Glass compositions, glass fibers and glass fillers

Abstract

This invention provides glass compositions with low linear expansion and high Young's modulus, suitable for mass production. The invention provides, expressed as a percentage by mass: i) glass compositions containing 56≤SiO2≤70, 0.1≤B2O3≤8, 15≤Al2O3≤24, 4≤MgO≤14, 0≤CaO≤4, 0≤ZnO≤10, 0≤(Li2O+Na2O+K2O)≤4, and 0.1≤ZrO2≤5, and substantially free of TiO2; ii) glass compositions containing 56≤SiO2≤70, 0.1≤B2O3≤8, 15≤Al2O3≤... 24. Glass compositions containing the following components: 4≤MgO≤14, 0≤CaO≤4, 0.1≤ZnO≤3, 0≤(Li2O+Na2O+K2O)≤4, and substantially not containing TiO2 and ZrO2; iii) Glass compositions containing the following components: 56≤SiO2≤70, 0.1≤B2O3≤8, 15≤Al2O3≤24, 4≤MgO≤14, 0≤CaO≤4, 0≤ZnO≤10, 0≤(Li2O+Na2O+K2O)≤4, 1≤ZrO2≤5.

Description

Technical Field

[0001] This invention relates to glass compositions, glass fibers and glass fillers, and further to articles such as molded articles comprising glass fibers or glass fillers. Background Technology

[0002] In electronic devices, resin compositions are widely used to construct electrical insulating and mechanical components. Examples of electrical insulating components include SMT (surface mount technology), FPC (flexible printed circuits), board-to-board connectors, connector housings used in CPU (central processing unit) sockets, memory cards, card edges, and optical connectors, reactor spools used in LCD (liquid crystal display) backlights, coils, flat panels, transformers, and magnetic heads, relay housings, relay base switches, reflux dual in-line package switches, tactile switches, sensor housings, condenser housings, potentiometer housings, and trimmer housings. Examples of mechanical components include lens holders and pickup bases for optical pickups, insulators and terminals for micromotors, and drums for laser printers. Resin compositions are also used as base films for FPCs and copper-clad laminates. Furthermore, some printed circuit boards (PCBs) in electronic devices also contain substrates made of resin compositions. The printed wiring board, which is used before electronic components are mounted, also contains a substrate made of a resin composition. Hereinafter, both the printed circuit board and the printed wiring board will be referred to as "printed board".

[0003] The aforementioned resin composition comprises thermoplastic resin and glass fiber, and may further include curing agents, modifiers, etc., as needed. The printed circuit board sometimes further includes inorganic filler materials. Glass fillers are sometimes used as inorganic filler materials. In recent years, to meet the requirements of miniaturization of electronic devices and thinness 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 Document 1 discloses a glass composition with a low linear coefficient of thermal expansion and a high Young's modulus, and glass fibers composed of this glass composition.

[0004] The glass composition disclosed in the embodiments of Patent Document 1 includes SiO2, B2O3, Al2O3, MgO, etc., and contains titanium oxide (TiO2) at a mass ratio of 0.7% to 3.0% and the content of zirconium oxide (ZrO2) is limited to 0.6% 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%. Patent Document 2 does not disclose a glass composition containing zirconium oxide (ZrO2). It should be noted that the linear thermal expansion coefficient of the E-glass disclosed in Patent Document 2 within the temperature range (50–200°C) is 53 × 10⁻⁶. -7 / ℃ (Comparative Example 1, Patent Document 2), but the coefficient for E-glass in the slightly wider temperature range (50~350℃) described later is slightly larger, at 60×10. -7 / ℃ (Comparative Example 1 of this application).

[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 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] With the trend towards miniaturization and increased functionality in electronic devices, dimensional stability is required for the resin compositions constituting these devices, and low linear coefficients of thermal expansion and high elastic moduli are required for the glass fibers and glass fillers used as constituent materials. Therefore, the object of this invention is to provide a new glass composition that has a low linear coefficient of thermal expansion and high Young's modulus, and is also suitable for mass production.

