Glass composition, glass fiber and glass filler

Abstract

Provided are a glass composition, a glass fiber, and a glass filler, which have a low linear expansion coefficient, a low dielectric constant, and a low dielectric loss tangent, and are suitable for mass production. A glass composition having, in mass%, 55 < = SiO2 < = 65, 6 < B2O3 < = 20, 12 < = Al2O3 < = 20, 0 < = MgO < = 10, 0 < = CaO < = 4, 0 < = SrO < = 4, 3 < = ZnO < = 12, 0 < = (Li2O + Na2O + K2O) < = 2, 0.1 < = TiO2 < = 5, 0 < = ZrO2 < = 5, and at least one selected from the group consisting of a) 0.1 < = ZrO2 < = 5, b) 56 < = SiO2 < = 65 and 12 < = Al2O3 < = 19, and c) 56 < = SiO2 < = 65, 12 < = Al2O3 < = 19 and 3 < ZnO < = 12, and substantially not containing As2O3.

Description

Technical Field

[0001] This invention relates to glass compositions, glass fibers and glass fillers, and articles containing glass fibers or glass fillers. Background Technology

[0002] Resin compositions are widely used in electronic devices to form electrical insulation components and mechanical components. Examples of electrical insulation components include connector housings for SMT (surface mount technology), FPC (flexible printed circuits), board-to-board (BOT) connections, CPU (central processing unit) sockets, memory cards, card edges, and optical connectors; coil frames for reactance in LCD (liquid crystal display) backlights, coils, flat panels, transformers, and magnetic heads; switching devices for relay housings, relay base switches, reflow soldering switches, and tactile switches; sensor housings; capacitor housings; potentiometer housings; and fine-tuning potentiometer housings. Examples of mechanical components include lens frames and pickup head bases for optical pickup heads; insulators and terminals for micro motors; and drums for laser printers. Resin compositions are also used as base films for FPCs, copper-clad laminates, and other similar materials. Furthermore, printed circuit boards (PCBs) in electronic devices also have substrates made of resin compositions. Printed wiring boards (PCBs) used before electronic components are mounted also have substrates made of resin compositions. In this specification, both printed circuit boards and printed circuit boards will be referred to as "printed boards".

[0003] The aforementioned resin composition contains thermoplastic resin and glass fiber, and may further contain hardeners, modifiers, etc., as needed. Printed substrates may also contain inorganic filler materials. Glass fillers can be used as inorganic fillers. In recent years, to meet the miniaturization requirements of electronic devices and the need for thinner profiles for high functionality, dimensional stability is required for resin compositions. Correspondingly, low coefficients of thermal expansion and high elastic moduli are required for their constituent materials. Patent documents 1 and 2 disclose glass compositions with low linear thermal expansion coefficients and low dielectric loss tangents, and glass fibers composed of such glass compositions. Patent document 3 discloses a glass for resin composite substrates that integrates the optical properties of transparent resin, but has a relatively low linear thermal expansion coefficient.

[0004] The glass composition disclosed in the embodiments of Patent Document 1 includes SiO2, Al2O3, MgO, CaO, etc., and contains titanium oxide (TiO2) at a mass ratio of 0.6% to 4.0% and the content of boron oxide (B2O3) is limited to 5.0% or less. The glass composition disclosed in the embodiments of Patent Document 2 includes SiO2, B2O3, Al2O3, MgO, etc., and contains zinc oxide (ZnO) at a mass ratio of 4.0% to 7.5%. The embodiments of Patent Document 2 do not disclose a glass composition containing titanium oxide (TiO2). The glass composition disclosed in the embodiments of Patent Document 3 includes SiO2, B2O3, Al2O3, CaO, etc., and contains titanium oxide (TiO2) at a mass ratio of 1.2% to 4.0%.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2011-105554

[0008] Patent Document 2: International Publication No. 2012 / 104999

[0009] Patent Document 3: Japanese Patent Application Publication No. 2012-51773 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] With the trend towards miniaturization and increased functionality in electronic devices, dimensional stability is required for the resin compositions constituting these devices. Consequently, glass fibers and glass fillers, as constituent materials, require low coefficients of linear thermal expansion. Furthermore, low dielectric loss is also required for the resin compositions constituting these devices, necessitating low dielectric constants and low dielectric loss tangents for the glass fibers and glass fillers. Therefore, the object of this invention is to provide a novel glass composition that exhibits low coefficients of linear thermal expansion, low dielectric constants, and low dielectric loss tangents, and is also suitable for mass production.

[0012] Problem-solving methods

[0013] This invention provides a glass composition, wherein, expressed in mass %

[0014] 55≤SiO2≤65,

[0015] 6 < B₂O₃ ≤ 20

[0016] 12≤Al2O3≤20,

[0017] 0≤MgO≤10,

[0018] 0≤CaO≤4,

[0019] 0≤SrO≤4,

[0020] 3≤ZnO≤12,

[0021] 0≤(Li2O+Na2O+K2O)≤2,

[0022] 0.1≤TiO2≤5,

[0023] 0.1≤ZrO2≤5.

[0024] The present invention provides, in another aspect, a glass composition, wherein, expressed in mass %

[0025] 56≤SiO2≤65,

[0026] 6 < B₂O₃ ≤ 20

[0027] 12≤Al2O3≤19,

[0028] 0≤MgO≤10,

[0029] 0≤CaO≤4,

[0030] 0≤SrO≤4,

[0031] 3≤ZnO≤12,

[0032] 0≤(Li2O+Na2O+K2O)≤2,

[0033] 0.1≤TiO2≤5,

[0034] 0≤ZrO2≤5,

[0035] It does not actually contain BaO and As2O3.

[0036] The present invention provides, in another aspect, a glass composition, wherein, expressed in mass %

[0037] 56≤SiO2≤65,

[0038] 6 < B₂O₃ ≤ 20

[0039] 12≤Al2O3≤19,

[0040] 0≤MgO≤10,

[0041] 0≤CaO≤4,

[0042] 0≤SrO≤4,

[0043] 3 < ZnO ≤ 12,

[0044] 0≤(Li2O+Na2O+K2O)≤2,

[0045] 0.1≤TiO2≤5,

[0046] 0≤ZrO2≤5,

[0047] It does not actually contain As2O3.

[0048] The present invention can also be described in the following manner.

[0049] A glass composition, wherein, expressed in mass %

[0050] 55≤SiO2≤65,

[0051] 6 < B₂O₃ ≤ 20

[0052] 12≤Al2O3≤20,

[0053] 0≤MgO≤10,

[0054] 0≤CaO≤4,

[0055] 0≤SrO≤4,

[0056] 3≤ZnO≤12,

[0057] 0≤(Li2O+Na2O+K2O)≤2,

[0058] 0.1≤TiO2≤5,

[0059] 0≤ZrO2≤5,

[0060] At least one of the choices from the group consisting of a), b), and c) is true.

[0061] a) 0.1≤ZrO2≤5 holds true.

[0062] b) 56≤SiO2≤65 and 12≤Al2O3≤19 hold true, and in fact, BaO and As2O3 are not present.

[0063] c) 56≤SiO2≤65, 12≤Al2O3≤19, and 3<ZnO≤12 hold true, but in reality, As2O3 is not present.

[0064] The effects of the invention

[0065] According to the present invention, novel glass compositions with low coefficient of linear thermal expansion, low dielectric constant and low dielectric loss tangent can be provided, and are suitable for mass production. Detailed Implementation

[0066] The following describes embodiments of the present invention, but the description is not intended to limit the invention to specific embodiments. In this specification, "substantially free of" means a content of less than 0.1% by mass, less than 0.05% by mass, less than 0.01% by mass, even less than 0.005% by mass, particularly less than 0.003% by mass, and sometimes less than 0.001% by mass. "Substantially" means that trace amounts of impurities from glass raw materials, manufacturing apparatus, forming apparatus, etc., are permissible. "Main component" means the component with the highest content by mass. "T-Fe2O3" means total iron oxide converted to ferric oxide (Fe2O3). "T-SnO2" means total tin oxide converted to tin dioxide (SnO2). "T-CeO2" means total cerium oxide converted to cerium dioxide (CeO2). "T-MnO2" means total manganese oxide converted to manganese dioxide (MnO2). "T-CuO" means total copper oxide converted to copper oxide (CuO). "Alkali metal oxides" refers to lithium oxide (Li₂O), sodium oxide (Na₂O), and potassium oxide (K₂O). The upper and lower limits of the content percentages described below can be combined arbitrarily. The content percentages of all components can be combined arbitrarily as long as the total content does not exceed 100%. Hereinafter, the glass composition is sometimes simply referred to as glass, and the coefficient of linear thermal expansion is sometimes simply referred to as the coefficient of linear expansion.

[0067] [Glass composition]

[0068] <Ingredients>

[0069] (SiO2)

[0070] SiO2 is a component that forms the framework of glass and is a major component of glass compositions. In addition, SiO2 is a component that regulates the devitrification temperature and viscosity during glass formation, and improves the acid and water resistance of glass. Furthermore, SiO2 reduces the coefficient of linear expansion of glass. Moreover, SiO2 has the effect of reducing the dielectric constant and the dielectric loss tangent. The SiO2 content is 55% by mass or more and 65% by mass or less. The lower limit of the SiO2 content can be 55.5% by mass or more, 56% by mass or more, 56.5% by mass or more, 57% by mass or more, 57.5% by mass or more, 58% by mass or more, 58.5% by mass or more, and even 59% by mass or more. The upper limit of the SiO2 content can be 64.5% by mass or less, 64% by mass or less, 63.5% by mass or less, 63% by mass or less, 62.5% by mass or less, 62% by mass or less, 61.5% by mass or less, and even 61% by mass or less.

