WO2024034546A1 - ガラス組成物、ガラス繊維、ガラスフィラー、ガラス繊維の製造方法、及びガラスフィラーの製造方法 - Google Patents

ガラス組成物、ガラス繊維、ガラスフィラー、ガラス繊維の製造方法、及びガラスフィラーの製造方法 Download PDF

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WO2024034546A1
WO2024034546A1 PCT/JP2023/028654 JP2023028654W WO2024034546A1 WO 2024034546 A1 WO2024034546 A1 WO 2024034546A1 JP 2023028654 W JP2023028654 W JP 2023028654W WO 2024034546 A1 WO2024034546 A1 WO 2024034546A1
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Prior art keywords
mass
glass
less
glass composition
content
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PCT/JP2023/028654
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English (en)
French (fr)
Japanese (ja)
Inventor
浩輔 藤原
文 中村
英俊 福地
裕 深澤
芳弘 澤
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Nippon Sheet Glass Co Ltd
Nippon Fiber Corp KK
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Nippon Sheet Glass Co Ltd
Nippon Fiber Corp KK
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Application filed by Nippon Sheet Glass Co Ltd, Nippon Fiber Corp KK filed Critical Nippon Sheet Glass Co Ltd
Priority to EP23852508.3A priority Critical patent/EP4570768A1/en
Priority to JP2024540449A priority patent/JPWO2024034546A1/ja
Priority to US19/102,281 priority patent/US20260042699A1/en
Priority to CN202380057951.XA priority patent/CN119585219A/zh
Publication of WO2024034546A1 publication Critical patent/WO2024034546A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • 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
    • C03C12/00—Powdered glass; Bead 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
    • 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
    • C03C13/00—Fibre or filament compositions
    • C03C13/001—Alkali-resistant fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C03C2203/00—Production processes
    • C03C2203/10—Melting processes

Definitions

  • the present invention relates to a glass composition, a glass fiber, a glass filler, a method for producing glass fiber, and a method for producing a glass filler.
  • Glass whose main raw material is silica (SiO 2 ) has been used for bottles and window glasses for a long time.
  • silica SiO 2
  • glass is now widely used in the form of glass fibers and glass flakes, as well as sheet glass, and as a filler for resins and concrete.
  • composition of glass greatly affects the physical properties and chemical resistance of plate glass, glass fibers and glass flakes processed from glass.
  • E-glass which has the content of alkaline components (Na 2 O, K 2 O) as low as possible, has excellent electrical insulation properties, but has the disadvantage of poor acid resistance.
  • C glass has been devised which has improved acid resistance compared to E glass by increasing the content of Na 2 O, but C glass has inferior alkali resistance.
  • alkali-resistant glass (AR glass) characterized by containing ZrO 2 as a subcomponent has been developed.
  • AR glass has acid resistance equal to or higher than C glass, and at the same time exhibits excellent alkali resistance, so it is suitable as a reinforcing material for concrete.
  • the constituent component ZrO 2 of AR glass is more expensive than other glass raw materials, it is difficult to use it for general purposes.
  • the above E glass, C glass, and AR glass all have low elastic modulus, so there is room for improvement.
  • E glass, C glass, and AR glass all contain no iron oxide or have a content of less than 1% by mass.
  • Patent Document 1 discloses a composition containing SiO 2 , Al 2 O 3 , MgO, Fe 2 O 3 , TiO 2 , CaO, etc. as a high elastic composition for glass fiber.
  • an object of the present invention is to provide a glass composition having a high elastic modulus and improved moldability and alkali resistance.
  • the present inventors found that among the components contained in the glass composition, the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 , and the content of Al 2 By appropriately adjusting the mass ratio calculated by O 3 / (SiO 2 + Al 2 O 3 ) and MgO / (MgO + CaO), a glass composition with high elastic modulus and improved formability and alkali resistance can be obtained.
  • the present invention was completed based on the discovery that the present invention is possible.
  • the present inventors also discovered that the above glass composition can be obtained efficiently at low cost by using coal ash (fly ash) as a raw material.
  • the present invention The content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less,
  • a glass composition having a mass ratio calculated by MgO/(MgO+CaO) of 0.005 or more and 0.20 or less.
  • a glass filler composed of the above glass composition is provided.
  • the present invention Melting the above glass composition; spinning the molten glass composition to form glass fibers;
  • a method for manufacturing glass fiber including:
  • the present invention Melting the above glass composition; forming the molten glass composition into a glass filler; Provided is a method for producing a glass filler.
  • the present invention it is possible to provide a glass composition that has a high elastic modulus and improved moldability and alkali resistance.
  • FIG. 2 is a perspective view schematically showing an example of scaly glass.
  • FIG. 1B is a plan view of the scaly glass shown in FIG. 1A viewed from above.
  • FIG. 1 is a schematic diagram for explaining an example of an apparatus and method for producing scaly glass. It is a schematic diagram for demonstrating another example of the apparatus and method of manufacturing scaly glass.
  • FIG. 2 is a schematic diagram for explaining an example of a spinning device that can be used to manufacture chopped strands.
  • FIG. 5 is a schematic diagram for explaining an example of an apparatus for manufacturing chopped strands from a strand wound body obtained by the spinning apparatus shown in FIG. 4.
  • FIG. It is a perspective view showing an example of a concrete product.
  • FIG. 6B is an enlarged cross-sectional view of the concrete product shown in FIG. 6A. It is a figure which shows another example of a concrete product. It is a figure which shows an example of the structure of the rubber belt containing the cord for rubber reinforcement.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 is as follows: 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • iron oxide usually exists as Fe 2 O 3 or FeO in the glass composition. Therefore, iron oxide present as FeO is converted to Fe 2 O 3 , and the total content of iron oxide present as Fe 2 O 3 is taken as the content of total iron oxide in the glass composition. Accordingly, it is written as T-Fe 2 O 3 .
  • SiO 2 and Al 2 O 3 are main components forming the skeleton of the glass composition.
  • CaO is a component that suppresses the melt viscosity of the glass composition and also increases the elasticity of the glass composition.
  • Fe 2 O 3 is a component that increases the elasticity of the glass composition.
  • MgO is a component that improves the acid resistance of the glass composition.
  • substantially not contained means that the content is less than 0.1% by mass, preferably less than 0.05% by mass, more preferably less than 0.01% by mass, even more preferably It means less than 0.005% by weight, particularly preferably less than 0.003% by weight and most preferably less than 0.001% by weight.
  • the content, characteristics, and other preferable ranges of each component can be determined by arbitrarily combining the upper and lower limits described individually below.
  • the component ratio in the above mixture can be regarded as the component ratio of the materials of the glass composition.
  • the glass composition of the present invention has a content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 , and a content of Al 2 O 3 /(SiO 2 +Al 2 O 3 ) and MgO. It is obtained by preparing a mixture by adjusting the blending ratio of raw materials so that the mass ratio of /(MgO+CaO) falls within the above range, and then crushing, melting, and solidifying the mixture.
  • SiO2 SiO 2 is a component that forms the skeleton of the glass composition. Further, SiO 2 is a component that adjusts the devitrification temperature and viscosity during the formation of the glass composition, and is also a component that improves the acid resistance of the glass composition.
  • the lower limit of the content of SiO 2 in the glass composition is, for example, 40% by mass or more, more than 40% by mass, 42% by mass or more, 45% by mass or more, 46% by mass or more, 47% by mass or more, 48% by mass or more, More than 50% by mass, 51% by mass or more, 52% by mass or more, and 53% by mass or more are preferable.
  • the upper limit of the content of SiO 2 is, for example, 66% by mass or less, 64% by mass or less, 62% by mass or less, 60% by mass or less, 59% by mass or less, 58% by mass or less, 57% by mass or less, 56% by mass. The following are preferred.
  • the content of SiO 2 is, for example, 40% by mass ⁇ SiO 2 ⁇ 66% by mass.