[0011] Methods for solving problems

[0012] The present invention provides the following glass composition, which contains, expressed in mass percent:

[0013] 56≤SiO2≤70、

[0014] 0.1≤B2O3≤8

[0015] 15≤Al2O3≤24、

[0016] 4≤MgO≤14

[0017] 0≤CaO≤4、

[0018] 0≤ZnO≤10

[0019] 0≤(Li2O+Na2O+K2O)≤4,

[0020] The composition is 0.1 ≤ ZrO2 ≤ 5, and,

[0021] It does not actually contain TiO2.

[0022] From another perspective, the present invention provides the following glass composition, which contains, expressed in mass percent:

[0023] 56≤SiO2≤70、

[0024] 0.1≤B2O3≤8

[0025] 15≤Al2O3≤24、

[0026] 4≤MgO≤14

[0027] 0≤CaO≤4、

[0028] 0.1≤ZnO≤3、

[0029] The composition is 0 ≤ (Li₂O + Na₂O + K₂O) ≤ 4, and,

[0030] It does not actually contain TiO2 or ZrO2.

[0031] From another perspective, the present invention provides the following glass composition, which contains, expressed in mass percent:

[0032] 56≤SiO2≤70、

[0033] 0.1≤B2O3≤8

[0034] 15≤Al2O3≤24、

[0035] 4≤MgO≤14

[0036] 0≤CaO≤4、

[0037] 0≤ZnO≤10

[0038] 0≤(Li2O+Na2O+K2O)≤4,

[0039] The composition of ZrO2 ≤ 5.

[0040] The present invention may also be described as follows.

[0041] The present invention provides the following glass composition, which contains, expressed in mass percent:

[0042] 56≤SiO2≤70、

[0043] 0.1≤B2O3≤8

[0044] 15≤Al2O3≤24、

[0045] 4≤MgO≤14

[0046] 0≤CaO≤4、

[0047] The composition is 0 ≤ (Li₂O + Na₂O + K₂O) ≤ 4, and,

[0048] At least one of a) and c), or b) is true.

[0049] a) Further contains components of 0 ≤ ZnO ≤ 10 and 0.1 ≤ ZrO2 ≤ 5.

[0050] It does not actually contain TiO2.

[0051] b) Further contains components of 0.1 ≤ ZnO ≤ 3.

[0052] It does not actually contain TiO2 or ZrO2.

[0053] c) Further contains components of 0≤ZnO≤10 and 1≤ZrO2≤5.

[0054] Invention Effects

[0055] According to the present invention, a new glass composition having a low linear coefficient of thermal expansion and a high Young's modulus is provided, and is suitable for mass production. Detailed Implementation

[0056] The following describes embodiments of the present invention, but the purpose of this description is not to limit the invention to specific embodiments. In this specification, "substantially not containing" and "substantially not contained" mean a content of less than 0.1% by mass, less than 0.05% by mass, less than 0.01% by mass, further less than 0.005% by mass, particularly less than 0.003% by mass, and in some cases less than 0.001% by mass. The meaning of "substantially" is to allow the presence of trace impurities from glass raw materials, manufacturing equipment, forming equipment, etc. "Main component" refers to the component with the highest content by mass. "T-Fe2O3" refers to total iron oxide converted to ferric oxide (Fe2O3). "T-SnO2" refers to total tin oxide converted to tin dioxide (SnO2). "Alkali metal oxides" refer to lithium oxide (Li2O), sodium oxide (Na2O), and potassium oxide (K2O). The upper and lower limits of the content described below can be arbitrarily combined. Hereinafter, the glass composition will sometimes be abbreviated as glass, and the linear thermal expansion coefficient will be abbreviated as linear expansion coefficient.

[0057] [Glass composition]

[0058] <Ingredients>

[0059] (SiO2)

[0060] SiO2 is a component that forms the framework of glass and is a major component of the glass composition. In addition, SiO2 is a component that adjusts the devitrification temperature and viscosity during glass formation and improves the water resistance of the glass. Furthermore, SiO2 reduces the coefficient of linear expansion of the glass. Also, SiO2 has the effect of reducing the dielectric constant and dielectric loss tangent. The SiO2 content is 56% by mass or more and 70% by mass or less. The lower limit of the SiO2 content can be 57% by mass or more, 58% by mass or more, 58.5% by mass or more, 59% by mass or more, 59.5% by mass or more, 60% by mass or more, and further 60.1% by mass or more. The upper limit of the SiO2 content can be 68% by mass or less, 66% by mass or less, 65% 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, and further 61.9% by mass or less, and depending on the situation, it can be 61.8% by mass or less.