[0071] (B2O3)

[0072] B₂O₃ is a component that forms the framework of glass. Additionally, B₂O₃ is also a component that regulates the devitrification temperature and viscosity during glass formation. On the other hand, excessive B₂O₃ content reduces the Young's modulus of the glass and increases its coefficient of linear expansion. Furthermore, B₂O₃ is a component that reduces the dielectric constant and the dielectric loss tangent. The B₂O₃ content is higher than 6% by mass and lower than 20% by mass. The lower limit of the B₂O₃ content can be 6.5% by mass or higher, 7% by mass or higher, 7.5% by mass or higher, 8% by mass or higher, exceeding 8% by mass, 8.1% by mass or higher, 8.5% by mass or higher, 9% by mass or higher, 9.5% by mass or higher, 10% by mass or higher, higher than 10% by mass, 10.1% by mass or higher, 10.5% by mass or higher, and even 11% by mass or higher. The upper limit of the B2O3 content can be below 19.5% by mass, below 19% by mass, below 18.5% by mass, below 18% by mass, below 18% by mass, below 17.5% by mass, below 17% by mass, below 16.5% by mass, below 16% by mass, below 16% by mass, below 16% by mass, below 15.5% by mass, below 15% by mass, below 14.5% by mass, below 14% by mass, or even below 13% by mass.

[0073] (Al2O3)

[0074] Al₂O₃ is a component that forms the framework of glass. Additionally, Al₂O₃ is a component that regulates the devitrification temperature and viscosity during glass formation. Furthermore, Al₂O₃ increases the Young's modulus of glass and decreases its coefficient of linear expansion. Moreover, Al₂O₃ regulates the dielectric constant and loss tangent of glass. When the Al₂O₃ content is 12% by mass or more and 20% by mass or less, the rise in the devitrification temperature of the glass is suppressed, the melting point of the glass does not increase excessively, and the uniformity of the raw material melting increases. The lower limit of the Al₂O₃ content can be 12.5% ​​by mass or more, 13% by mass or more, higher than 13% by mass, 13.1% by mass or more, 13.5% by mass or more, 14% by mass or more, higher than 14% by mass, and even 14.1% by mass or more. The upper limit of the Al2O3 content can be below 19.5% by mass, below 19% by mass, below 19% by mass, below 18.5% by mass, below 18% by mass, below 18% by mass, below 17.5% by mass, below 17% by mass, below 16.5% by mass, below 16% by mass, below 15.5% by mass, below 15% by mass, below 15% by mass, and further below 14.9% by mass.

[0075] (MgO)

[0076] MgO can be any component. MgO is used to adjust the devitrification temperature and viscosity during glass formation, and it also increases the Young's modulus of the glass. On the other hand, excessive MgO content increases the coefficient of linear expansion of the glass. Additionally, MgO is used to adjust the dielectric constant and loss tangent of the glass. The lower limit of MgO content can be above 0% by mass, above 0%, above 0.1% by mass, above 0.2% by mass, above 0.3% by mass, above 0.4% by mass, above 0.5% by mass, above 1% by mass, and even above 1.5% by mass. The upper limit for the MgO content can be below 10% by mass, below 9.5% by mass, below 9% by mass, below 8.5% by mass, below 8% by mass, below 7.5% by mass, below 7% by mass, below 6.5% by mass, below 6% by mass, below 5.5% by mass, below 5% by mass, below 5% by mass, below 5% by mass, below 5% by mass, below 4.9% by mass, below 4.5% by mass, below 4% by mass, below 4% by mass, below 4% by mass, below 3.9% by mass, below 3.5% by mass, below 3% by mass, below 3% by mass, below 3% by mass, below 2.9% by mass, below 2.5% by mass, or even below 2% by mass. It can also be substantially free of MgO.

[0077] (CaO)

[0078] CaO can be any component. CaO is used to adjust the devitrification temperature and viscosity during glass formation. On the other hand, excessive CaO content reduces the Young's modulus of the glass and increases its coefficient of linear expansion. The lower limit of CaO content can be above 0% by mass, above 0.1%, above 0.2%, above 0.3%, above 0.4%, above 0.5%, above 0.5%, above 0.6%, above 0.7%, and even above 0.8% by mass. The upper limit of CaO content can be below 4% by mass, below 3.5% by mass, below 3% by mass, below 2.5% by mass, below 2% by mass, below 2% by mass, below 1.5% by mass, and even below 1% by mass. It can also be substantially free of CaO.

[0079] (MgO + CaO)

[0080] Regarding the meltability and formability of glass, the sum of the contents of MgO and CaO (MgO + CaO) is important. From the viewpoint of obtaining meltability and formability suitable for glass manufacturing, the lower limit of (MgO + CaO) can be above 0% by mass, above 0%, above 0.1% by mass, above 0.2% by mass, above 0.3% by mass, above 0.4% by mass, above 0.5% by mass, above 0.6% by mass, above 0.7% by mass, above 0.8% by mass, above 0.9% by mass, above 1% by mass, above 1.5% by mass, above 2% by mass, and even above 2.5% by mass. Additionally, the upper limits for (MgO + CaO) can be 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 10% by mass or less, 9.5% by mass or less, 9% by mass or less, 8.5% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6.9% by mass or less, 6.8% by mass or less, 6.7% by mass or less, 6.6% by mass or less, 6.5% by mass or less, 6.4% by mass or less, 6.3% by mass or less, 6.2% by mass or less, 6.1% by mass or less, 6% by mass or less, 5.9% by mass or less, 5.8% by mass or less, 5.7% by mass or less, and 5.6% by mass or less. Below 5.5% quality, below 5.4% quality, below 5.3% quality, below 5.2% quality, below 5.1% quality, below 5% quality, below 4.9% quality, below 4.8% quality, below 4.7% quality, below 4.6% quality, below 4.5% quality, below 4.4% quality, below 4.3% quality, below 4.2% quality, below 4.1% quality, below 4% quality, below 3.9% quality, below 3.8% quality, below 3.7% quality, below 3.6% quality, below 3.5% quality, below 3.4% quality, below 3.3% quality, below 3.2% quality, below 3.1% quality, and even below 3% quality.

[0081] (SrO)

[0082] SrO can be any component. SrO is a component used to adjust the devitrification temperature and viscosity during glass formation. On the other hand, excessive SrO content reduces the Young's modulus of the glass and increases its coefficient of linear expansion. The upper limit of SrO content can be below 4% by mass, below 3.9% by mass, below 3.8% by mass, below 3.7% by mass, below 3.6% by mass, below 3.5% by mass, below 3.4% by mass, below 3.3% by mass, below 3.2% by mass, below 3.1% by mass, below 3% by mass, below 2.5% by mass, below 2% by mass, and even below 2% by mass. The lower limit of SrO content can be above 0% by mass, above 0%, above 0.1% by mass, above 0.2% by mass, above 0.3% by mass, above 0.4% by mass, above 0.5% by mass, above 0.6% by mass, above 0.7% by mass, above 0.8% by mass, above 0.9% by mass, and even above 1% by mass. It may also be that it does not actually contain SrO.

[0083] (MgO + CaO + SrO)

[0084] Regarding the meltability and formability of glass, the total content of MgO, CaO, and SrO (MgO + CaO + SrO) is important. From the viewpoint of obtaining meltability and formability suitable for glass manufacturing, the lower limit of (MgO + CaO + SrO) can be above 0% by mass, above 0%, above 0.1% by mass, above 0.2% by mass, above 0.3% by mass, above 0.4% by mass, above 0.5% by mass, above 0.6% by mass, above 0.7% by mass, above 0.8% by mass, above 0.9% by mass, above 1% by mass, above 1.5% by mass, and even above 2% by mass. Additionally, the upper limits for (MgO + CaO + SrO) can be below 18% by mass, below 17% by mass, below 16% by mass, below 15% by mass, below 14% by mass, below 13% by mass, below 12% by mass, below 11% by mass, below 10% by mass, below 9.5% by mass, below 9% by mass, below 8.5% by mass, below 8% by mass, below 7.5% by mass, below 7% by mass, below 6.9% by mass, below 6.8% by mass, below 6.7% by mass, below 6.6% by mass, below 6.5% by mass, below 6.4% by mass, below 6.3% by mass, below 6.2% by mass, below 6.1% by mass, below 6% by mass, below 5.9% by mass, and below 5.8% by mass. Below 5.7% quality, below 5.6% quality, below 5.5% quality, below 5.4% quality, below 5.3% quality, below 5.2% quality, below 5.1% quality, below 5% quality, below 4.9% quality, below 4.8% quality, below 4.7% quality, below 4.6% quality, below 4.5% quality, below 4.4% quality, below 4.3% quality, below 4.2% quality, below 4.1% quality, below 4% quality, below 3.9% quality, below 3.8% quality, below 3.7% quality, below 3.6% quality, below 3.5% quality, below 3.4% quality, below 3.3% quality, below 3.2% quality, below 3.1% quality, and even below 3% quality.