  • Al2O3 Al 2 O 3 is a component that forms the skeleton of the glass composition. Furthermore, Al 2 O 3 is a component that adjusts the devitrification temperature and viscosity during the formation of the glass composition, and is also a component that improves the water resistance of the glass composition. On the other hand, if the glass composition contains too much Al 2 O 3 , acid resistance and alkali resistance may decrease and devitrification may occur.
  • the lower limit of the content of Al 2 O 3 is, for example, 3% by mass or more, 4% by mass or more, 4.5% by mass or more, 5% by mass or more, 5.5% by mass or more, 6% by mass or more, 6.
  • Al 2 O 3 is preferably 5% by mass or more, 7% by mass or more, 7.5% by mass or more, 8% by mass or more, 8.5% by mass or more, and 9% by mass or more.
  • the upper limit of the content of Al 2 O 3 is, for example, 25% by mass or less, 20% by mass or less, 18% by mass or less, 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.
  • the content is preferably 12% by mass or less, 11.9% by mass or less.
  • the total content of SiO 2 and Al 2 O 3 is important because it affects the physical properties of the glass composition.
  • the devitrification temperature becomes high and it tends to be difficult to obtain a homogeneous glass.
  • the melting point of the raw material mixture becomes excessively high, it tends to be difficult to maintain a uniform composition of the melt in the melting furnace during mass production of glass compositions using a melting furnace.
  • (SiO 2 +Al 2 O 3 ) in the glass composition is 50% by mass or more and 70% by mass or less.
  • the lower limit of (SiO 2 +Al 2 O 3 ) is, for example, 52% by mass or more, preferably 53% by mass or more, 54% by mass or more, and 55% by mass or more.
  • the upper limit of (SiO 2 +Al 2 O 3 ) is, for example, 68% by mass or less, preferably 66% by mass or less, 65% by mass or less, and 64% by mass or less.
  • Al 2 O 3 /(SiO 2 +Al 2 O 3 ) In the glass composition of the present invention, Al 2 O 3 / (which is the ratio of the content of Al 2 O 3 (based on mass) to the total content of SiO 2 and Al 2 O 3 (SiO 2 +Al 2 O 3 ) SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less. When Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is less than 0.05 or more than 0.40, the acid resistance and alkali resistance of the glass composition tend to be poor.
  • Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is less than 0.05, phase separation tends to occur easily.
  • Al 2 O 3 /(SiO 2 +Al 2 O 3 ) exceeds 0.40, crystal phases tend to precipitate in the glass composition.
  • the lower limit of Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is, for example, 0.06 or more, preferably 0.07 or more, 0.08 or more, 0.09 or more, or 0.10 or more.
  • the lower limit of Al 2 O 3 /(SiO 2 +Al 2 O 3 ) may be 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, or 0.15 or more.
  • the upper limit of Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is, for example, 0.35 or less, preferably 0.30 or less, 0.25 or less, or 0.20 or less.
  • the upper limit of Al 2 O 3 /(SiO 2 +Al 2 O 3 ) may be 0.19 or less, 0.18 or less, 0.17 or less, or less than 0.16.
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) may be 0.05 or more and less than 0.16.
  • the content of CaO in the glass composition of the present invention is 5% by mass or more and 30% by mass or less.
  • the lower limit of the content of CaO is, for example, 10% by mass or more, 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, 16% by mass or more, 17% by mass or more, 18% by mass or more.
  • the upper limit of the CaO content is, for example, 28% by mass or less, preferably 26% by mass or less, 25% by mass or less, 24% by mass or less, and 23% by mass or less.
  • Fe2O3 In the glass composition of the present invention, Fe 2 O 3 plays an important role. That is, when Fe 2 O 3 is contained in a glass composition in an appropriate range, the acid resistance and alkali resistance of the glass composition are improved. Furthermore, Fe 2 O 3 improves the elastic modulus of the glass composition. On the other hand, if the glass composition contains too much Fe 2 O 3 , acid resistance and alkali resistance may decrease and devitrification may occur. Therefore, the content of T-Fe 2 O 3 (total iron oxide converted to Fe 2 O 3 ) in the glass composition is more than 10% by mass and less than 16% by mass. The lower limit of the content of T-Fe 2 O 3 in the glass composition is preferably 10.1% by mass or more.
  • the lower limit of the content of T-Fe 2 O 3 in the glass composition may be 10.5% by mass or more, 11% by mass or more, 11.5% by mass or more, or 12% by mass or more.
  • the upper limit of the content of T-Fe 2 O 3 is, for example, 15% by mass or less, preferably 14.5% by mass or less, 14% by mass or less, and 13.5% by mass or less.
  • the content of T-Fe 2 O 3 is, for example, 10.1% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass.
  • the glass composition of the present invention contains MgO. By containing an appropriate amount of MgO, the acid resistance of the glass composition is improved. However, if excessive MgO is contained, the glass composition tends to devitrify, and the alkali resistance of the glass composition tends to decrease.
  • the glass composition of the present invention tends to have a high elastic modulus by appropriately adjusting the content of Fe 2 O 3 and the content of MgO.
  • the lower limit of the MgO content is, for example, 0.1% by mass or more, preferably 0.2% by mass or more.
  • the upper limit of the content of MgO is, for example, 10% by mass or less, and preferably 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, and 2% by mass or less.
  • the content of MgO is, for example, 0.1% by mass ⁇ MgO ⁇ 10% by mass.
  • the total content of MgO and CaO affects the physical properties of the glass composition.
  • (MgO+CaO) in the glass composition is less than 5% by mass, the devitrification temperature tends to be high and it is difficult to obtain a homogeneous glass.
  • (MgO+CaO) exceeds 30% by mass the viscosity of the melt may be too low, resulting in poor moldability.
  • the lower limit of (MgO+CaO) is, for example, 5% by mass or more, 8% by mass or more, 10% by mass or more, 11% by mass or more, 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, It is preferably 16% by mass or more, 17% by mass or more, 18% by mass or more, 19% by mass or more, 20% by mass or more, 20.1% by mass or more, and 20.2% by mass or more.
  • the upper limit of (MgO+CaO) is, for example, 30% by mass or less, preferably 28% by mass or less, 27% by mass or less, 26% by mass or less, 25% by mass or less, and 24% by mass or less.
  • MgO/(MgO+CaO) MgO/(MgO+CaO)
  • MgO/(MgO+CaO) which is the ratio of the MgO content (based on mass) to the total content of MgO and CaO (MgO+CaO)
  • MgO/(MgO+CaO) exceeds 0.20, devitrification tends to occur and the alkali resistance of the glass composition tends to decrease.
  • MgO/(MgO+CaO) is less than 0.005, the effect of improving acid resistance by containing MgO tends to be insufficient.
  • the lower limit of MgO/(MgO+CaO) is, for example, 0.006 or more, 0.007 or more, 0.008 or more, 0.009 or more, 0.01 or more, 0.011 or more, 0.012 or more, 0.013 or more, It is preferably 0.014 or more, 0.015 or more, 0.016 or more, 0.017 or more, 0.018 or more, 0.019 or more, and 0.02 or more.
  • the upper limit of MgO/(MgO+CaO) is, for example, 0.18 or less, 0.16 or less, 0.15 or less, 0.14 or less, 0.13 or less, 0.12 or less, 0.11 or less, 0 .10 or less, 0.08 or less, 0.05 or less, and 0.03 or less are preferable.
  • the glass composition of the present invention may contain the following components.
  • (B 2 O 3 ) B2O3 can form the skeleton of the glass composition.
  • the glass composition of the present invention may contain B 2 O 3 .
  • the content of B 2 O 3 in the glass composition of the present invention is 0% by mass or more and 10% by mass or less.
  • the lower limit of the content of B 2 O 3 is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and preferably 1% by mass or more. Further, the upper limit of the content of B 2 O 3 is, for example, 8% by mass or less, preferably 7% by mass or less, 6% by mass or less, 5% by mass or less, and 4% by mass or less.
  • the content of B 2 O 3 may be 0.1% by mass ⁇ B 2 O 3 ⁇ 10% by mass. Note that B 2 O 3 does not need to be substantially contained.
  • the total content of SiO 2 and B 2 O 3 affects the physical properties of the glass composition.