[0061] (B2O3)

[0062] B₂O₃ is a component that forms the framework of glass. Additionally, B₂O₃ is also a component that adjusts 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 has the effect of reducing the dielectric constant and dielectric loss tangent. The content of B₂O₃ is 0.1% by mass or more and 8% by mass or less. The lower limit of the B₂O₃ content can be 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, 2.6% by mass or more, 2.7% by mass or more, 2.8% by mass or more, 2.9% by mass or more, 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, and can be 3.5% by mass or more depending on the circumstances. The upper limit for the content of B2O3 can be below 7% by mass, below 6% by mass, and further below 5.8% by mass, below 5.5% by mass, below 5% by mass, below 4.5% by mass, below 4.4% by mass, below 4.3% by mass, below 4.2% by mass, below 4.1% by mass, below 4.0% by mass, and below 3.9% by mass, and may be below 3.5% by mass depending on the circumstances. The content of B2O3 can also be above 0.1% by mass and below 6% by mass.

[0063] (Al2O3)

[0064] Al₂O₃ is a component that forms the framework of glass. Additionally, Al₂O₃ is a component that adjusts the devitrification temperature and viscosity during glass formation. Furthermore, Al₂O₃ increases the Young's modulus of glass and decreases its coefficient of linear expansion. It also adjusts the dielectric constant and dielectric loss tangent of the glass. If the Al₂O₃ content is 15% by mass or more and 24% by mass or less, the rise in the devitrification temperature of the glass can be suppressed, the melting point of the glass will not become excessively high, and the uniformity of the raw material melting will be increased. The lower limit of the Al₂O₃ content can be 16% by mass or more, 17% by mass or more, 18% by mass or more, 18.5% by mass or more, 19% by mass or more, 19.5% by mass or more, 20% by mass or more, 20.1% by mass or more, and further 20.5% by mass or more. The upper limit of the Al2O3 content can be below 23.5% by mass, below 23% by mass, below 22.5% by mass, below 22% by mass, and further below 21.8% by mass and below 21.5% by mass. Depending on the situation, it can be below 21% by mass, below 20.9% by mass, below 20.8% by mass, below 20.7% by mass, below 20.6% by mass, and below 20.5% by mass.

[0065] (MgO)

[0066] MgO is a component used to adjust the devitrification temperature and viscosity during glass formation, and it also increases the Young's modulus of the glass. Additionally, MgO is used to adjust the dielectric constant and dielectric loss tangent of the glass. The MgO content is 4% by mass or more and 14% by mass or less. The lower limit of the MgO content can be 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 further, 9% by mass or more. The upper limit of the MgO content can be 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, and depending on the circumstances, it can be 8% by mass or less.

[0067] (CaO)

[0068] CaO is an optional 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 for CaO content can be 0.05% by mass or more, 0.06% by mass or more, 0.07% by mass or more, 0.08% by mass or more, 0.09% by mass or more, or 0.1% by mass or more. The upper limit for CaO content can be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, and further, 0.15% by mass or less. CaO may also be substantially absent.

[0069] (MgO + CaO)

[0070] Regarding the meltability and formability of glass, the sum of the contents of MgO and CaO (MgO + CaO) is sometimes important. From the viewpoint of obtaining meltability and formability suitable for glass manufacturing, the lower limit of (MgO + CaO) can be 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 8.5% by mass or more, and further 9% by mass or more. Furthermore, the upper limit of (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, and depending on the circumstances, 8.5% by mass or less, and further 8% by mass or less.