[0085] (ZnO)

[0086] ZnO is a component used to adjust the devitrification temperature and viscosity during glass formation. Additionally, ZnO increases the Young's modulus of glass and reduces its coefficient of linear expansion. Furthermore, ZnO adjusts the dielectric constant and loss tangent of glass. When the ZnO content is 3% by mass or more and 12% by mass or less, the rise in the devitrification temperature of the glass is suppressed, and the uniformity of the raw material melting is increased. The lower limit of ZnO content can be higher than 3% by mass, 3.1% by mass or more, 3.2% by mass or more, 3.3% by mass or more, 3.4% by mass or more, 3.5% 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, 6.5% by mass or more, 7% by mass or more, and even higher than 7% by mass or 7.1% by mass or more. The upper limit for ZnO can be below 11% by mass, below 10.5% by mass, below 10% by mass, below 9.5% by mass, below 9% by mass, below 8.5% by mass, below 8% by mass, below 8% by mass, or even below 7.9% by mass.

[0087] (MgO + CaO + SrO + ZnO)

[0088] The sum of the contents of MgO, CaO, SrO, and ZnO (MgO + CaO + SrO + ZnO) is important for adjusting various properties. Proper adjustment of (MgO + CaO + SrO + ZnO) is effective in suppressing excessive rises in devitrification temperature, and also in keeping the devitrification temperature and viscosity of the molten glass within a suitable range for glass manufacturing. The lower limit of (MgO + CaO + SrO + ZnO) can be 3% by mass or more, 3.1% by mass or more, 3.2% by mass or more, 3.3% by mass or more, 3.4% by mass or more, 3.5% by mass or more, 3.6% by mass or more, 3.7% by mass or more, 3.8% by mass or more, 3.9% 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, 6.5% 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 even 9% by mass or more. The upper limit for (MgO + CaO + SrO + ZnO) can be below 25% by mass, below 24% by mass, below 23% by mass, below 22% by mass, below 21% by mass, below 20% by mass, below 19% by mass, below 18% by mass, below 17% by mass, below 16% by mass, below 15% by mass, below 14% by mass, below 13% by mass, below 12% by mass, below 11% by mass, and even below 10% by mass.

[0089] (Li2O, Na2O, K2O)

[0090] Alkali metal oxides (Li₂O, Na₂O, K₂O) are components used to adjust the devitrification temperature and viscosity during glass formation. When the total content of alkali metal oxides (Li₂O + Na₂O + K₂O) is 0% by mass or more and 2% by mass or less, it can suppress excessive rise in devitrification temperature while ensuring that the devitrification temperature and viscosity of the molten glass are within a range suitable for glass manufacturing. Furthermore, even while suppressing the rise in the glass melting point and achieving more uniform melting of the glass raw materials, it prevents an excessive decrease in the glass transition temperature, ensuring high heat resistance of the glass. The lower limit for (Li₂O + Na₂O + K₂O) can be 0% by mass or more, above 0% by mass, 0.05% by mass or more, 0.1% by mass or more, above 0.1% by mass, and even above 0.15% by mass or more. The addition of trace amounts of alkali metal oxides is effective in reducing bubbles in the glass. The upper limit for (Li₂O + Na₂O + K₂O) can be below 1.5% by mass, below 1% by mass, below 0.9% by mass, below 0.8% by mass, below 0.7% by mass, below 0.6% by mass, below 0.5% by mass, below 0.4% by mass, or even below 0.3% by mass. It can also substantially not contain alkali metal oxides. Li₂O, Na₂O, and K₂O are arbitrary components. In other words, the lower limit for the content of each component can be 0.

[0091] The lower limit of Li₂O content can be above 0% by mass, above 0%, above 0.01% by mass, above 0.02% by mass, above 0.03% by mass, above 0.04% by mass, above 0.05% by mass, above 0.06% by mass, above 0.07% by mass, and even above 0.08% by mass. The upper limit of Li₂O content can be below 2% by mass, below 1.5% by mass, below 1% by mass, below 1% by mass, below 0.9% by mass, below 0.8% by mass, below 0.7% by mass, below 0.6% by mass, below 0.5% by mass, below 0.4% by mass, below 0.3% by mass, and even below 0.2% by mass. It can also be substantially free of Li₂O.

[0092] The lower limit of Na₂O content can be above 0% by mass, above 0%, above 0.01% by mass, above 0.02% by mass, above 0.03% by mass, above 0.04% by mass, above 0.05% by mass, above 0.06% by mass, above 0.07% by mass, and even above 0.08% by mass. The upper limit of Na₂O content can be below 2% by mass, below 1.5% by mass, below 1% by mass, below 1% by mass, below 0.9% by mass, below 0.8% by mass, below 0.7% by mass, below 0.6% by mass, below 0.5% by mass, below 0.4% by mass, below 0.3% by mass, and even below 0.2% by mass. It can also be substantially free of Na₂O.

[0093] The lower limit of K2O content can be above 0% by mass, above 0%, above 0.01%, above 0.02%, above 0.03%, above 0.04%, above 0.05%, above 0.06%, above 0.07%, and even above 0.08% by mass. The upper limit of K2O content can be below 2% by mass, below 1.5% by mass, below 1% by mass, below 1% by mass, below 0.9% by mass, below 0.8% by mass, below 0.7% by mass, below 0.6% by mass, below 0.5% by mass, below 0.4% by mass, below 0.3% by mass, and even below 0.2% by mass. It can also be substantially free of K2O.

[0094] Regarding the meltability and formability of glass, the sum of the contents of Na₂O and K₂O (Na₂O + K₂O) is important. The content of (Na₂O + K₂O) can be below 2% by mass, below 1.5% by mass, below 1% by mass, below 1% by mass, below 0.9% by mass, below 0.8% by mass, below 0.7% by mass, below 0.6% by mass, below 0.5% by mass, below 0.4% by mass, below 0.3% by mass, below 0.2% by mass, and even below 0.15% by mass, and can be below 0.1% depending on the situation. The lower limit of the (Na₂O + K₂O) content can be above 0% by mass, above 0% by mass, and above 0.05% by mass.

[0095] (TiO2)

[0096] TiO2 is a component used to adjust the devitrification temperature and viscosity during glass formation. Additionally, TiO2 increases the Young's modulus of glass and reduces its coefficient of linear expansion. Furthermore, TiO2 improves the melt flow properties and chemical durability of glass, as well as its ultraviolet absorption characteristics. Moreover, TiO2 adjusts the dielectric constant and dielectric loss tangent of glass. The TiO2 content is 0.1% by mass or more and 5% by mass or less. The lower limit of the TiO2 content can be higher than 0.2% by mass, 0.25% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 1.6% by mass or more, 1.7% by mass or more, 1.8% by mass or more, 1.9% by mass or more, 2% by mass or more, higher than 2% by mass, 2.1% by mass or more, and even 2.2% by mass or more. The upper limit of TiO2 content can be below 4.5% by mass, below 4% by mass, below 3.8% by mass, below 3.5% by mass, below 3% by mass, below 3% by mass, below 3% by mass, below 2.9% by mass, or even below 2.8% by mass.

[0097] (ZnO + TiO2)

[0098] The sum of the contents of ZnO and TiO2 (ZnO + TiO2) is important in regulating the devitrification temperature and viscosity during glass formation. Furthermore, it is crucial in regulating the Young's modulus and coefficient of linear expansion of the glass, as well as its dielectric constant and loss tangent. The lower limit for (ZnO + TiO2) can be 3.1% by mass or more, 3.2% by mass or more, 3.3% by mass or more, 3.4% by mass or more, 3.5% by mass or more, 3.6% by mass or more, 3.7% by mass or more, 3.8% by mass or more, 3.9% 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, 6.5% 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, 9% by mass or more, 9.5% by mass or more, and even 10% by mass or more. The upper limit for (ZnO + TiO2) can be below 17% by mass, below 16% by mass, below 15% by mass, below 14% by mass, below 13% by mass, below 12% by mass, or even below 11% by mass.

[0099] (P2O5)

[0100] P2O5 is an arbitrary component. P2O5 forms the framework of the glass. Additionally, P2O5 is a component that adjusts the devitrification temperature and viscosity during glass formation. Furthermore, P2O5 reduces the coefficient of linear expansion of the glass. Moreover, P2O5 adjusts the dielectric constant and loss tangent of the glass. The upper limit of P2O5 content can be below 10% by mass, below 9% by mass, below 8% by mass, below 7% by mass, below 6.5% by mass, below 6% by mass, below 5% by mass, below 4% by mass, below 3% by mass, below 2% by mass, below 1% by mass, below 0.5% by mass, below 0.2% by mass, below 0.2% by mass, or even below 0.1% by mass. It can also be substantially free of P2O5. The lower limit of P2O5 content can be above 0% by mass and above 0.1% by mass.

[0101] (BaO)

[0102] BaO can be any component. BaO is a component used to adjust the devitrification temperature and viscosity during glass formation. On the other hand, excessive BaO content reduces the Young's modulus of the glass and increases its coefficient of linear expansion. The upper limit of BaO content can be below 5% by mass, below 4% by mass, below 3% by mass, below 2% by mass, below 2% by mass, below 1.5% by mass, below 1% by mass, below 1% by mass, below 1% by mass, below 0.5% by mass, below 0.2% by mass, or even below 0.1% by mass. It can also be substantially free of BaO. The lower limit of BaO content can be above 0% by mass and above 0.1% by mass.