  • the devitrification temperature becomes high and it may be difficult to obtain a homogeneous glass.
  • the melting point of the raw material mixture becomes excessively high, it may be difficult to maintain a uniform composition of the melt in the melting furnace during mass production of glass compositions using a melting furnace. Therefore, (SiO 2 +B 2 O 3 ) in the glass composition is preferably 50% by mass or more and 70% by mass or less.
  • the lower limit of (SiO 2 +B 2 O 3 ) is, for example, 52% by mass or more, preferably 53% by mass or more, 54% by mass or more, and 55% by mass or more.
  • the upper limit of (SiO 2 +B 2 O 3 ) is, for example, 68% by mass or less, 66% by mass or less, 65% by mass or less, 64% by mass or less, 63% by mass or less, 62% by mass or less, 61% by mass.
  • Alkali metal oxides lower the melting point of the glass composition and increase the fluidity of the melt. Therefore, in mass production of glass compositions using a melting furnace, the composition of the melt in the melting furnace can be kept uniform. Therefore, the glass composition of the present invention can also contain an appropriate amount of alkali metal oxides (Li 2 O, Na 2 O, K 2 O). However, if it is contained in an excessive amount, Young's modulus and alkali resistance may decrease and devitrification may occur.
  • the upper limit of the content of Li 2 O is, for example, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, less than 1% by mass, 0.9% by mass or less, 0.8% by mass.
  • the content is preferably 0.7% by mass or less, 0.6% by mass or less, and 0.5% by mass or less.
  • the lower limit of the Na 2 O content is, for example, 0.1% by mass or more, preferably 0.2% by mass or more.
  • the upper limit of the content of Na 2 O is, for example, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, less than 1% by mass, 0.9% by mass or less, 0.8% by mass.
  • the content is preferably 0.7% by mass or less, 0.6% by mass or less, and 0.5% by mass or less.
  • the lower limit of the content of K 2 O is, for example, 0.1% by mass or more, preferably 0.2% by mass or more.
  • the upper limit of the content of K 2 O is, for example, 5% by mass or less, 4% by mass or less, less than 3% by mass, 2% by mass or less, less than 1% by mass, 0.9% by mass or less, 0.8% by mass or less. , 0.7% by mass or less, preferably 0.6% by mass or less.
  • the lower limit of the total content of Na 2 O and K 2 O is, for example, 0.1% by mass or more, preferably 0.2% by mass or more.
  • the upper limit of (Na 2 O + K 2 O) is, for example, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, less than 1% by mass, 0.9% by mass or less, 0.8% by mass % or less is preferable.
  • the lower limit of the total content of alkali metal oxides is, for example, 0.1% by mass or more, preferably 0.2% by mass or more.
  • the upper limit of (Li 2 O + Na 2 O + K 2 O) is, for example, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, less than 1% by mass, 0.9% by mass or less, 0. It is preferably 8% by mass or less.
  • the content of Li 2 O, Na 2 O and K 2 O is, for example, 0.1% by mass ⁇ Li 2 O+Na 2 O+K 2 O ⁇ 5% by mass.
  • the glass composition of the present invention may contain SrO.
  • SrO is a component suitable for adjusting the temperature difference ⁇ T obtained by subtracting the devitrification temperature from the working temperature to a large value, which will be described later.
  • the glass composition contains too much SrO, the Young's modulus, acid resistance, and alkali resistance of the glass composition will decrease.
  • the upper limit of the SrO content in the glass composition is, for example, 15% by mass or less, 12% by mass or less, 10% by mass or less, 9% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less. % 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% by mass or less, and 0.1% by mass or less. SrO may not be substantially included. In some cases, the lower limit of the SrO content is, for example, 0.1% by mass or more, and may be 0.5% by mass or more, or 1% by mass or more.
  • the glass composition of the present invention may contain BaO.
  • BaO By including BaO in the glass composition, the devitrification temperature and viscosity during melting can be set within a range suitable for glass production.
  • the upper limit of the BaO content in the glass composition is, for example, 10% by mass or less, 8% by mass or less, 6% by mass or less, 4% by mass or less, 2% by mass or less, 1% by mass or less, 0. It is preferably 5% by mass or less, preferably 0.1% by mass or less. BaO may not be substantially included.
  • the glass composition of the present invention may contain ZnO.
  • ZnO By including ZnO in the glass composition, the devitrification temperature and viscosity during melting can be set within a range suitable for glass production.
  • the upper limit of the content of ZnO in the glass composition is, for example, 10% by mass or less, 8% by mass or less, 6% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less. % or less, preferably 0.5% by mass or less, and preferably 0.1% by mass or less.
  • ZnO may not be substantially included.
  • the glass composition of the present invention may also contain TiO2 .
  • TiO2 By including TiO 2 in the glass composition, the viscosity at the time of melting can be made into a range suitable for manufacturing glass.
  • the upper limit of the content of TiO 2 in the glass composition is, for example, 10% 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
  • the content is preferably .5% by mass or less.
  • the lower limit of the TiO 2 content is, for example, 0.1% by mass or more, and may be 0.2% by mass or more. TiO 2 may not be substantially included.
  • the content of TiO 2 may be 0.1% by mass ⁇ TiO 2 ⁇ 10% by mass.
  • the glass composition of the present invention may also contain ZrO2 .
  • ZrO2 By including ZrO 2 in the glass composition, the viscosity at the time of melting can be adjusted to a range suitable for glass production. On the other hand, if the glass composition contains too much ZrO 2 , devitrification tends to occur. Therefore, the upper limit of the content of ZrO 2 in the glass composition is, for example, 10% by mass or less, 9% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less.
  • ZrO 2 may not be substantially included.
  • the lower limit of the ZrO 2 content is, for example, 0.1% by mass or more, and may be 0.2% by mass or more.
  • the content of ZrO 2 may be 0.1% by mass ⁇ ZrO 2 ⁇ 10% by mass.
  • the glass composition of the present invention may also contain MnO2 .
  • MnO2 By including MnO 2 in the glass composition, the viscosity at the time of melting can be made into a range suitable for manufacturing glass.
  • the upper limit of the content of T-MnO 2 (total manganese oxide converted to MnO 2 ) in the glass composition is, for example, 5% by mass or less, 2% by mass or less, 1% by mass or less, and 0.5% by mass. % or less, preferably 0.1% by mass or less.
  • T—MnO 2 may not be substantially contained.
  • the glass composition of the present invention contains P 2 O 5 , PbO, Bi 2 O 3 , La 2 O 3 , WO 3 , Nb 2 O 5 , Y 2 O 3 , MoO 3 , Ta 2 O 5 as other components. , Cr 2 O 3 , CuO, and CoO at a content of 0% by mass or more and 5% by mass or less, respectively.
  • the permissible content of each of these components is, for example, less than 2% by weight, and may be less than 1% by weight, less than 0.5% by weight, and less than 0.1% by weight.
  • the total allowable content of these components is, for example, 5% by mass or less, and may be less than 2% by mass, less than 1% by mass, less than 0.5% by mass, or less than 0.1% by mass. However, the other components mentioned above may not be substantially contained.
  • the glass composition of the present invention contains at least one additive selected from the group consisting of SO 3 , F 2 , Cl 2 , Br 2 , I 2 , SnO 2 , CeO 2 , As 2 O 3 and Sb 2 O 3 .
  • Each seed may be contained at a content of 0% by mass or more and 1% by mass or less.
  • the permissible content of each of these components is, for example, less than 0.5% by weight, may be less than 0.2% by weight, and may be less than 0.1% by weight.
  • the total allowable content of these components is, for example, 1% by mass or less, and may be less than 0.5% by mass, less than 0.2% by mass, or less than 0.1% by mass.
  • each of the above additives may not be substantially contained.
  • the glass composition of the present invention contains at least one selected from the group consisting of H 2 O, OH, H 2 , CO 2 , CO, He, Ne, Ar, and N 2 in an amount of 0% by mass or more and 0.1% by mass or more, respectively.
  • the content may be less than % by mass.