[0071] (MgO / CaO)

[0072] The ratio of MgO content to CaO content (MgO / CaO) is sometimes important in adjusting the devitrification temperature and viscosity during glass formation, as well as the Young's modulus and coefficient of linear expansion of the glass. Here, the content also serves as a quality benchmark. The lower limit for (MgO / CaO) can be 30 or higher, 50 or higher, 80 or higher, 90 or higher, and even 95 or higher, and depending on the circumstances, it can be 100 or higher. The upper limit for (MgO / CaO) is not particularly limited and can be below 10,000, below 1,000, and even below 500.

[0073] (SrO)

[0074] SrO is an optional component. SrO is used to adjust the devitrification temperature and viscosity during glass formation. On the other hand, excessive SrO content will reduce the Young's modulus of the glass and increase its coefficient of linear expansion. The upper limit for SrO content can be 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 further, 0.1% by mass or less. SrO can also be substantially absent.

[0075] (BaO)

[0076] BaO is also an optional component. BaO is used to adjust the devitrification temperature and viscosity during glass formation. On the other hand, excessive BaO content will reduce the Young's modulus of the glass and increase its coefficient of linear expansion. The upper limit of BaO content can be 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 further, 0.1% by mass or less. BaO can also be substantially absent.

[0077] (MgO + CaO + SrO + BaO)

[0078] Regarding the meltability and formability of glass, the total content of MgO, CaO, SrO, and BaO (MgO + CaO + SrO + BaO) is sometimes important. From the viewpoint of obtaining meltability and formability suitable for glass manufacturing, the lower limit of (MgO + CaO + SrO + BaO) can be 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 8.5% by mass or more, and further 9% by mass or more. Furthermore, the upper limit of (MgO + CaO + SrO + BaO) 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, and depending on the circumstances, 8.5% by mass or less, and further 8% by mass or less.

[0079] (ZnO, ZrO2)

[0080] ZnO and ZrO2 are components used to adjust the devitrification temperature and viscosity during glass formation. Furthermore, ZnO and ZrO2 are components that increase the Young's modulus of the glass and decrease its coefficient of linear expansion. Additionally, ZnO and ZrO2 are components that adjust the dielectric constant and dielectric loss tangent of the glass. From the viewpoint of suppressing the rise in devitrification temperature while setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass manufacturing, the sum of the contents of ZnO and ZrO2 (ZnO + ZrO2) can be adjusted to a range of 0.1% by mass or more and 15% by mass or less. This range is also suitable from the viewpoint of ensuring a low coefficient of linear expansion and a high Young's modulus. The lower limit of (ZnO + ZrO2) can be 0.5% by mass or more, 1% by mass or more, 1.1% by mass or more, 1.3% by mass or more, and further 1.5% by mass or more, and depending on the situation, it can be 2% by mass or more, 2.5% by mass or more, 3% by mass or more, and further more than 3% by mass. The upper limit of (ZnO + ZrO2) can be less than 14% by mass, less than 13% by mass, less than 12% by mass, less than 11% by mass, less than 10% by mass, less than 9% by mass, less than 8% by mass, less than 7.5% by mass, less than 7% by mass, and further less than 6.5% by mass, less than 6% by mass, less than 5.8% by mass, less than 5.5% by mass, less than 5% by mass, and depending on the situation, less than 4.5% by mass, less than 4% by mass, less than 3.5% by mass, less than 3% by mass, less than 2.5% by mass, and further less than 2% by mass. ZnO and ZrO2 are optional components. In other words, the lower limit of the content of these components can be 0. (ZnO + ZrO2) can also be more than 0.1% by mass and less than 8% by mass.

[0081] The lower limit of ZnO content can be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.1% by mass or more, 2.5% by mass or more, 3% by mass or more, and further 3.5% by mass or more. The upper limit of ZnO content can be less than 10% by mass, less than 9% by mass, less than 8% by mass, less than 7.5% by mass, less than 7% by mass, less than 6.5% by mass, less than 6% by mass, less than 5.5% by mass, less than 5.3% by mass, less than 5.2% by mass, less than 5.1% by mass, less than 5% by mass, less than 4.5% by mass, less than 4% by mass, less than 3.5% by mass, less than 3% by mass, less than 2.9% by mass, less than 2.8% by mass, less than 2.7% by mass, less than 2.5% by mass, and further less than 2% by mass. Alternatively, ZnO may be substantially absent.

