibers described above.
• the filter material is, for example, a bag filter. These members can be manufactured using known manufacturing methods.
• the bag filter is, for example, a woven or non-woven glass fiber fabric.
• Example and comparative example Ordinary glass raw materials such as silica sand were prepared so as to have the composition shown in Table 1, and batches of glass raw materials were prepared for each of Examples and Comparative Examples. Using an electric furnace, each batch was heated to 1500-1600° C. to melt it and maintained there for about 4 hours until the composition became uniform. Thereafter, a part of the molten glass (glass melt) was poured out onto an iron plate and slowly cooled to room temperature in an electric furnace to obtain a bulk glass composition (plate-like material, glass sample).
• glass melt glass melt
• the platinum ball pulling method refers to the relationship between the load (resistance) applied when a platinum ball is immersed in molten glass and pulled up with uniform motion, and the gravity and buoyancy force acting on the platinum ball. This is a method of measuring viscosity by applying Stokes' law, which describes the relationship between viscosity and falling speed when minute particles settle in a fluid.
• devitrification temperature A glass composition pulverized to a particle size of 1.0 to 2.8 mm was placed in a platinum boat, held in an electric furnace with a temperature gradient (800 to 1400°C) for 2 hours, and placed at the position where crystals appeared.
• the devitrification temperature was determined from the maximum temperature of the corresponding electric furnace. When the glass became cloudy and crystals could not be observed, the maximum temperature of the electric furnace corresponding to the position where the cloudiness appeared was taken as the devitrification temperature.
• the particle size is a value measured by a sieving method.
• the temperature difference ⁇ T is the temperature difference obtained by subtracting the devitrification temperature from the working temperature.
• Glass single fibers were produced using the obtained glass composition (bulk). That is, the glass composition (bulk) was remelted in an electric furnace and then molded into pellets while being cooled. Using this pellet, a single glass fiber having a diameter of 15 ⁇ m was produced.
• - Acid resistance Cut a single glass fiber with a diameter of 15 ⁇ m into a length of 20 mm, weigh out the same number of grams as the specific gravity of the glass, and immerse this glass fiber in 100 mL of a 10 mass % sulfuric acid aqueous solution at 80°C for 24 hours. Loss in mass The mass reduction rate was determined as ⁇ W 1 .
• a single glass fiber with a diameter of 15 ⁇ m was cut into a length of 20 mm, weighed out in grams equal to the specific gravity of the glass, and the glass fiber was immersed in 100 mL of a 10% by mass sulfuric acid aqueous solution at 80° C. for 24 hours.
• the mass of the alkali metal oxides (Li 2 O, Na 2 O, K 2 O) eluted into the sulfuric acid aqueous solution at this time was determined, and the ratio of the eluted alkali metal oxides (Li 2 O, Na 2 O) to the mass of the glass fiber was determined.
• the ratio of the sum of the masses of O, K 2 O) was defined as ⁇ W 2 .
• the glass composition of Comparative Example 1 has a conventional sheet glass composition.
• the sheet glass composition has somewhat poor water resistance.
• the glass composition of Comparative Example 2 has a C glass composition.
• C glass is slightly inferior in electrolyte resistance.
• C glass has a high B 2 O 3 content, and there is concern that it may affect manufacturing equipment.

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• 2023
  • 2023-03-30 JP JP2024512853A patent/JPWO2023190983A1/ja active Pending
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