  • the permissible content of each of these components is, for example, less than 0.05% by weight, may be less than 0.03% by weight, and may be less than 0.01% by weight.
  • the total allowable content of these components is, for example, 0.1% by mass or less, and may be less than 0.05% by mass, less than 0.03% by mass, or less than 0.01% by mass.
  • each of the above components may not be substantially contained.
  • the glass composition of the present invention may contain trace amounts of noble metal elements.
  • noble metal elements such as Pt, Rh, Au, and Os may be contained at a content of 0% by mass or more and 0.1% by mass or less, respectively.
  • the permissible content of each of these components is, for example, less than 0.1% by weight, and may be less than 0.05% by weight, less than 0.03% by weight, and less than 0.01% by weight.
  • the total allowable content of these components is, for example, 0.1% by mass or less, and may be less than 0.05% by mass, less than 0.03% by mass, or even less than 0.01% by mass.
  • each of the above noble metal elements may not be substantially contained.
  • a preferred example of the glass composition of the present invention is The content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 is 40% by mass ⁇ SiO 2 ⁇ 66% by mass, 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0.1% by mass ⁇ B 2 O 3 ⁇ 10% by mass, 5% by mass ⁇ CaO ⁇ 30% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , MgO, CaO and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 0.1% by mass ⁇ MgO ⁇ 10% by mass, 5% by mass ⁇ CaO ⁇ 30% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO, TiO 2 and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 0.1 mass% ⁇ SrO ⁇ 15 mass% 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO, TiO 2 and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 0.1% by mass ⁇ TiO 2 ⁇ 10% by mass 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO, ZrO 2 and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 0.1% by mass ⁇ ZrO 2 ⁇ 10% by mass 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO, Li 2 O, Na 2 O, K 2 O and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 0.1% by mass ⁇ Li 2 O + Na 2 O + K 2 O ⁇ 5% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 / (SiO 2 + Al 2 O 3 ) is 0.05 or more and less than 0.16
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 50% by mass ⁇ SiO 2 +B 2 O 3 ⁇ 70% by mass 5% by mass ⁇ CaO ⁇ 30% by mass, 10% by mass ⁇ T-Fe 2 O 3 ⁇ 16% by mass, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the content of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO and T-Fe 2 O 3 is 50% by mass ⁇ SiO 2 +Al 2 O 3 ⁇ 70% by mass, 0 mass% ⁇ B 2 O 3 ⁇ 10 mass%, 5% by mass ⁇ CaO ⁇ 30% by mass, 10.1 mass% ⁇ T-Fe 2 O 3 ⁇ 16 mass%, and
  • the mass ratio calculated by Al 2 O 3 /(SiO 2 +Al 2 O 3 ) is 0.05 or more and 0.40 or less
  • the mass ratio calculated by MgO/(MgO+CaO) is 0.005 or more and 0.20 or less.
  • the glass composition of the present invention When obtaining the glass composition of the present invention, there are no restrictions on the raw materials as long as they fall within the above-mentioned composition range. In particular, it is preferable to use coal ash as part of the raw material. In other words, the glass composition of the present invention preferably contains coal ash as a raw material. However, it is not necessary to use coal ash.
  • Young's modulus The higher the Young's modulus of a glass composition, the better the elasticity.
  • a glass composition with a high Young's modulus can improve the mechanical properties of a composite material reinforced with glass fibers or glass fillers.
  • Young's modulus (GPa) is determined by measuring the longitudinal wave velocity and shear wave velocity of an elastic wave propagating in glass using a normal ultrasonic method, and calculating these velocities and the density of the glass separately measured using the Archimedean method. It can be found from.
  • the lower limit of Young's modulus is, for example, 85 GPa or more, and may be 86 GPa or more, 87 GPa or more, 88 GPa or more, 89 GPa or more, or 90 GPa or more.
  • the upper limit of Young's modulus is, for example, 100 GPa or less, and may be 99 GPa or less, 98 GPa or less, 97 GPa or less, 96 GPa or less, 95 GPa or less, 94 GPa or less, or 93 GPa or less.
  • Glass transition temperature (glass transition point) is an index of the heat resistance of glass.
  • the lower limits of glass transition temperature are 560°C or higher, 580°C or higher, 600°C or higher, 610°C or higher, 620°C or higher, 630°C or higher, 640°C or higher, 650°C or higher, 660°C or higher, 670°C or higher, 680°C or higher. , and further may be 685°C or higher.
  • the upper limit of the glass transition temperature can be 800°C or less, 780°C or less, 760°C or less, 750°C or less, 740°C or less, 730°C or less, and further 720°C or less.
  • the temperature at which the viscosity of molten glass becomes 1000 dPa ⁇ sec (1000 poise) is called the working temperature of the glass, and is the most suitable temperature for molding glass fibers and glass fillers.
  • the working temperature of the glass is 1000° C. or higher, variations in the thickness of the glass flakes or the diameter of the glass fibers can be reduced. If the working temperature is 1450° 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 is, for example, 1000°C or higher, and may be 1050°C or higher, or 1100°C or higher.
  • the upper limit of the working temperature is, for example, 1450°C or less, 1400°C or less, 1350°C or less, 1300°C or less, 1250°C or less, 1240°C or less, 1230°C or less, 1220°C or less, 1210°C or less, 1200°C or less, 1190°C or less.
  • the temperature may be below °C.
  • the lower limit of ⁇ T of the glass composition is, for example, 0°C or higher, and may be 10°C or higher, 20°C or higher, or 30°C or higher.
  • the upper limit of ⁇ T of the glass composition is, for example, 200°C or less, and may be 150°C or less, or 100°C or less. In the glass composition of this embodiment, ⁇ T tends to be large by adjusting the T-Fe 2 O 3 content, MgO/(MgO+CaO), etc. to appropriate values.
  • the upper limit of the devitrification temperature of the glass composition is, for example, 1400°C or lower, and may be 1350°C or lower, 1300°C or lower, 1250°C or lower, or 1200°C or lower.
  • the lower limit of the devitrification temperature is, for example, 1000°C or higher, and may be 1050°C or higher, or 1100°C or higher.
  • ⁇ W 1 of the glass composition is 0.50% by mass or less.
  • ⁇ W 1 of the glass composition of the present invention is, for example, 0.40% by mass or less, 0.30% by mass or less, 0.20% by mass or less, 0.15% by mass or less, and further 0.10% by mass or less.
  • the lower limit of ⁇ W 1 is not particularly limited, and is, for example, 0.02% by mass or more.
  • ⁇ W 2 of the glass composition is 0.50% by mass or less.
  • ⁇ W 2 of the glass composition of the present invention is, for example, 0.40% by mass or less, 0.30% by mass or less, 0.20% by mass or less, 0.18% by mass or less, 0.15% by mass or less, 0 It is preferably at most .10% by mass, more preferably at most 0.05% by mass.
  • the lower limit of ⁇ W 2 is not particularly limited, and is, for example, 0.02% by mass or more.
  • 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. 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 method for manufacturing glass fiber of the present embodiment includes a step of melting the above-mentioned glass composition, and a step of spinning the molten glass composition to form glass fiber.
  • long glass fibers are produced by causing a glass melt whose viscosity is controlled to flow out of a nozzle and winding it up using a winding machine. 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.
  • the glass filler of this embodiment is composed of the glass composition described above.
  • the form of the glass filler is not particularly limited.
  • the glass filler may be, for example, at least one selected from glass flakes, chopped strands, milled fibers, glass powder, and glass beads. However, these forms are not strictly distinguishable from each other.
  • the glass filler of this embodiment may be a combination of two or more types of glass fillers having different forms.
  • the method for manufacturing a glass filler of this embodiment includes the steps of melting the above-mentioned glass composition and molding the molten glass composition into a glass filler. Below, each form of the glass filler will be explained.
  • a preferable example of the glass filler of this embodiment is scaly glass.
  • Scaly glass has a flake-like shape and is also called flake glass.
  • 1A and 1B show an example of scaly glass.
  • the average thickness t of the glass flakes 1 shown in FIG. 1A is, for example, 0.1 to 15 ⁇ m.