[0082] The lower limit of the ZrO2 content can be 0.1% by mass or more, 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass or more, 0.3% by mass or more, 0.35% by mass or more, 0.4% by mass or more, 0.45% by mass or more, and further 0.5% by mass or more. The upper limit of the ZrO2 content can be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, 1.4% by mass or less, 1.2% by mass or less, and further 1% by mass or less. In particular, in glasses that do not substantially contain TiO2, the ZrO2 content can be 1% by mass or less, 0.8% by mass or less, 0.7% by mass or less, and further 0.6% by mass or less. On the other hand, in glasses that contain TiO2, the ZrO2 content can be 1% by mass or more, 1.1% by mass or more, and further 1.2% by mass or more, or 5% by mass or less. Furthermore, regardless of the TiO2 content, ZrO2 can be substantially absent. However, the ZrO2 content suitable for achieving a low dielectric loss tangent is 0.7% by mass or more, and further 0.8% by mass or more.

[0083] (B2O3 + ZnO + ZrO2)

[0084] The total content of B2O3, ZnO, and ZrO2 (B2O3 + ZnO + ZrO2) is sometimes important in adjusting various properties. Appropriate adjustment of (B2O3 + ZnO + ZrO2) is effective in suppressing excessive rises in devitrification temperature while setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass manufacturing. The lower limits for (B2O3 + ZnO + ZrO2) can be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, 3% by mass or more, 3.5% by mass or more, 4% by mass or more, and further 4.5% by mass or more, and depending on the circumstances, can be 5% by mass or more. The upper limit of (B2O3+ZnO+ZrO2) can be less than 18% by mass, less than 16% by mass, less than 15% by mass, less than 14% by mass, less than 13% by mass, less than 12% by mass, less than 11% by mass, less than 10% by mass, less than 9% by mass, less than 8% by mass, less than 7% by mass, and further less than 6% by mass.

[0085] (MgO + ZnO)

[0086] The sum of the contents of MgO and ZnO (MgO + ZnO) is sometimes important in adjusting various properties. Appropriate adjustment of (MgO + ZnO) is effective in suppressing excessive rises in devitrification temperature while setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass manufacturing. The lower limit of (MgO + ZnO) can be 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, and further 9% by mass or more, and depending on the situation, 10% by mass or more. The upper limit of (MgO + ZnO) can be 17% by mass or less, 16.5% by mass or less, 16% by mass or less, 15.5% by mass or less, 15% by mass or less, 14.5% by mass or less, 14% by mass or less, 13.8% by mass or less, and further 13.7% by mass or less.

[0087] (Li2O, Na2O, K2O)

[0088] Alkali metal oxides (Li₂O, Na₂O, K₂O) are components used to adjust the devitrification temperature and viscosity during glass formation. If the total content of alkali metal oxides (Li₂O + Na₂O + K₂O) is 0% by mass or more and 4% by mass or less, it is possible to suppress excessive rise in devitrification temperature while setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass manufacturing. Furthermore, it is possible to suppress the rise in the glass melting point, achieve more uniform melting of the glass raw materials, but prevent excessive decrease in the glass transition temperature, thus ensuring high heat resistance of the glass. The lower limit for (Li₂O + Na₂O + K₂O) can be 0.1% by mass or more, 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass or more, and further 0.3% by mass or more. The addition of trace amounts of alkali metal oxides is effective in reducing bubbles in the glass. The upper limits for (Li₂O + Na₂O + K₂O) can be less than 3% by mass, less than 2% by mass, less than 2% by mass, less than 1.5% by mass, less than 1% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.8% by mass, less than 0.7% by mass, less than 0.6% by mass, less than 0.5% by mass, less than 0.4% by mass, and less than 0.3% by mass. Alkali metal oxides may also be substantially absent. Li₂O, Na₂O, and K₂O are optional components. In other words, the lower limit for the content of these components can be 0.