[0103] (MgO + CaO + SrO + BaO)

[0104] Regarding the meltability and formability of glass, the total content of MgO, CaO, SrO, and BaO (MgO + CaO + SrO + BaO) is important. From the viewpoint of obtaining meltability and formability suitable for glass manufacturing, the lower limit of (MgO + CaO + SrO + BaO) can be above 0% by mass, above 0%, above 0.1% by mass, above 0.2% by mass, above 0.3% by mass, above 0.4% by mass, above 0.5% by mass, above 0.6% by mass, above 0.7% by mass, above 0.8% by mass, above 0.9% by mass, above 1% by mass, above 1.5% by mass, and even above 2% by mass. In addition, the upper limit of (MgO + CaO + SrO + BaO) can be below 18% by mass, below 17% by mass, below 16% by mass, below 15% by mass, below 14% by mass, below 13% by mass, below 12% by mass, below 11% by mass, below 10% by mass, below 9.5% by mass, below 9% by mass, below 8.5% by mass, below 8% by mass, below 7.5% by mass, below 7% by mass, below 6.5% by mass, below 6% by mass, below 5.5% by mass, below 5% by mass, below 4.5% by mass, below 4% by mass, below 3.5% by mass, and even below 3% by mass.

[0105] (ZrO2)

[0106] ZrO2 can be any component. ZrO2 is used to adjust the devitrification temperature and viscosity during glass formation. Additionally, ZrO2 increases the Young's modulus of the glass and reduces its coefficient of linear expansion. Furthermore, ZrO2 adjusts the dielectric constant and loss tangent of the glass. The lower limit of ZrO2 content can be above 0% by mass, above 0%, above 0.1% by mass, above 0.1% by mass, above 0.1% by mass, above 0.15% by mass, above 0.2% by mass, above 0.25% by mass, above 0.3% by mass, above 0.35% by mass, above 0.4% by mass, above 0.45% by mass, and even above 0.5% by mass. The maximum ZrO2 content can be below 5% by mass, below 4.5% by mass, below 4% by mass, below 3.5% by mass, below 3% by mass, below 2.5% by mass, below 2% by mass, below 1.5% by mass, below 1.4% by mass, below 1.3% by mass, below 1.2% by mass, below 1.1% by mass, or even below 1% by mass. It can also be substantially free of ZrO2.

[0107] (ZnO + TiO2 + ZrO2)

[0108] The sum of the contents of ZnO, TiO2, and ZrO2 (ZnO + TiO2 + ZrO2) can be adjusted to a range of 3.1% by mass or more and 22% by mass or less, from the viewpoint of suppressing the rise in devitrification temperature while keeping the devitrification temperature and viscosity of the molten glass within a range suitable for glass manufacturing. This range is also preferred from the viewpoint of ensuring a low coefficient of linear expansion and a high Young's modulus. Furthermore, this range is also preferred from the viewpoint of ensuring a low dielectric constant and a low dielectric loss tangent. The lower limit for (ZnO + TiO2 + ZrO2) can be above 3.5% by mass, above 3.6% by mass, above 3.7% by mass, above 3.8% by mass, above 3.9% by mass, above 4% by mass, above 4.5% by mass, above 5% by mass, above 5.5% by mass, above 6% by mass, above 6.5% by mass, above 7% by mass, above 7.5% by mass, above 8% by mass, above 8.5% by mass, above 9% by mass, above 9.5% by mass, and even above 10% by mass. The upper limit for (ZnO + TiO2 + ZrO2) can be below 21% by mass, below 20% by mass, below 19% by mass, below 18% by mass, below 17% by mass, below 16% by mass, below 15% by mass, below 14% by mass, below 13% by mass, below 12% by mass, and even below 11% by mass.

[0109] (TiO2 + ZrO2)

[0110] The sum of the contents of TiO2 and ZrO2 (TiO2 + ZrO2) is important in regulating the devitrification temperature and viscosity during glass formation. Furthermore, it is crucial in regulating the Young's modulus and coefficient of linear expansion of the glass, as well as its dielectric constant and loss tangent. The lower limit for (TiO2 + ZrO2) can be above 0.1% by mass, exceeding 0.2%, 0.25% by mass, 0.3% by mass, 0.4% by mass, 0.5% by mass, 1% by mass, 1.5% by mass, and even above 2% by mass. The upper limit for (TiO2 + ZrO2) can be below 10% by mass, below 9.5% by mass, below 9% by mass, below 8.5% by mass, below 8% by mass, below 7.5% by mass, below 7% by mass, below 6.5% by mass, below 6% by mass, below 5.5% by mass, below 5% by mass, below 4.5% by mass, and even below 4% by mass.

[0111] (ZnO + ZrO2)

[0112] The sum of the contents of ZnO and ZrO2 (ZnO + ZrO2) is important in regulating the devitrification temperature and viscosity during glass formation. Furthermore, it is crucial in regulating the Young's modulus and coefficient of linear expansion of the glass, as well as its dielectric constant and loss tangent. The lower limit for (ZnO + ZrO2) can be 3% by mass or higher, 3.1% by mass or higher, 3.2% by mass or higher, 3.3% by mass or higher, 3.4% by mass or higher, 3.5% by mass or higher, 4% by mass or higher, 4.5% by mass or higher, 5% by mass or higher, 5.5% by mass or higher, 6% by mass or higher, 6.5% by mass or higher, 7% by mass or higher, exceeding 7% by mass, 7.1% by mass or higher, and even exceeding 7.5% by mass. The upper limit for (ZnO + ZrO2) can be below 17% by mass, below 16% by mass, below 15% by mass, below 14% by mass, below 13% by mass, below 12% by mass, below 11% by mass, below 10% by mass, below 9.5% by mass, below 9% by mass, below 8.5% by mass, below 8% by mass, below 8% by mass, even below 7.9% by mass.

[0113] (B2O3 + ZnO + TiO2)

[0114] The total content of B₂O₃, ZnO, and TiO₂ (B₂O₃ + ZnO + TiO₂) is important for adjusting various properties. Proper adjustment of (B₂O₃ + ZnO + TiO₂) is effective in suppressing excessive rises in devitrification temperature, and also in keeping the devitrification temperature and viscosity of the molten glass within a suitable range for glass manufacturing. Furthermore, proper adjustment of (B₂O₃ + ZnO + TiO₂) is also effective from the viewpoint of ensuring a low dielectric constant and a low dielectric loss tangent. The lower limit for (B₂O₃ + ZnO + TiO₂) can be above 9.1% by mass, above 9.2% by mass, above 9.3% by mass, above 9.4% by mass, above 9.5% by mass, above 10% by mass, above 11% by mass, above 12% by mass, above 13% by mass, above 14% by mass, above 15% by mass, above 16% by mass, above 17% by mass, above 18% by mass, above 19% by mass, above 20% by mass, and even above 21% by mass. The upper limit for (B₂O₃ + ZnO + TiO₂) can be below 32% by mass, below 31% by mass, below 30% by mass, below 29% by mass, below 28% by mass, below 27% by mass, below 26% by mass, below 25% by mass, and even below 24% by mass.

[0115] (B2O3+ZnO+TiO2+ZrO2)

[0116] The total content of B₂O₃, ZnO, TiO₂, and ZrO₂ (B₂O₃ + ZnO + TiO₂ + ZrO₂) is important for adjusting various properties. Proper adjustment of (B₂O₃ + ZnO + TiO₂ + ZrO₂) is effective in suppressing excessive rises in devitrification temperature, and also in keeping the devitrification temperature and viscosity of the molten glass within a suitable range for glass manufacturing. Furthermore, proper adjustment of (B₂O₃ + ZnO + TiO₂ + ZrO₂) is also effective from the viewpoint of ensuring a low dielectric constant and a low dielectric loss tangent. The lower limit for (B₂O₃ + ZnO + TiO₂ + ZrO₂) can be above 9.1% by mass, above 9.2% by mass, above 9.3% by mass, above 9.4% by mass, above 9.5% by mass, above 10% by mass, above 11% by mass, above 12% by mass, above 13% by mass, above 14% by mass, above 15% by mass, above 16% by mass, above 17% by mass, above 18% by mass, above 19% by mass, above 20% by mass, and even above 21% by mass. The upper limit for (B₂O₃ + ZnO + TiO₂ + ZrO₂) can be below 32% by mass, below 31% by mass, below 30% by mass, below 29% by mass, below 28% by mass, below 27% by mass, below 26% by mass, below 25% by mass, and even below 24% by mass.

[0117] (Fe)

[0118] In glass, Fe is usually in the form of Fe2+. 2+ or Fe 3+ The state exists. Fe 3+ It is a component that improves the ultraviolet absorption properties of glass, Fe. 2+ Fe is a component that enhances the infrared absorption properties of glass. The upper limit of Fe content, expressed as T-Fe₂O₃, is below 5% by mass, below 4% by mass, below 3% by mass, below 2% by mass, below 1% by mass, below 0.5% by mass, below 0.4% by mass, below 0.3% by mass, below 0.2% by mass, and even below 0.15% by mass. The lower limit of Fe content, also expressed as T-Fe₂O₃, is above 0% by mass, above 0%, above 0.04% by mass, above 0.05% by mass, above 0.06% by mass, above 0.07% by mass, and even above 0.08% by mass. Especially in glass compositions with low alkali metal oxide content, trace amounts of iron oxide can promote glass clarification and help reduce bubbles. Alternatively, it may be substantially free of Fe.

[0119] (CeO2, SnO2)

[0120] CeO2 and / or SnO2 are optional components. Especially in glass compositions with low alkali metal oxide content, trace amounts of CeO2 and / or SnO2 help promote glass clarification. CeO2 and / or SnO2 are components that regulate the devitrification temperature and viscosity during glass formation. Furthermore, CeO2 and / or SnO2 are components that increase the Young's modulus of the glass and reduce its coefficient of linear expansion. The lower limits of CeO2 and / or SnO2 content can be above 0% by mass, above 0% by mass, above 0.05% by mass, above 0.1% by mass, and even above 0.15% by mass, respectively. The upper limits of CeO2 and / or SnO2 content can be below 2% by mass, below 1% by mass, below 0.5% by mass, below 0.4% by mass, below 0.3% by mass, below 0.25% by mass, and even below 0.2% by mass, respectively. It is also possible to substantially exclude CeO2. It is also possible to substantially exclude SnO2. Furthermore, the CeO2 content is expressed as T-CeO2. The SnO2 content is expressed as T-SnO2.