  • the average particle diameter is, for example, 0.2 to 15000 ⁇ m.
  • the aspect ratio of the glass flakes 1 is, for example, 2 to 1000. The aspect ratio can be determined by dividing the average particle diameter by the average thickness t.
  • the scaly glass 1 can be manufactured using the apparatus shown in FIG. 2, for example.
  • a glass base 11 melted in a refractory kiln tank 12 is inflated into a balloon shape by gas sent into a blow nozzle 15 to form a hollow glass membrane 16.
  • the hollow glass membrane 16 is crushed by the press roll 17 to obtain the glass flakes 1.
  • the glass flakes 1 can also be manufactured using the apparatus shown in FIG. 3, for example.
  • the molten glass base 11 poured into the rotating cup 22 from the nozzle 21 flows out radially from the upper edge of the cup 22 due to the centrifugal force generated by the rotation of the rotating cup 22.
  • the flowed-out material 11 is sucked by an air flow through annular plates 23 arranged above and below, and introduced into an annular cyclone collector 24 . While passing through the annular plate 23, the glass is cooled and solidified as a thin film, and is further crushed into minute pieces to obtain the scaly glass 1.
  • the chopped strand has a shape obtained by cutting glass fiber into short pieces.
  • the fiber diameter of the chopped strand is, for example, 1 to 50 ⁇ m, and the aspect ratio is, for example, 2 to 10,000.
  • the aspect ratio of the chopped strand can be determined by dividing the fiber length by the fiber diameter.
  • chopped strands can be manufactured using the apparatus shown in FIGS. 4 and 5.
  • a glass base having a predetermined composition melted in a refractory kiln tank is pulled out from a bushing 30 having a large number (for example, 2,400) nozzles at the bottom, and a large number of glass filaments 31 are drawn out.
  • a binder (sizing agent) 34 is applied by an application roller 33 of a binder applicator 32.
  • a large number of glass filaments 31 coated with a binder 34 are bundled by a reinforcing pad 35 into a strand 36 each consisting of, for example, about 800 glass filaments 31 .
  • Each strand 36 is wound around a cylindrical tube 39 fitted in a collet 38 while being traversed by a traverse finger 37 . Then, the cylindrical tube 39 around which the strand 36 is wound is removed from the collet 38 to obtain a cake (strand wound body) 40.
  • the cake 40 is housed in the creel 41, and the strands 36 are pulled out from the cake 40 and bundled into a strand bundle 43 by the collection guide 42. Water or a treatment liquid is sprayed onto this strand bundle 43 by a spraying device 44 . Further, the strand bundle 43 is cut by the rotary blade 46 of the cutting device 45 to obtain chopped strands 47.
  • Milled fiber has a shape obtained by cutting glass fiber into powder.
  • the fiber diameter of the milled fiber is, for example, 1 to 50 ⁇ m, and the aspect ratio thereof is, for example, 2 to 500.
  • the aspect ratio of milled fibers can be determined by dividing the fiber length by the fiber diameter. Milled fibers can be obtained by known methods.
  • Glass powder is powdered glass and is manufactured by crushing glass.
  • the average particle size of the glass powder is, for example, 1 to 500 ⁇ m.
  • the particle size of glass powder is defined as the diameter of a sphere with the same volume as the particle of glass powder.
  • Glass powder can be obtained by a known method.
  • Glass beads have a spherical or approximately spherical shape.
  • the average particle diameter of the glass beads is, for example, 1 to 500 ⁇ m.
  • the particle size of a glass bead is defined as the diameter of a sphere with the same volume as the glass bead particle. Glass beads can be obtained by known methods.
  • the glass fiber and glass filler of this embodiment can be used to reinforce various products.
  • glass fibers and glass fillers may be used to reinforce concrete products, rubber products, or plastic products.
  • the present invention provides a concrete product comprising at least one selected from the group consisting of the glass fiber and glass filler of the present embodiment.
  • the concrete product has a cement composition and glass fibers or glass filler embedded in the cement composition.
  • the concrete product includes a main body and a covering member that covers the surface of the main body, and the covering member contains glass fiber or glass filler.
  • the covering member may further contain a material such as resin or cement.
  • Glass fillers may be used to reinforce concrete products.
  • Glass fibers and glass fillers used for reinforcing concrete products may be processed as appropriate depending on the type of concrete product. Specifically, fiber sheets or rods containing glass fiber or glass filler can be used to reinforce concrete products.
  • chopped strands can be used, for example, mixed with cement compositions.
  • chopped strands can be classified into "focused chopped strands" formed from a strand bundle and "non-focused chopped strands" formed from a single strand.
  • a mixture of unfocused chopped strands and a cement composition can be sprayed onto the surface of a body of a concrete product to form a coating covering the surface of the body. According to this covering member, it is possible to suppress the concrete material from peeling off from the surface of the main body.
  • mixtures of focused chopped strands and cement compositions are suitable for reinforcing entire concrete products. The chopped strands in this mixture play a role similar to that of straw used in earthen walls and mortar.
  • chopped strands have a large specific surface area and a large area of contact with cement. Therefore, it is particularly preferable that chopped strands used for reinforcing concrete products have excellent alkali resistance. This chopped strand also needs to have a practically sufficient elastic modulus.
  • the fiber sheet may be a woven fabric or a nonwoven fabric.
  • the woven fabric include cloth using roving or yarn as the warp and/or weft.
  • the nonwoven fabric include chopped strand mats formed from chopped strands.
  • the nonwoven fabric may be formed from short glass fibers.
  • the fiber sheet can be used by being impregnated with cement mortar or resin such as epoxy resin, for example.
  • the fiber sheet may be used with its surface covered with a layer made of resin (resin layer).
  • resin layer a layer made of resin
  • a fiber sheet impregnated with cement mortar or resin, or a fiber sheet whose surface is covered with a resin layer may be referred to as a protective sheet.
  • known methods such as hand lay-up molding, SMC (Sheet Molding Compound) molding, BMC (Bulk Molding Compound) molding method, etc. can be used.
  • FIGS. 6A and 6B show an example of a concrete product containing the above-mentioned protective sheet.
  • FIGS. 6A and 6B show a segment 51 used as a concrete product for lining a tunnel by the shield method.
  • the segments 51 have an arcuate plate shape, and can form a cylindrical lining body by being joined to each other in an excavated hole excavated by a shield machine.
  • a plurality of segments 51 can form a ring by joining each other in the circumferential direction.
  • a lining body can be formed by joining a plurality of segments 51 to each other in the axial direction of the ring.
  • a joint plate 53 is provided on the joint end surface 51A of the segment 51 in the circumferential direction. By fastening and fixing the joint plates 53 of the plurality of segments 51 to each other, the plurality of segments 51 can be joined in the circumferential direction.
  • One joint end surface 51B of the segment 51 in the axial direction of the ring is provided with a joint rod (not shown) protruding from the joint end surface 51B.
  • the other joining end surface 51B is provided with a joining tool 52 that engages the above-mentioned joining rod.
  • the joining tool 52 has an insertion hole H into which a joining rod is inserted.
  • FIG. 6B is an enlarged cross-sectional view of the segment 51 near the joint end surface 51B.
  • the segment 51 further includes a protective sheet 61 disposed on the joint end surface 51B.
  • the surface of the protective sheet 61 constitutes the joint end surface 51B.
  • the protective sheet 61 functions as a covering member that covers the surface of the main body of the segment 51.
  • the segments 51 may further include a sealing member 64 that seals the segments 51 when the segments 51 are joined to each other.
  • the shield machine extends the rod of the jack while excavating the ground with the cutter at its tip while keeping the spreader of the jack in contact with the lining made of segments 51. Thereby, the shield machine can obtain reaction force from the lining body through the jack, and can be propelled by this reaction force. Since the shield machine is equipped with a plurality of jacks, a plurality of spreaders are in contact with the lining body. Therefore, when the pressing force on the lining body from the plurality of spreaders acts toward the outside of the lining body, stress may be generated between two adjacent segments 51 in the lining body. By buffering this stress, the protective sheet 61 can suppress the occurrence of cracks near the joint end surface 51B.