[0089] The lower limit of the Li2O content can be 0.1% by mass or more, and further 0.2% by mass or more. The upper limit of the Li2O content can be less than 4% by mass, less than 3% by mass, less than 2% by mass, less than 1.5% by mass, less than 1% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.8% by mass, less than 0.7% by mass, less than 0.6% by mass, less than 0.5% by mass, less than 0.4% by mass, less than 0.3% by mass, and further less than 0.2% by mass. Li2O may also be substantially absent.

[0090] The upper and lower limits of the content of Na₂O and K₂O can be defined as the upper and lower limits of the content of Li₂O, respectively. The sum of the contents of Na₂O and K₂O (Na₂O + K₂O) can be less than 4% by mass, less than 3% by mass, less than 2% by mass, less than 2% by mass, less than 1.5% by mass, less than 1% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.8% by mass, less than 0.7% by mass, less than 0.6% by mass, less than 0.5% by mass, less than 0.4% by mass, less than 0.3% by mass, less than 0.2% by mass, and further less than 0.15% by mass, and may be less than 0.1% by mass depending on the circumstances. The lower limit of the content of (Na₂O + K₂O) can be more than 0.1% by mass, and further more than 0.2% by mass. Na₂O may also be substantially absent. K₂O may also be substantially absent.

[0091] (TiO2)

[0092] 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 decreases its coefficient of linear expansion. Furthermore, TiO2 improves the melt flow properties and chemical durability of glass, as well as its UV absorption characteristics. The lower limit of TiO2 content can be 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, and, depending on the circumstances, 1.2% by mass or more. However, it is desirable to avoid excessive TiO2 content in order to achieve a good balance in adjusting the Young's modulus, coefficient of linear expansion, and mass production adaptability. The upper limit of TiO2 content can be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, 1.4% by mass or less, 1.3% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, and further, 0.1% by mass or less. TiO2 may also be substantially absent.

[0093] (TiO2 + ZrO2)

[0094] The sum of the contents of TiO2 and ZrO2 (TiO2 + ZrO2) is sometimes important in adjusting the devitrification temperature and viscosity during glass formation, as well as the Young's modulus and coefficient of linear expansion of the glass. The lower limit of (TiO2 + ZrO2) can be 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, and further 0.4% by mass or more, and depending on the situation, it can be 0.5% by mass or more. The upper limit of (TiO2 + ZrO2) can be 5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3.3% by mass or less, 3% by mass or less, 2.5% by mass or less, and depending on the situation, it can be 2% by mass or less, 1.5% by mass or less, 1.2% by mass or less, 1% by mass or less, 0.7% by mass or less, and further 0.6% by mass or less. However, according to the embodiments, both TiO2 and ZrO2 may also be substantially absent.

[0095] (Fe)

[0096] 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+ It is a component that improves the heat radiation absorption properties of glass. The upper limit of Fe content, expressed by T-Fe₂O₃, can be less than 5% by mass, less than 4% by mass, less than 3% by mass, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, less than 0.4% by mass, and further less than 0.3% by mass. The lower limit of Fe content, expressed by T-Fe₂O₃, can be more than 0.1% by mass, more than 0.15% by mass, and further more than 0.2% 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. Fe can also be substantially absent.

[0097] (CeO2, SnO2)

[0098] CeO2 and SnO2 are optional components. Especially in glass compositions with low alkali metal oxide content, trace amounts of CeO2 and SnO2 can sometimes help promote glass clarification. CeO2 and SnO2 are components that adjust the devitrification temperature and viscosity during glass formation. Furthermore, CeO2 and SnO2 are components that increase the Young's modulus of the glass and also reduce its coefficient of linear expansion. The upper limits for the content of CeO2 and SnO2 can be 0.1% by mass or more, respectively. The upper limits for the content of CeO2 and SnO2 can be 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.3% by mass or less, and further 0.2% by mass or less, respectively. CeO2 can also be substantially absent. SnO2 can also be substantially absent. It should be noted that the SnO2 content is expressed as T-SnO2.