[0121] (MnO2)

[0122] MnO2 can be any component. MnO2 is used to adjust the devitrification temperature and viscosity during glass formation. The upper limits for MnO2 content can be below 2% by mass, below 1% by mass, below 0.5% by mass, below 0.2% by mass, or even below 0.1% by mass. It can also be substantially free of MnO2. Furthermore, the MnO2 content is expressed as T - MnO2.

[0123] (CuO)

[0124] CuO can be any component. CuO is used to adjust the devitrification temperature and viscosity during glass formation. The upper limit of CuO content can be below 2% by mass, below 1% by mass, below 0.5% by mass, below 0.2% by mass, or even below 0.1% by mass. It can also be substantially devoid of CuO. The CuO content is expressed as T-CuO.

[0125] (SO3)

[0126] SO3 can be any component. Trace amounts of SO3 can reduce residual bubbles in glass and help improve the glass's suitability for mass production. The lower limit of SO3 content can be above 0% by mass, above 0.001% by mass, and further above 0.002% by mass. The upper limit of SO3 content can be below 0.5% by mass, below 0.2% by mass, below 0.1% by mass, below 0.05% by mass, below 0.04% by mass, below 0.03% by mass, below 0.02% by mass, and even below 0.01% by mass. It can also be substantially free of SO3.

[0127] (Nb2O5)

[0128] Nb₂O₅ is an optional component. Trace amounts of Nb₂O₅ contribute to the clarification of glass. Nb₂O₅ is a component that regulates the devitrification temperature and viscosity during glass formation. Additionally, Nb₂O₅ increases the Young's modulus of glass and reduces its coefficient of linear expansion. The lower limit for Nb₂O₅ content can be above 0% by mass, above 0%, above 0.001% by mass, or even above 0.002% by mass. The upper limit for Nb₂O₅ content can be below 3% by mass, below 2% by mass, below 2% by mass, below 1% by mass, below 0.5% by mass, below 3% by mass, below 2% by mass, below 2% by mass, below 1% by mass, below 0.5% by mass, or even below 0.1% by mass. It is also possible to have virtually no Nb₂O₅.

[0129] (F2, Cl2)

[0130] Fluorine (F2) and / or chlorine (Cl2) are also optional components. Especially in glass compositions with low alkali metal oxide content, F2 and / or Cl2 can help promote glass clarification. However, F2 and / or Cl2 are volatile, and therefore there is a possibility of dispersion during melting. The upper limits for the content of F2 and / or Cl2 can be below 5% by mass, below 4% by mass, below 3% by mass, below 2% by mass, below 1% by mass, below 0.5% by mass, below 0.2% by mass, and even below 0.1% by mass. It is also possible to substantially exclude F2. The lower limits for the content of F2 and / or Cl2 can be above 0% by mass, above 0%, above 0.1% by mass, above 0.2% by mass, above 0.3% by mass, above 0.35% by mass, and even above 0.4% by mass. It is also possible to substantially exclude Cl2.

[0131] (Total of ingredients)

[0132] The total of the aforementioned components, namely from SiO2 to F2 and Cl2, can be 95% by mass or more, 96% by mass or more, 97% by mass or more, 98% by mass or more, or even 99% by mass or more, and depending on the circumstances, it can be 99.5% by mass or more.

[0133] (Other ingredients)

[0134] Other arbitrary components may include at least one selected from the group consisting of HfO2, Ga2O3, La2O3, Pr2O3, Nd2O3, Pm2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, WO3, Sc2O3, Y2O3, MoO3, Ta2O5, Cr2O3, CoO, PbO, Bi2O3, Br2, I2, As2O3, and Sb2O3. However, other arbitrary components are not limited to this. Other arbitrary components may each be contained in a concentration of 3% by mass or less. The permissible concentrations of other arbitrary components may be 2% by mass or less, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, or even less than 0.1% by mass. Other arbitrary components may also be substantially excluded. For example, from an environmental protection perspective, it is desirable that As₂O₃ and / or Sb₂O₃ are substantially absent. The total content of any other components listed above can be less than 5% by mass, less than 3% by mass, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, or even less than 0.1% by mass.

[0135] <Preferred Composition>

[0136] The following examples illustrate preferred compositions. The range within which each component is described simultaneously in parentheses represents a more preferred range.

[0137] Expressed as a percentage of mass,

[0138] 56≤SiO2≤64 (58≤SiO2≤63).

[0139] 8 < B2O3 ≤ 15 (8.5 ≤ B2O3 ≤ 14).

[0140] 14 < Al2O3 ≤ 19 (14 < Al2O3 ≤ 17).

[0141] 0≤MgO≤6 (0≤MgO≤5)

[0142] 0.5≤CaO≤4 (0.5≤CaO≤3.5)

[0143] 0≤SrO≤4 (0≤SrO≤2.5)

[0144] 3 < ZnO ≤ 12 (4 ≤ ZnO < 8).

[0145] 0≤(Li2O+Na2O+K2O)≤1(0.1≤(Li2O+Na2O+K2O)≤0.8),

[0146] 0.1≤TiO2≤4 (1≤TiO2≤3.8)

[0147] 0.1≤ZrO2≤3 (0.1≤ZrO2≤2).

[0148] <Characteristics>

[0149] The properties of the glass composition of this embodiment will be described below.

[0150] (Melting characteristics)

[0151] The temperature at which the viscosity of molten glass reaches 1000 dPa·sec (1000 poise) is called the operating temperature of that glass, which is the suitable temperature for glass forming. If the operating temperature is above 1100℃, dimensional deviations such as glass fiber diameter can be reduced. If the operating temperature is below 1450℃, fuel costs during glass melting can be reduced, and glass manufacturing equipment is less susceptible to thermal corrosion, extending its lifespan. The lower limit of the operating temperature can be above 1200℃, 1300℃, 1320℃, 1330℃, 1340℃, 1350℃, 1360℃, 1370℃, and even above 1380℃. The upper limit of the operating temperature can be below 1440℃, 1430℃, 1420℃, 1410℃, and even below 1405℃.

[0152] The larger the temperature difference ΔT between the operating temperature and the devitrification temperature, the less likely devitrification will occur during glass forming, enabling the production of homogeneous glass with high yield. ΔT can be above 0°C, above 5°C, above 10°C, or even above 15°C. There is no particular upper limit to ΔT, but it is, for example, below 150°C, below 120°C, below 100°C, below 90°C, below 80°C, below 70°C, below 60°C, and further below 50°C. Furthermore, the devitrification temperature is the temperature at which crystals form and begin to grow in the molten glass preform, and can be measured by the methods described later.

[0153] (Coefficient of linear expansion)

[0154] The coefficient of linear expansion, more precisely, is the average coefficient of linear expansion between 50 and 350°C. The low coefficient of linear expansion of glass contributes to improved dimensional stability of resin compositions containing glass. The lower limit of the coefficient of linear expansion can be 20 × 10⁻⁶. -7 / ℃ or above, 21×10 -7 / ℃ or above, 22×10 -7 / ℃ or above, 23×10 -7 / ℃ or above, 24×10 -7 / ℃ or higher, even 25×10 -7 Above / ℃. The upper limit of the linear expansion coefficient can be 30×10. -7 / ℃ below, 29×10 -7 / ℃ below, 28×10 -7 Below / ℃, even 27×10 -7 / ℃ below.

[0155] (Glass transition temperature)

[0156] The glass transition temperature (glass transition point) is an indicator of the heat resistance of glass. When glass-containing resin compositions are used for heat treatment, a high glass transition temperature is desirable. The lower limit of the glass transition temperature can be above 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, 610℃, 620℃, 630℃, 640℃, and even above 650℃. The upper limit of the glass transition temperature can be below 750℃, below 740℃, below 730℃, above 720℃, above 710℃, above 700℃, above 690℃, and even below 680℃.

[0157] (Young's modulus)

[0158] A high Young's modulus in glass contributes to improved mechanical properties and dimensional stability of resin compositions containing glass fibers or fillers. Young's modulus can be calculated from the longitudinal and transverse wave velocities of the elastic wave propagating in the glass, measured by conventional ultrasonic methods, and the glass density, measured by the Archimedes method. The lower limit of Young's modulus can be above 65 GPa, 66 GPa, 67 GPa, 68 GPa, 69 GPa, and even above 70 GPa. The upper limit of Young's modulus can be below 85 GPa, 84 GPa, 83 GPa, 82 GPa, 81 GPa, and even below 80 GPa.

[0159] (Dielectric constant, dielectric loss tangent)

[0160] The low dielectric constant of glass contributes to improved dielectric properties of resin compositions containing glass fibers or glass fillers. The dielectric constant measured at 1 GHz is 6.0 or less, 5.9 or less, 5.8 or less, 5.7 or less, 5.6 or less, 5.5 or less, 5.4 or less, 5.3 or less, 5.2 or less, 5.1 or less, 5.0 or less, 4.9 or less, and further can be 4.8 or less. Strictly speaking, dielectric constant means specific dielectric constant, but in this specification it is conventionally referred to simply as dielectric constant. The dielectric constant is the value at room temperature (25°C). The dielectric constant can be 4.5 or greater.