  • the rod is made of, for example, bundled glass fibers.
  • the rod is made by braiding glass fibers.
  • the bundled glass fibers may be hardened with cement or resin such as epoxy resin.
  • Rods can be used, for example, as an alternative to reinforcing bars.
  • FIG. 7 shows an example of a concrete product including the above rod.
  • a utility pole 70 as a concrete product.
  • the utility pole 70 is partially embedded in the ground 80 and extends upward.
  • the utility pole 70 includes a cement composition 72 containing mortar or the like filled therein, and a plurality of rods 75 embedded in the cement composition 72.
  • the rods 75 are arranged parallel to each other from the bottom of the utility pole 70 along the direction in which the utility pole 70 extends.
  • glass fiber has an excellent modulus of elasticity. This glass fiber also needs to have sufficient alkali resistance for practical purposes.
  • the utility pole 70 shown in FIG. 7 is constructed by, for example, inserting a rod 75 into the utility pole through an opening or the like in a utility pole having a hollow interior, and then filling the interior of the utility pole with a cement composition 72. It can be made by Details of this manufacturing method are described in, for example, Japanese Patent Laid-Open No. 2006-2543. Note that, in JP-A-2006-2543, an aramid rod made of aramid fibers is used. The rod 75 containing glass fiber of this embodiment tends to have better alkali resistance than an aramid rod.
  • Examples of concrete products reinforced with glass fibers or glass fillers are not limited to those mentioned above.
  • Glass fibers and glass fillers can be used as aggregates, reinforcing materials, etc. for various concrete products. Glass fibers and glass fillers also tend to have good mechanical properties and thermal stability, making them ideal for concrete products where heat resistance is required (e.g. concrete products used in power plants, melting furnaces, coke ovens, etc.); Alternatively, it can also be used for building materials that require fire resistance (for example, fire-resistant structures of buildings, fire-resistant coatings, etc.).
  • glass fibers and glass fillers can also be processed into forms other than the above-mentioned chopped strands, fiber sheets, and rods, such as strands, rovings, yarns, and cords. Note that the yarn is obtained by twisting one or more strands.
  • the present invention provides a rubber product comprising at least one selected from the group consisting of the glass fiber and glass filler of the present embodiment.
  • a rubber product has a rubber composition (matrix rubber) and glass fibers or glass fillers embedded in the rubber composition.
  • Glass fibers and glass fillers used for reinforcing rubber products may be processed as appropriate depending on the type of rubber product. Specifically, a cord containing glass fiber or the like can be used to reinforce the rubber product.
  • the cord (rubber reinforcing cord) includes a strand formed by bundling the above-mentioned glass fibers (rubber reinforcing fibers).
  • the number of glass fibers contained in the strand is not particularly limited, and is, for example, 100 to 2000, typically 200 to 600.
  • the strand can be formed by bundling a predetermined number of spun glass fibers using a sizing agent, such as an elastomer-based sizing agent, that is commonly used for forming strands when spinning glass fibers.
  • the formed strand may be wound around a collet or the like and subjected to a predetermined treatment such as drying.
  • a plurality of strands are preferably bundled to form a strand assembly.
  • the number of strands forming the cord may be one.
  • the strand or strand aggregate preferably contains 200 to 36,000 glass fibers, more preferably 200 to 7,800 glass fibers.
  • the wire diameter of the strand or strand aggregate is preferably 10 tex to 8350 tex, more preferably 68 tex to 1430 tex.
  • the strands may be coated with a first coating layer formed from a treatment liquid A containing latex and at least one selected from a resorcinol-formaldehyde condensate and a vulcanizing agent.
  • a first coating layer formed from a treatment liquid A containing latex and at least one selected from a resorcinol-formaldehyde condensate and a vulcanizing agent.
  • the type of latex is not particularly limited, but examples include vinylpyridine-styrene-butadiene terpolymer (VP) latex, chlorosulfonated polystyrene (CSM) latex, acrylonitrile-butadiene copolymer (NBR) latex, and highly saturated polymers containing nitrile groups. It may be at least one type selected from latex. By using these materials, the heat resistance and water resistance of the reinforcing cord can be improved.
  • VP vinylpyridine-styrene-butadiene terpolymer
  • CSM chlorosulfonated polystyrene
  • NBR acrylonitrile-butadiene copolymer
  • the nitrile group-containing highly saturated polymer may be a material obtained by hydrogenating a copolymer or terpolymer containing acrylonitrile as a constituent unit, such as a material obtained by hydrogenating NBR (H-NBR), or a butadiene-ethylene-acrylonitrile terpolymer.
  • H-NBR hydrogenating NBR
  • H-NBR butadiene-ethylene-acrylonitrile terpolymer
  • examples include materials containing acrylonitrile and a saturated hydrocarbon as structural units.
  • the resorcinol-formaldehyde condensate (RF) is not particularly limited, and a novolak type, resol type, or a mixture thereof may be used.
  • RF is generally commercially available as a liquid containing solids, but one with a solids content in the range of about 5% by weight to 10% by weight can be suitably used.
  • the vulcanizing agent is not particularly limited, and examples thereof include at least one selected from maleimide compounds and organic diisocyanate compounds.
  • the content of the vulcanizing agent in the treatment liquid A may be in the range of 5 to 100 parts by weight, preferably 20 parts by weight, based on 100 parts by weight of the solid content of the latex. ⁇ 75 parts by weight. In this case, a better balance can be achieved between the flexibility of the cord and the adhesion to the matrix rubber.
  • the organic diisocyanate compound is not particularly limited, but for example, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, methylene bis(phenylisocyanate), etc. may be used.
  • the treatment liquid A may contain one or more types of these organic diisocyanate compounds, and for substances that have isomers regarding substituents, such as toluene diisocyanate and methylene bis(phenylisocyanate), the isomers may not interact with each other. It may be a mixture of. Further, the organic diisocyanate compound may be used with its isocyanate group protected by phenols or lactams.
  • the maleimide compound is not particularly limited, but for example, bismaleimide, phenylmaleimide, diphenylmethane-4,4'-bismaleimide, etc. may be used.
  • the solid content in the treatment liquid A is preferably in the range of 10% to 40% by weight, more preferably in the range of 25% to 35% by weight. If the content is too low, the formation of the first coating layer will be insufficient, and if it is too high, it will be difficult to control the amount of treatment liquid A applied to the strand, resulting in uneven thickness of the first coating layer. Prone.
  • the treatment liquid A may contain bases such as ammonia for adjusting the pH, and may also contain stabilizers, anti-aging agents, etc., as necessary.
  • the treatment liquid A may contain a filler such as carbon black, and in this case, the cord can have better adhesion to the matrix rubber.
  • the strand (including the aggregate) may be continuously immersed in a coating bath containing treatment liquid A, and after the strand is pulled up from the coating bath, excess treatment liquid may be removed and, if necessary, it may be dried.
  • the strand on which the first coating has been formed may be used as a cord as it is, or may be subjected to various treatments such as twisting and formation of a second coating layer, which will be described later, as necessary.
  • the first coating layer may be formed in an amount corresponding to about 10% to 30% by weight based on the weight of the strand.
  • the cord may have a structure in which two or more yarns formed by first twisting strands covered with the first coating layer are bundled and further twisted. In this case, the strength can be further improved and the cord can have better bending fatigue resistance.
  • the number of times of first twisting may be about 0.5 to 4 times, preferably about 1.2 to 3 times per 2.54 cm (1 inch) in the length direction.
  • the yarns formed by pre-twisting are bundled into a bundle of about 2 to 20 yarns, preferably about 6 to 15 yarns, and then twisted in the length direction 0.5 to 4 times, preferably 1 to 2 times, per 2.54 cm. It may be twisted approximately 8 times.
  • the cord may be covered with a second coating layer containing rubber.
  • a cord with improved adhesiveness to the matrix rubber can be obtained.
  • the type of rubber is not particularly limited, and may be selected appropriately depending on the type of matrix rubber.