[0099] (SO3)

[0100] SO3 is also an optional component. Trace amounts of SO3 can reduce residual bubbles in the glass, helping to improve the adaptability of the glass for mass production. The lower limit of SO3 content can be 0.001% by mass or more, and further 0.002% by mass or more. The upper limit of SO3 content can be less than 0.5% by mass, less than 0.2% by mass, less than 0.1% by mass, less than 0.05% by mass, less than 0.04% by mass, less than 0.03% by mass, less than 0.02% by mass, and further less than 0.01% by mass. SO3 may also be substantially absent.

[0101] (F2, Cl2)

[0102] Fluorine (F2) and chlorine (Cl2) are also optional components. Especially in glass compositions with low alkali metal oxide content, F2 and Cl2 can help promote glass clarity. However, F2 and Cl2 are volatile and may disperse during melting. The upper limits for the content of F2 and Cl2 can be 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, 0.2% by mass or less, and further 0.1% by mass or less, respectively. F2 may also be substantially absent. The lower limits for the content of F2 can be 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.35% by mass or more, and further 0.4% by mass or more. Cl2 may also be substantially absent.

[0103] (Total of ingredients)

[0104] The total content of the components described above, namely SiO2 to F2 and Cl2, can be 95% by mass or more, 97% by mass or more, and further 99% by mass or more, and may be 99.5% by mass or more, depending on the situation. The lower limit of the total content of the components shown in (SiO2 + B2O3 + Al2O3 + MgO + CaO + ZnO) can be 75% by mass or more, less than 85% by mass, more than 90% by mass, and further 95% by mass or more, and may be 97% by mass or more, depending on the situation. The upper limit of the total content of the components shown in (SiO2 + B2O3 + Al2O3 + MgO + CaO + ZnO) can be less than 99% by mass. The lower limit of the total content of the components shown in (Li2O + Na2O + K2O + TiO2 + ZrO2 + T-Fe2O3) can be 0.5% by mass or more, 0.7% by mass or more, and further 1% by mass or more. The upper limit of the total of the components shown in (Li2O+Na2O+K2O+TiO2+ZrO2+T-Fe2O3) can be less than 19% by mass, less than 10% by mass, less than 5% by mass, and further less than 3% by mass.

[0105] (Other ingredients)

[0106] Other optional components may include at least one selected from P2O5, HfO2, Ga2O3, La2O3, Pr2O3, Nd2O3, Pm2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, WO3, Nb2O5, Sc2O3, Y2O3, MoO3, Ta2O5, MnO2, Cr2O3, CuO, CoO, PbO, Bi2O3, Br2, I2, As2O3, and Sb2O3. However, other optional components are not limited to these. Other optional components may be contained in a concentration of 3% by mass or less. The permissible concentrations of other optional components may be 2% by mass or less, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, and further less than 0.1% by mass. Other optional components may also be substantially absent. Y₂O₃ and La₂O₃ are components that adjust the devitrification temperature and viscosity during glass formation. Additionally, Y₂O₃ and La₂O₃ are components that increase the Young's modulus of the glass. For example, the sum of the contents of Y₂O₃ and La₂O₃ (Y₂O₃ + La₂O₃) can be less than 5% by mass, less than 3% by mass, less than 2% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, and further less than 0.1% by mass. For example, from an environmental protection perspective, it is desirable that As₂O₃ and Sb₂O₃ be substantially absent. The total contents of the other optional 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, and further less than 0.1% by mass.

[0107] <Preferred Composition>

[0108] Preferred compositions are illustrated below. For each component, the range indicated in parentheses represents a more preferred range.

[0109] (Composition A1)

[0110] A glass composition, expressed in mass percent, contains:

[0111] 58≤SiO2≤64 (58.5≤SiO2≤63)

[0112] 1≤B2O3≤6 (1.5≤B2O3≤5)

[0113] 17≤Al2O3≤23(18≤Al2O3≤22)

[0114] 4≤MgO≤13 (7≤MgO≤12)

[0115] 0≤CaO≤3 (0≤CaO≤1)

[0116] 1≤ZnO≤8 (1.1≤ZnO≤7)

[0117] 0≤(Li2O+Na2O+K2O)≤3(0≤(Li2O+Na2O+K2O)≤2),

[0118] The composition is 0.2 ≤ ZrO2 ≤ 4 (0.3 ≤ ZrO2 ≤ 3), and,

[0119] It does not actually contain TiO2.