[0161] The low dielectric loss tangent of glass also helps to improve the dielectric properties of resin compositions containing glass fibers or glass fillers. The dielectric loss tangent at a measurement frequency of 1 GHz can be below 0.0045, 0.0044, 0.0043, 0.0042, 0.0041, 0.0040, 0.0039, 0.0038, 0.0037, 0.0036, 0.0035, 0.0034, 0.0033, 0.0032, 0.0031, 0.0030, 0.0029, 0.0028, 0.0027, 0.0026, 0.0025, 0.0024, 0.0023, 0.0022, 0.0021, and even below 0.0020. The dielectric loss tangent is the value at room temperature (25°C). The dielectric loss tangent can be above 0.0010, above 0.0011, above 0.0012, above 0.0013, above 0.0014, or even above 0.0015.

[0162] [Glass products]

[0163] <Glass fiber>

[0164] The glass fiber of this embodiment is composed of the glass composition described above. According to this embodiment, even when the fiber diameter is small, the glass fiber can be a glass fiber with a very small fiber diameter because it is possible to further suppress the occurrence of devitrification and bubble incorporation.

[0165] The average fiber diameter of the glass fiber is, for example, 0.1–50 μm. The average fiber diameter can be 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 1 μm or more, 2 μm or more, and even 3 μm or more. Alternatively, the average fiber diameter can be 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 8 μm or less, 6 μm or less, 5 μm or less, 4.6 μm or less, and even 4.3 μm or less. A glass composition having a characteristic temperature suitable for mass production is suitable for stable manufacturing into fine glass fibers. In a preferred embodiment, the average fiber diameter is even finer, for example, 3.9 μm or less, or even 3.5 μm or less. The glass fiber is, for example, a long glass fiber (filament: monofilament).

[0166] Glass fibers can have at least one shape selected from the group consisting of: roving, roving fabric, continuous filament mat, ground fiber, flat fiber, monofilament mat, chopped strand, yarn, glass cloth, and glass tape.

[0167] Flat fibers are glass fibers with a flattened cross-section, such as an ellipse. The major axis D2 is larger than the minor axis D1 of the flat fiber's cross-section, with a D2 / D1 ratio of, for example, 1.2 or more. The minor axis D1 is, for example, 0.5–25 μm. The major axis D2 is, for example, 0.6–300 μm. The length L of the flat fiber is, for example, 10–100,000 μm. Flat fibers can be obtained by known methods. The cross-sectional shape of the flat fiber can also have a concave shape where the surface extending along the major axis D2 is recessed at the center compared to the ends.

[0168] Glass fibers can be manufactured by a method including the following steps: a step of melting the glass composition of this embodiment; and a step of forming the molten glass composition into glass fibers.

[0169] <Glass packing>

[0170] The glass filler of this embodiment is composed of the glass composition described above. The glass filler may be at least one selected from the group consisting of sheet glass, glass powder, glass beads, and fine flakes.

[0171] Flake glass, also known as sheet glass, has a sheet-like shape. The average grain size of flake glass is, for example, 0.2–15000 μm. The aspect ratio of flake glass is, for example, 2–1000. The aspect ratio can be obtained by dividing the average grain size by the average thickness. The average thickness can be obtained by measuring the thickness t of more than 100 flake glass pieces using a scanning electron microscope (SEM) and calculating the average value. The average grain size of the glass filler other than the flake glass can be determined based on the grain size distribution measured by laser diffraction scattering, where the cumulative volume percentage corresponds to the grain size (D50). Flake glass can be obtained by known methods such as glass blowing and rotating cup methods.

[0172] Glass powder is powdered glass, manufactured by crushing glass. The average particle size of glass powder is, for example, 1–500 μm. The particle size of glass powder is defined as the diameter of a sphere of the same volume as the glass powder particles. Glass powder can be obtained by known methods.

[0173] Glass beads have a spherical or near-spherical shape. The average particle size of glass beads is, for example, 1–500 μm. The particle size of a glass bead is defined as the diameter of a sphere with the same volume as the glass bead particles. Glass beads can be obtained by known methods.

[0174] Micro-flakes are thin, sheet-like glass particles. For example, micro-flakes can be composed of sheet-like glass with an average thickness of 0.1 to 2.0 μm, or, for example, can contain sheet-like glass with a thickness in the range of 0.01 to 2.0 μm in a proportion of 90% by mass or more. Micro-flakes with such a thin average thickness and very small thickness deviation have a high effect on reinforcing the resin and an excellent effect on reducing the molding shrinkage rate of the resin. Compared with conventional methods, micro-flakes are also more suitable for mitigating limitations such as the thickness of resin molded articles. Micro-flakes are preferably composed of sheet-like glass with an average thickness of 0.1 to 1.0 μm. Micro-flakes preferably contain sheet-like glass with a thickness in the range of 0.05 to 1.0 μm in a proportion of 90% by mass or more. Micro-flakes can be obtained by the methods described for sheet-like glass.

[0175] The glass filler can be manufactured by a method including the following steps: a step of melting the glass composition of this embodiment; and a step of shaping the molten glass composition into a glass filler.

[0176] [Articles containing glass fibers and / or glass fillers]

[0177] The glass fiber and glass filler of this embodiment can be used in various articles exemplified below. These articles have sides that serve as molded bodies, filler-containing articles, resin articles, etc.

[0178] <Molded body>

[0179] The molded body of this embodiment contains the aforementioned glass fiber and is molded into a predetermined shape. While not limited to the following, the molded body may be at least one selected from the group consisting of rubber-reinforced cord, nonwoven fabric, prepreg, reinforced plastic, printed circuit board, inorganic cured body, filter material, heat-insulating material, sound-absorbing material, and battery separator.

[0180] <Products containing fillers>

[0181] The filler-containing article of this embodiment contains the glass filler described above. While not limited to the following, the filler-containing article may be at least one selected from the group consisting of reinforced plastics, coatings, inks, printed circuit boards, inorganic cured bodies, and cosmetics.

[0182] <Resin Products>

[0183] The resin article of this embodiment contains the aforementioned glass fibers and / or glass fillers, as well as resin. The resin article can be an electrical insulating component or a structural component. Examples of such components are as described above. The resin can be a thermoplastic resin. Thermoplastic resins are not particularly limited, and for example, are polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyester, polyamide, polycarbonate, polybutene, polybutylene terephthalate, and copolymers thereof. If polybutylene terephthalate is used, the effect of suppressing warpage and improving dimensional stability of the molded article caused by mixing with glass fillers is greatly enhanced. Sheet glass, flat fibers, and fine flakes have a relatively large specific surface area, which is suitable for ensuring bonding strength with the thermoplastic resin.

[0184] [Technology provided by this embodiment]

[0185] The technology provided by this embodiment is as follows.

[0186] (Technology 1)

[0187] A glass composition, wherein, expressed in mass %

[0188] 55≤SiO2≤65,

[0189] 6 < B₂O₃ ≤ 20

[0190] 12≤Al2O3≤20,

[0191] 0≤MgO≤10,

[0192] 0≤CaO≤4,

[0193] 0≤SrO≤4,

[0194] 3≤ZnO≤12,

[0195] 0≤(Li2O+Na2O+K2O)≤2,

[0196] 0.1≤TiO2≤5,

[0197] 0.1≤ZrO2≤5.

[0198] (Technology 2)

[0199] A glass composition, wherein, expressed in mass %

[0200] 56≤SiO2≤65,

[0201] 6 < B₂O₃ ≤ 20

[0202] 12≤Al2O3≤19,

[0203] 0≤MgO≤10,

[0204] 0≤CaO≤4,

[0205] 0≤SrO≤4,

[0206] 3≤ZnO≤12,

[0207] 0≤(Li2O+Na2O+K2O)≤2,

[0208] 0.1≤TiO2≤5,

[0209] 0≤ZrO2≤5,

[0210] It does not actually contain BaO and As2O3.

[0211] (Technology 3)

[0212] A glass composition, wherein, expressed in mass %

[0213] 56≤SiO2≤65,

[0214] 6 < B₂O₃ ≤ 20

[0215] 12≤Al2O3≤19,

[0216] 0≤MgO≤10,

[0217] 0≤CaO≤4,

[0218] 0≤SrO≤4,

[0219] 3 < ZnO ≤ 12,

[0220] 0≤(Li2O+Na2O+K2O)≤2,

[0221] 0.1≤TiO2≤5,

[0222] 0≤ZrO2≤5,

[0223] It does not actually contain As2O3.

[0224] (Technology 4)

[0225] According to any one of techniques 1 to 3, the glass composition contains, in mass % of, 56 ≤ SiO2 ≤ 64.

[0226] (Technology 5)

[0227] According to any one of techniques 1 to 4, the glass composition contains, in mass % of, 8 < B2O3 ≤ 15.

[0228] (Technology 6)

[0229] According to any one of techniques 1 to 5, the glass composition wherein, expressed as a percentage by mass, the content of Al2O3 is 14 < Al2O3 ≤ 19.

[0230] (Technology 7)

[0231] A glass composition according to any one of techniques 1 to 6, wherein, expressed as a percentage by mass, the content of P2O5 is 0 ≤ P2O5 ≤ 6.

[0232] (Technology 8)

[0233] According to any one of techniques 1 to 7, the glass composition wherein, expressed as a percentage by mass, the content of MgO is 0 ≤ MgO ≤ 6.

[0234] (Technology 9)

[0235] According to any one of techniques 1 to 8, the glass composition contains, in mass % of, 0.5 ≤ CaO ≤ 4.

[0236] (Technology 10)

[0237] According to any one of techniques 1 to 9, the glass composition wherein, expressed as a percentage by mass, the content of SrO is 0.1 ≤ SrO ≤ 3.