  • the coating layer contains CSM as the rubber.
  • the second coating layer may be made of nitrile as the above rubber because it has better adhesion. It is preferable to include a group-containing highly saturated copolymer or a mixed rubber having the same composition as the matrix rubber.
  • the second covering layer may be, for example, a strand (including an aggregate), a strand (including an aggregate) covered by the first covering layer, or a yarn obtained by further twisting the strand, using rubber or a rubber precursor. It may be formed by impregnating the body with the treatment liquid B in which the body is dissolved and then drying it.
  • CSM and highly saturated polymers containing nitrile groups dissolve in aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as trichloroethylene, ketones such as methyl ethyl ketone, and esters such as ethyl acetate, so they cannot be used in processing liquids.
  • B may contain these organic substances as a solvent.
  • the treatment liquid B may contain a vulcanizing agent, and examples of the vulcanizing agent include, in addition to the above-mentioned maleimide compound and organic diisocyanate compound, sulfur; dicumyl peroxide, and 1,3-bis(t-butyl). Organic peroxides such as peroxy-m-isopropyl)benzene; aromatic nitroso compounds such as p-dinitronaphthalene and p-dinitrosobenzene may also be used.
  • the treatment liquid B may contain an inorganic filler, an anti-aging agent, a vulcanization aid, a plasticizer, etc., as necessary.
  • the content of substances other than the solvent (rubber, vulcanizing agent, etc.) in treatment liquid B may be set appropriately depending on the type of substance, but is in the range of about 3% by weight to 25% by weight, preferably 5% by weight to If the amount is in the range of about 15% by weight, the second coating layer can be easily formed.
  • the content of rubber or rubber precursor in the substance other than the solvent is preferably about 20% to 60% by weight, and if the treatment liquid B contains a vulcanizing agent, the content of the vulcanizing agent in the substance other than the solvent is preferably in the range of about 0.5% to 30% by weight.
  • the amount of the substance other than the solvent may be 1
  • the treatment liquid B may be applied in an amount of about 15% by weight, preferably about 2% by weight to 6% by weight.
  • Examples of rubber products reinforced with the above cords include rubber belts, rubber tires, and rubber hoses.
  • An example of a rubber belt is a power transmission belt.
  • Examples of transmission belts include meshing transmission belts and friction transmission belts.
  • An example of a meshing power transmission belt is a toothed belt typified by an automotive timing belt.
  • Examples of friction transmission belts include flat belts, round belts, V belts, and V-ribbed belts. Rubber tires are typically automobile tires or bicycle tires. In cords used for reinforcing rubber products, it is particularly preferred that glass fibers have an excellent modulus of elasticity.
  • FIG. 8 shows an example of the structure of a rubber belt including a cord.
  • the rubber belt 91 has a so-called toothed belt shape and includes a matrix rubber 93 and a plurality of cords 92 embedded in the matrix rubber 93.
  • the cords 92 are arranged parallel to each other along the longitudinal direction of the rubber belt 91, in other words, along a direction perpendicular to the belt width direction that is traversed by the protruding portions 94 serving as "teeth.”
  • a tooth cloth 95 is attached to the surface of the rubber belt 91 on which the protruding portions 94 are formed for the purpose of suppressing wear and the like.
  • the glass fiber or glass filler can also be processed and used in other forms than the above-mentioned cord.
  • Other forms include those described above for concrete products.
  • the present invention provides a plastic product comprising at least one selected from the group consisting of the glass fiber and glass filler of the present embodiment.
  • the plastic product includes a resin composition (matrix resin) and glass fibers or glass filler embedded in the resin composition.
  • the plastic product includes a main body and a covering member that covers the surface of the main body, and the covering member contains glass fiber or glass filler. The covering member may further contain a material such as resin.
  • Plastic products reinforced with glass fiber are sometimes called FRP (Fiber Reinforced Plastic).
  • the matrix resin may contain a thermosetting resin or a thermoplastic resin.
  • the thermosetting resin is not particularly limited, and examples thereof include epoxy resins, modified epoxy resins such as vinyl ester resins, phenol resins, unsaturated polyester resins, polyimide resins, and bismaleimide resins.
  • the thermoplastic resin is not particularly limited, and examples thereof include polyolefin resin, polyamide resin, polycarbonate resin, polyphenylene sulfide resin, polyether ether ketone resin, and the like. Resin products containing thermoplastic resins can be easily produced by injection molding, stampable molding, and the like.
  • Glass filler (especially chopped strands) may be used to reinforce plastic products.
  • Glass fibers and glass fillers used for reinforcing plastic products may be processed as appropriate depending on the type of plastic product. Specifically, fiber sheets containing glass fibers or glass fillers can be used to reinforce plastic products. Glass fibers or glass fillers can also be processed and used in forms other than chopped strands and fiber sheets. Other forms include those described above for concrete products.
  • Plastic products reinforced with glass fiber or glass filler of this embodiment include, for example, sports equipment, vehicles such as automobiles, ships, building materials, aircraft, septic tanks, bathtubs, blades for wind power generation, square timbers, poles, tanks, and pipes. It can be used for applications such as sewage pipes (drain pipes), fuel tanks, and home appliances.
  • vehicles such as automobiles, ships, building materials, aircraft, septic tanks, bathtubs, blades for wind power generation, square timbers, poles, tanks, and pipes. It can be used for applications such as sewage pipes (drain pipes), fuel tanks, and home appliances.
  • plastic products used for sporting goods include fishing lines, fishing rods, golf club shafts, skis, canoes, tennis and badminton rackets and strings.
  • Plastic products used in vehicle applications include vehicle bodies, lamp housings, front end panels, bumpers, seat housings, drive shafts, etc.
  • Plastic products used for ships include ship bodies, masts, decks, etc.
  • Plastic products used in aircraft include primary structural materials, secondary structural materials, interior materials, seats, and accessory members.
  • Plastic products used in home appliances include circuit boards, panels, switchgear, insulators, and the main body of home appliances.
  • glass fibers and glass fillers may come into contact with acidic liquids such as acid rain. Therefore, in this application, it is particularly preferable that the glass fibers and glass fillers have excellent acid resistance. Glass fibers and glass fillers also need to have a practically sufficient modulus of elasticity.
  • glass fiber and glass filler of this embodiment can also be used in high-temperature insulation materials used in vehicle mufflers, engine parts, blast furnaces, and the like.
  • the glass fiber and glass filler of this embodiment can also be used in separators used in batteries such as lead-acid batteries.
  • Examples 1 to 26 and Comparative Examples 1 to 12 The raw materials for general glass compositions such as silicon dioxide are weighed so as to have the respective compositions shown in Tables 2 to 5 (the unit of content of the components is mass %), and mixed to a homogeneous state. A raw material mixed batch was prepared.
  • coal ash, silicon dioxide, diboron trioxide, aluminum oxide, magnesium oxide, calcium carbonate, strontium carbonate, zinc oxide, lithium carbonate, sodium carbonate, potassium carbonate , titanium dioxide, zirconium oxide, and diiron trioxide were used.
  • the composition of the coal ash used is shown in Table 1.
  • the prepared raw material mixed batch was melted at 1500 to 1600°C using an electric furnace, and the molten state was maintained for about 4 hours so that the composition was uniform.
  • a part of the obtained molten glass composition (glass melt) is poured out onto an iron plate and slowly cooled to room temperature in an electric furnace to obtain a bulk glass composition sample (plate shape) to be used for evaluation. Obtained.
  • sample For the prepared glass composition sample (hereinafter abbreviated as sample), Young's modulus E, working temperature, devitrification temperature, mass reduction rate ⁇ W 1 under acidic solution, and mass reduction rate ⁇ W 2 under alkaline solution were measured. did.
  • the measurement method is as follows.
  • the platinum ball lifting 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.
  • the produced glass composition was pulverized, and glasses of a size that passed through a standard mesh sieve of 1.0 mm specified in JIS Z8801 and did not pass through a standard mesh sieve of 2.8 mm were separated.
  • This glass was placed in a platinum boat and heated for 2 hours in an electric furnace with a temperature gradient (900 to 1400°C).
  • the devitrification temperature was determined. Note that the temperature (temperature distribution in the electric furnace) that varies depending on the location in the electric furnace is measured in advance, and the glass composition placed at a predetermined location in the electric furnace is Heated at a given location temperature.
  • the temperature difference ⁇ T is the temperature difference obtained by subtracting the devitrification temperature from the working temperature. Considering the manufacturing process of glass fibers and glass fillers, it is desirable that the glass composition has a devitrification temperature lower than the working temperature.
  • Measurement follows the steps below. 1. Grind the glass composition sample. 2. For the ground sample, a powder sample having a size that passes through a test sieve of 600 ⁇ m and remains on a test sieve of 425 ⁇ m is separated. Note that the test sieve is one specified in JIS Z8801. 3. Weigh 5 g of the separated powder sample. 4. The weighed powder sample is immersed in 80 mL of a 21.2% by mass sulfuric acid aqueous solution at 99° C. for 1 hour. 5. After immersion, the supernatant is removed by decantation, the remaining sample is dried, and its mass is measured. 6.
  • the mass reduction rate ⁇ W 1 is calculated as the ratio of the difference between the mass of the sample and the mass of the remaining sample to the mass of the sample before being immersed in the sulfuric acid aqueous solution. Note that, as described above, ⁇ W 1 is an index of acid resistance.
  • Measurement follows the steps below. 1. Grind the glass composition sample. 2. For the ground sample, a powder sample having a size that passes through a test sieve of 600 ⁇ m and remains on a test sieve of 425 ⁇ m is separated. Note that the test sieve is one specified in JIS Z8801. 3. Weigh 5 g of the separated powder sample. 4. The weighed powder sample is immersed in 80 mL of a 10% by mass aqueous sodium hydroxide solution at 99° C. for 1 hour. 5. After immersion, the supernatant is removed by decantation, the remaining sample is dried, and its mass is measured. 6.
  • the mass reduction rate ⁇ W 2 is calculated as the ratio of the difference between the mass of the sample and the mass of the remaining sample to the mass of the sample before being immersed in the sodium hydroxide aqueous solution. Note that, as described above, ⁇ W 2 is an index of alkali resistance.
  • Tables 2 to 5 show the Young's modulus, glass transition temperature, devitrification temperature, working temperature, temperature difference ⁇ T, mass loss rate ⁇ W 1 under acidic solution, and mass loss rate ⁇ W 2 under alkaline solution of the glass compositions.
  • the glass compositions of Examples 1 to 26 had Young's moduli in the range of 90 to 93 GPa, working temperatures in the range of 1047 to 1189°C, and ⁇ T in the range of 0 to 37°C.
  • the mass reduction rate ⁇ W 2 under alkaline solution was in the range of 0.02 to 0.18 mass%.
  • the glass compositions of Examples had high elastic modulus and improved moldability and alkali resistance.
  • the glass composition of Comparative Example 1 had a T-Fe 2 O 3 content of 16.8% by mass, which exceeded 16% by mass.
  • the glass composition of Comparative Example 1 had a ⁇ T of ⁇ 82° C. and was inferior in moldability compared to the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 1 had a mass reduction rate ⁇ W 2 in an alkaline solution of 0.22% by mass, and was inferior in alkali resistance compared to the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 3 had a T-Fe 2 O 3 content of 9.5% by mass, which was less than 10% by mass.
  • the Young's modulus of the glass composition was 86 GPa, and the elasticity was lower than that of the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 4 had a (SiO 2 +Al 2 O 3 ) content of 70.8% by mass, which exceeded 70% by mass. Furthermore, the content of T-Fe 2 O 3 was 8.7% by mass, which was less than 10% by mass. In Comparative Example 4, a crystal phase was precipitated in the glass composition, and a homogeneous glass material could not be obtained.
  • the glass composition of Comparative Example 5 had a T-Fe 2 O 3 content of 16.9% by mass, which exceeded 16% by mass.
  • ⁇ T was ⁇ 11° C., and the moldability was inferior to that of the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 5 had a mass reduction rate ⁇ W 2 in an alkaline solution of more than 0.50% by mass, and was inferior in alkali resistance compared to the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 6 had a T-Fe 2 O 3 content of 16.9% by mass, which exceeded 16% by mass.
  • ⁇ T was ⁇ 79° C., and the moldability was inferior to that of the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 6 had a mass reduction rate ⁇ W 2 in an alkaline solution of 0.39% by mass, and was inferior in alkali resistance compared to the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 8 had a B 2 O 3 content of 12.1% by mass, which exceeded 10% by mass.
  • ⁇ T was ⁇ 13° C., and the moldability was inferior to that of the glass compositions of Examples 1 to 26.
  • Comparative Example 9 did not contain MgO and had MgO/(MgO+CaO) of 0.
  • ⁇ T was ⁇ 96° C., and the moldability was inferior to the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 10 which had a composition corresponding to conventional C glass, had a Young's modulus of 78 GPa, and had lower elasticity than the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 11 which had a composition corresponding to conventional E glass, had a Young's modulus of 83 GPa, and had lower elasticity than the glass compositions of Examples 1 to 26. Furthermore, the glass composition of Comparative Example 11 had a mass reduction rate ⁇ W 2 in an alkaline solution of 0.27% by mass, and was inferior in alkali resistance compared to the glass compositions of Examples 1 to 26.
  • the glass composition of Comparative Example 12 which has a composition equivalent to conventional alkali-resistant glass (AR glass), had a Young's modulus of 83 GPa, and had lower elasticity than the glass compositions of Examples 1 to 26.
  • the glass composition of the present invention has a high elastic modulus and improved formability and alkali resistance, so it can be used not only as a structural member but also as a filler for glass flakes, chopped strands, milled fibers, glass powder, glass beads, etc. Useful. Due to its alkali resistance and high elasticity, it is also particularly useful as a filler for cement.

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PCT/JP2023/028654 2022-08-08 2023-08-04 ガラス組成物、ガラス繊維、ガラスフィラー、ガラス繊維の製造方法、及びガラスフィラーの製造方法 Ceased WO2024034546A1 (ja)

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JP2001524063A (ja) * 1996-10-31 2001-11-27 オウェンス コーニング 無機繊維組成物
JP2006002543A (ja) 2004-06-21 2006-01-05 Hiroyasu Minayoshi コンクリート製の電柱の補強方法およびコンクリート製の電柱
WO2010133522A1 (de) * 2009-05-18 2010-11-25 Tu Bergakademie Freiberg Verwendung von alumosilikatgläsern als substratgläser für die photovoltaik
JP2020529378A (ja) 2018-07-03 2020-10-08 タイシャン ファイバーグラス インクＴａｉｓｈａｎ Ｆｉｂｅｒｇｌａｓｓ Ｉｎｃ． 玄武岩を原料とするハイモジュラスガラス繊維組成物
WO2020218356A1 (ja) * 2019-04-25 2020-10-29 新日本繊維株式会社 耐放射線性無機材料及びその繊維
WO2022131222A1 (ja) * 2020-12-15 2022-06-23 日本板硝子株式会社 補強用ガラス繊維、チョップドストランド、繊維シート及びロッド

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JP2006002543A (ja) 2004-06-21 2006-01-05 Hiroyasu Minayoshi コンクリート製の電柱の補強方法およびコンクリート製の電柱
WO2010133522A1 (de) * 2009-05-18 2010-11-25 Tu Bergakademie Freiberg Verwendung von alumosilikatgläsern als substratgläser für die photovoltaik
JP2020529378A (ja) 2018-07-03 2020-10-08 タイシャン ファイバーグラス インクＴａｉｓｈａｎ Ｆｉｂｅｒｇｌａｓｓ Ｉｎｃ． 玄武岩を原料とするハイモジュラスガラス繊維組成物
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WO2022131222A1 (ja) * 2020-12-15 2022-06-23 日本板硝子株式会社 補強用ガラス繊維、チョップドストランド、繊維シート及びロッド

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