[0238] (Technology 11)

[0239] A glass composition according to any one of techniques 1 to 10, wherein it substantially does not contain BaO.

[0240] (Technology 12)

[0241] A glass composition according to any one of techniques 1 to 11, wherein, expressed as a percentage by mass, the content of ZnO is 3 < ZnO < 8.

[0242] (Technology 13)

[0243] According to any one of techniques 1 to 12, the glass composition wherein, expressed as a percentage by mass, the content of (MgO + CaO + SrO) is 1 ≤ (MgO + CaO + SrO) ≤ 15.

[0244] (Technology 14)

[0245] According to any one of techniques 1 to 13, the glass composition wherein, expressed as a percentage by mass, the content of (MgO + CaO + SrO + ZnO) is 4 ≤ (MgO + CaO + SrO + ZnO) ≤ 20.

[0246] (Technology 15)

[0247] A glass composition according to any one of techniques 1 to 14, wherein, expressed as a percentage by mass, the content of (Li2O + Na2O + K2O) is 0 ≤ (Li2O + Na2O + K2O) ≤ 1.

[0248] (Technology 16)

[0249] According to the glass composition of Technique 15, the content of (Li2O + Na2O + K2O), expressed as a percentage by mass, is 0.1 ≤ (Li2O + Na2O + K2O) ≤ 1.

[0250] (Technology 17)

[0251] A glass composition according to any one of techniques 1 to 16, wherein, expressed as a percentage by mass, the content of (Na2O + K2O) is 0 ≤ (Na2O + K2O) ≤ 1.

[0252] (Technology 18)

[0253] A glass composition according to any one of techniques 1 to 17, wherein, expressed as a percentage by mass, the content of (TiO2 + ZrO2) is 1 ≤ (TiO2 + ZrO2) ≤ 8.

[0254] (Technology 19)

[0255] According to any one of techniques 1 to 18, the glass composition wherein, expressed as a percentage by mass, the content of (ZnO + TiO2 + ZrO2) is 6 ≤ (ZnO + TiO2 + ZrO2) ≤ 15.

[0256] (Technology 20)

[0257] A glass composition according to any one of techniques 1 to 19, wherein, expressed as a percentage by mass, the content of T-Fe2O3 is 0 ≤ T-Fe2O3 ≤ 5.

[0258] T-Fe2O3 is the total iron oxide converted to Fe2O3.

[0259] (Technology 21)

[0260] A glass composition according to any one of techniques 1 to 20, wherein, expressed as a percentage by mass, the content of T-SnO2 is 0 ≤ T-SnO2 ≤ 2.

[0261] T-SnO2 is the total tin oxide converted to SnO2.

[0262] (Technology 22)

[0263] A glass composition according to any one of techniques 1 to 21, wherein, expressed as a percentage by mass, the content of T-CeO2 is 0 ≤ T-CeO2 ≤ 2.

[0264] Wherein, T-CeO2 is the total cerium oxide converted to CeO2.

[0265] (Technology 23)

[0266] A glass composition according to any one of techniques 1 to 22, wherein it substantially does not contain CuO.

[0267] Wherein, T-CuO is the total copper oxide converted to CuO.

[0268] (Technology 24)

[0269] A glass composition according to any one of techniques 1 to 23, wherein it substantially does not contain T-MnO2.

[0270] Wherein, T-MnO2 is the total manganese oxide converted to MnO2.

[0271] (Technology 25)

[0272] A glass composition according to any one of techniques 1 to 24, wherein, expressed as a percentage by mass, the content of F2 is 0 ≤ F2 ≤ 5.

[0273] (Technology 26)

[0274] A glass composition according to any one of techniques 1 to 25, wherein, expressed as a percentage by mass, the content of SO3 is 0 ≤ SO3 ≤ 0.5.

[0275] (Technology 27)

[0276] According to any one of the art 1 to 26, the glass composition wherein, when the temperature at which the viscosity is 1000 dPa·sec is taken as the operating temperature, the operating temperature is 1450°C or below.

[0277] (Technology 28)

[0278] According to any one of the art 1 to 27, in a glass composition, when the temperature at which the viscosity is 1000 dPa·sec is taken as the operating temperature, the temperature difference ΔT between the operating temperature and the devitrification temperature is 0°C or more.

[0279] (Technology 29)

[0280] A glass composition according to any one of techniques 1 to 28, wherein the Young's modulus is 65 to 85 GPa.

[0281] (Technology 30)

[0282] According to any one of techniques 1 to 29, the glass composition wherein the average coefficient of linear expansion at 50–350°C is 20–30 × 10⁻⁶. -7 / ℃.

[0283] (Technology 31)

[0284] A glass composition according to any one of techniques 1 to 30, wherein the dielectric constant at a frequency of 1 GHz is 6.0 or less.

[0285] (Technology 32)

[0286] A glass composition according to any one of techniques 1 to 31, wherein the dielectric loss tangent at a frequency of 1 GHz is less than 0.0045.

[0287] (Technology 33)

[0288] A glass fiber comprising a glass composition according to any one of techniques 1 to 32.

[0289] (Technology 34)

[0290] According to technology 33, the glass fiber has at least one shape selected from the group consisting of roving, roving fabric, continuous filament mat, ground fiber, flat fiber, monofilament mat, chopped strand, yarn, glass cloth and glass tape.

[0291] (Technology 35)

[0292] A glass filler comprising a glass composition according to any one of techniques 1 to 32.

[0293] (Technology 36)

[0294] According to the glass filler of the technique 35, it is selected from at least one of the group consisting of sheet glass, glass powder, glass beads and fine flakes.

[0295] (Technology 37)

[0296] A molded body containing glass fibers of technique 33 or 34, selected from at least one of the group consisting of rubber-reinforced cords, nonwoven fabrics, prepregs, reinforced plastics, printed circuit boards, inorganic cured bodies, filter materials, thermal insulation materials, sound-absorbing materials, and battery separators.

[0297] (Technology 38)

[0298] A filler article containing glass filler of technique 35 or 36, selected from at least one group consisting of reinforced plastics, coatings, inks, printed circuit boards, inorganic cured bodies and cosmetics.

[0299] (Technology 39)

[0300] A method for manufacturing glass fiber, comprising the steps of: melting a glass composition according to any one of techniques 1 to 32; and forming the molten glass composition into glass fiber.

[0301] (Technology 40)

[0302] A method for manufacturing a glass filler, comprising the following steps: melting a glass composition according to any one of techniques 1 to 32; and shaping the molten glass composition into a glass filler.

[0303] Example

[0304] The following examples and comparative examples illustrate the implementation of the present invention in more detail.

[0305] (Examples and Comparative Examples)

[0306] Common glass raw materials such as silica sand were blended to achieve the compositions shown in Tables 1-10, and batches of glass raw materials were prepared according to each example and comparative example. Each batch was heated to 1500-1600°C in an electric furnace to melt it, and maintained in this state for approximately 4 hours until the composition was homogeneous. Subsequently, a portion of the molten glass (glass melt) was poured onto an iron plate and annealed in an electric furnace to room temperature to obtain a glass composition in block form (plate, glass sample). Furthermore, in Examples 14, 17, 24, 26, 39, 41, 42, 59, 62, and 63, tin(IV) oxide (SnO2) was used as the SnO2 source. In Examples 13, 36, and 43, cerium(IV) oxide (CeO2) was used as the CeO2 source. In Examples 8, 28, 43, and 49, sodium sulfate was used as the SO3 source, and in Example 21, lithium sulfate monohydrate was used as the SO3 source.

[0307] The following describes the evaluation method for characteristics.

[0308] (Operating temperature)

[0309] For the obtained glass composition, the relationship between viscosity and temperature was investigated using the conventional platinum ball pulling method, and the operating temperature was determined from the results. Here, the platinum ball pulling method is a method for measuring viscosity. Specifically, a platinum ball is immersed in molten glass, and the relationship between the load (resistance) when the platinum ball is pulled upwards at a uniform speed and the forces acting on the platinum ball, such as gravity and buoyancy, is applied to Stokes' law, which describes the relationship between viscosity and falling velocity of tiny particles settling in a fluid, to measure the viscosity.

[0310] (Devitrification temperature)

[0311] A glass composition pulverized to a particle size of 1.0–2.8 mm is placed in a platinum boat and held in an electric furnace with a temperature gradient (900–1500 °C) for 2 hours. The devitrification temperature is determined based on the highest temperature of the furnace corresponding to the location where crystals appear. When the glass becomes cloudy and no crystals are observed, the highest temperature of the furnace corresponding to the location where the cloudiness appears is taken as the devitrification temperature. Here, the particle size is measured by sieving. Furthermore, the different temperatures (temperature distribution within the furnace) corresponding to different locations can be measured in advance. The glass composition placed in a designated location within the furnace can be heated at the pre-measured temperature of that designated location. The temperature difference ΔT is the temperature difference between the operating temperature and the devitrification temperature.

[0312] (Coefficient of linear expansion)

[0313] For the obtained glass composition, the average linear expansion coefficient from 50 to 350 °C was measured using a commercially available dilatometer (Rigaku Corporation, Thermomechanical Analysis Apparatus, TMA8310). Furthermore, the glass transition temperature Tglass was obtained based on the thermal expansion curves obtained from the TMA apparatus. g .

[0314] (Young's modulus)

[0315] Young's modulus E is determined by measuring the longitudinal wave velocity vl and transverse wave velocity vt of an elastic wave propagating in glass using conventional ultrasonic methods. Additionally, it is derived from the glass density ρ measured using Archimedes' method, and E = 3ρ·vt. t 2 ·(v l 2 -4 / 3·v t 2 ) / (v l 2 -v t 2 The formula is used to obtain the result.

[0316] (Dielectric constant, dielectric loss tangent)

[0317] The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured using a dielectric constant measurement device based on the cavity resonator perturbation method. The measurement temperature was 25℃, and the sample used for measurement was a cuboid with a square base of 1.5 mm on each side and a height of 100 mm.

[0318] The measurement results are shown in Tables 1-10. Also, all glass compositions in the tables are expressed as mass % (%). Furthermore, Fe2O3 and SnO2 in the tables represent T-Fe2O3 and T-SnO2, respectively.

[0319] Table 1

[0320]

[0321] Table 2

[0322]

[0323] Table 3

[0324]

[0325] Table 4

[0326]

[0327] Table 5

[0328]

[0329] Table 6

[0330]

[0331] Table 7

[0332]

[0333] Table 8

[0334]

[0335] Table 9

[0336]

[0337] Table 10

[0338]

[0339] The following results can be obtained from the various embodiments: Young's modulus 69–82 GPa, linear expansion coefficient 25–27 × 10⁻⁶. -7 / ℃, glass transition temperature 637~714℃, operating temperature 1359~1412℃, temperature difference ΔT (operating temperature - devitrification temperature) 2~136℃, dielectric constant at 1GHz 4.4~5.1, dielectric loss tangent at 1GHz 0.0014~0.0036.

[0340] The glass composition of Comparative Example 1 has an E-glass composition. E-glass has a poor average coefficient of linear expansion at 50–350°C, and high dielectric constant and dielectric loss tangent at a frequency of 1 GHz. The glass composition of Comparative Example 2 has an S-glass composition. S-glass has a high operating temperature, a negative ΔT, and poor mass production. Furthermore, this glass has a slightly lower average coefficient of linear expansion at 50–350°C, and slightly higher dielectric constant and dielectric loss tangent at a frequency of 1 GHz. The glass composition of Comparative Example 3 has the glass composition of Example 2 of Patent Document 1. This glass has slightly higher operating temperature, dielectric constant, and dielectric loss tangent at a frequency of 1 GHz. The glass composition of Comparative Example 4 has the glass composition of Example 2 of Patent Document 2. This glass has a poor average coefficient of linear expansion at 50–350°C. Also, the coefficient of linear expansion of Comparative Example 4 (33 × 10⁻⁶) is... -7 / ℃) is higher than the measured value in Patent Document 2 (29×10 -7 The reason for the difference ( / ℃) is that the measured temperature ranges are different. Furthermore, during the inventors' follow-up tests, in Comparative Example 4, ΔT was negative, resulting in poor mass production. In addition, the dielectric constant and dielectric loss tangent of this glass at a frequency of 1 GHz are slightly high. The glass composition of Comparative Example 5 has the glass composition of Example 15 of Patent Document 3. This glass has a poor average linear expansion coefficient at 50–350°C, resulting in a negative ΔT and poor mass production. The glass compositions of Comparative Examples 6–20 have at least one of the following: average linear expansion coefficient, operating temperature, and difference ΔT, which is inferior to the ranges obtained from the examples.

Claims

1. A glass composition, wherein, Expressed as a percentage of mass, 55≤SiO2≤65, 6 < B₂O₃ ≤ 20 12≤Al2O3≤20, 0≤MgO≤10, 0≤CaO≤4, 0≤SrO≤4, 3≤ZnO≤12, 0≤(Li2O+Na2O+K2O)≤2, 0.1≤TiO2≤5, 0.1≤ZrO2≤5.

2. A glass composition, wherein, Expressed as a percentage of mass, 56≤SiO2≤65, 6 < B₂O₃ ≤ 20 12≤Al2O3≤19, 0≤MgO≤10, 0≤CaO≤4, 0≤SrO≤4, 3≤ZnO≤12, 0≤(Li2O+Na2O+K2O)≤2, 0.1≤TiO2≤5, 0≤ZrO2≤5, It does not actually contain BaO and As2O3.

3. A glass composition, wherein, Expressed as a percentage of mass, 56≤SiO2≤65, 6 < B₂O₃ ≤ 20 12≤Al2O3≤19, 0≤MgO≤10, 0≤CaO≤4, 0≤SrO≤4, 3 < ZnO ≤ 12, 0≤(Li2O+Na2O+K2O)≤2, 0.1≤TiO2≤5, 0≤ZrO2≤5, It does not actually contain As2O3.

4. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the SiO2 content is 56 ≤ SiO2 ≤ 64.

5. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of B2O3 is 8 < B2O3 ≤ 15%.

6. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of Al2O3 is 14 < Al2O3 ≤ 19.

7. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of P2O5 is 0 ≤ P2O5 ≤ 6.

8. The glass composition according to any one of claims 1 to 3, wherein, The percentage of MgO is expressed as a percentage by mass: 0 ≤ MgO ≤ 6%.

9. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the CaO content is 0.5 ≤ CaO ≤ 4%.

10. The glass composition according to any one of claims 1 to 3, wherein, The content of SrO is expressed as a percentage by mass: 0.1 ≤ SrO ≤ 3.

11. The glass composition according to any one of claims 1 to 3, wherein, It does not actually contain BaO.

12. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the ZnO content is 3 < ZnO < 8.

13. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of (MgO + CaO + SrO) is 1 ≤ (MgO + CaO + SrO) ≤ 15.

14. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of (MgO + CaO + SrO + ZnO) is 4 ≤ (MgO + CaO + SrO + ZnO) ≤ 20.

15. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of (Li2O + Na2O + K2O) is 0 ≤ (Li2O + Na2O + K2O) ≤ 1.

16. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of (Li2O + Na2O + K2O) is 0.1 ≤ (Li2O + Na2O + K2O) ≤ 1.

17. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of (Na2O + K2O) is 0 ≤ (Na2O + K2O) ≤ 1.

18. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of (TiO2 + ZrO2) is 1 ≤ (TiO2 + ZrO2) ≤ 8.

19. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of (ZnO + TiO2 + ZrO2) is 6 ≤ (ZnO + TiO2 + ZrO2) ≤ 15.

20. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of T-Fe2O3 is 0 ≤ T-Fe2O3 ≤ 5%. T-Fe2O3 is the total iron oxide converted to Fe2O3.

21. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of T-SnO2 is 0 ≤ T-SnO2 ≤ 2. T-SnO2 is the total tin oxide converted to SnO2.

22. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of T-CeO2 is 0 ≤ T-CeO2 ≤ 2. Wherein, T-CeO2 is the total cerium oxide converted to CeO2.

23. The glass composition according to any one of claims 1 to 3, wherein, It does not actually contain CuO, where T-CuO is the total copper oxide converted to CuO.

24. The glass composition according to any one of claims 1 to 3, wherein, It does not actually contain T-MnO2. Wherein, T-MnO2 is the total manganese oxide converted to MnO2.

25. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the content of F2 is 0 ≤ F2 ≤ 5.

26. The glass composition according to any one of claims 1 to 3, wherein, Expressed as a percentage by mass, the SO3 content is 0 ≤ SO3 ≤ 0.

5.

27. The glass composition according to any one of claims 1 to 3, wherein, When the temperature at which the viscosity is 1000 dPa·sec is taken as the operating temperature, the operating temperature is below 1450°C.

28. The glass composition according to any one of claims 1 to 3, wherein, When the temperature at which the viscosity is 1000 dPa·sec is taken as the operating temperature, the temperature difference ΔT obtained by subtracting the devitrification temperature from the operating temperature is above 0°C.

29. The glass composition according to any one of claims 1 to 3, wherein the Young's modulus is 65 GPa to 85 GPa.

30. The glass composition according to any one of claims 1 to 3, wherein the average coefficient of linear expansion at 50°C to 350°C is 20 × 10⁻⁶. -7 / ℃~30×10 -7 / ℃.

31. The glass composition according to any one of claims 1 to 3, wherein the dielectric constant at a frequency of 1 GHz is 6.0 or less.

32. The glass composition according to any one of claims 1 to 3, wherein the dielectric loss tangent at a frequency of 1 GHz is less than 0.0045.

33. A glass fiber comprising the glass composition according to any one of claims 1 to 3.

34. The glass fiber according to claim 33, having at least one shape selected from the group consisting of roving, roving fabric, continuous filament mat, ground fiber, flat fiber, monofilament mat, chopped strand, yarn, glass cloth and glass tape.

35. A glass filler comprising the glass composition according to any one of claims 1 to 3.

36. The glass filler according to claim 35, wherein it is selected from at least one of the group consisting of sheet glass, glass powder, glass beads and fine flakes.

37. A molded article comprising the glass fiber of claim 33, selected from at least one of the group consisting of rubber-reinforced cords, nonwoven fabrics, prepregs, reinforced plastics, printed circuit boards, inorganic cured bodies, filter materials, thermal insulation materials, sound-absorbing materials, and battery separators.

38. A filler article comprising the glass filler of claim 35, wherein at least one is selected from the group consisting of reinforced plastics, coatings, inks, printed circuit boards, inorganic cured bodies and cosmetics.

39. A method for manufacturing glass fiber, wherein, The process includes the following steps: The process of melting the glass composition according to any one of claims 1 to 3; and The process of forming the molten glass composition into glass fibers.

40. A method for manufacturing a glass filler, wherein, The process includes the following steps: The process of melting the glass composition according to any one of claims 1 to 3; and The process of shaping the molten glass composition into a glass filler.

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