[0120] Composition A1 has a low linear coefficient of thermal expansion and a high Young's modulus, and also exhibits excellent mass production adaptability. One example of its excellent mass production adaptability is that ΔT, obtained by subtracting the devitrification temperature from the operating temperature, is a positive value.

[0121] (Composition A2)

[0122] A glass composition, expressed in mass percent, contains:

[0123] 58.5≤SiO2≤62、

[0124] 1.5≤B2O3≤5、

[0125] 18≤Al2O3≤22、

[0126] 7≤MgO≤12

[0127] 0≤CaO≤1、

[0128] 1.1≤ZnO≤7、

[0129] 0.1≤(Li2O+Na2O+K2O)≤2,

[0130] The composition is 0.3 ≤ ZrO2 ≤ 3, and,

[0131] It satisfies 9≤(MgO+ZnO)≤13.8, and essentially does not contain TiO2.

[0132] Composition A2 exhibits a low coefficient of linear thermal expansion and a high Young's modulus, and also demonstrates excellent adaptability to mass production. An example of this excellent adaptability is its low operating temperature and large ΔT. Here, low operating temperature is, for example, below 1395°C, and large ΔT is, for example, above 10°C.

[0133] (Component B)

[0134] A glass composition, expressed in mass percent, contains:

[0135] 58≤SiO2≤64 (58.5≤SiO2≤63)

[0136] 1≤B2O3≤6 (1.5≤B2O3≤5)

[0137] 17≤Al2O3≤23(18≤Al2O3≤22)

[0138] 4≤MgO≤13 (7≤MgO≤12)

[0139] 0≤CaO≤3 (0≤CaO≤1)

[0140] 0.5≤ZnO≤2.8 (1.1≤ZnO≤2.8)

[0141] The composition is 0 ≤ (Li₂O + Na₂O + K₂O) ≤ 3 (0 ≤ (Li₂O + Na₂O + K₂O) ≤ 2), and,

[0142] It does not actually contain TiO2 or ZrO2.

[0143] Composition B differs from compositions A1-A2 and C, and substantially does not contain ZrO2. Composition B has a low coefficient of linear thermal expansion and a high Young's modulus, and also exhibits excellent adaptability for mass production.

[0144] (Composition C)

[0145] A glass composition, expressed in mass percent, contains:

[0146] 58≤SiO2≤64 (58.5≤SiO2≤63)

[0147] 1≤B2O3≤6 (1.5≤B2O3≤5)

[0148] 17≤Al2O3≤23(18≤Al2O3≤22)

[0149] 4≤MgO≤13 (7≤MgO≤12)

[0150] 0≤CaO≤3 (0≤CaO≤1)

[0151] 1≤ZnO≤8 (1.1≤ZnO≤7)

[0152] 0≤(Li2O+Na2O+K2O)≤3(0≤(Li2O+Na2O+K2O)≤2),

[0153] 0.1≤TiO2≤4 (0.3≤TiO2≤3)

[0154] The composition is 1.1≤ZrO2≤4 (1.1≤ZrO2≤3).

[0155] Composition C differs from compositions A1-A2 and B, and contains both TiO2 and ZrO2. Composition C exhibits a low linear coefficient of thermal expansion and a high Young's modulus, and also demonstrates excellent adaptability for mass production. Furthermore, composition C is suitable for achieving a low dielectric loss tangent.

[0156] Compositions A1, A2, B, and C may further include 0.1 ≤ T-Fe2O3 ≤ 3 (in a more preferred range, 0.1 ≤ T-Fe2O3 ≤ 2), and may also further include 0.001 ≤ SO3 ≤ 0.5 (in a more preferred range, 0.002 ≤ SO3 ≤ 0.3) together with T-Fe2O3 within this range. Additionally, as explained in the <Ingredients> section, the upper and / or lower limits of the content of each component in compositions A1, A2, B, and C may be changed. Furthermore, as explained in the <Ingredients> section, the total amount of components in compositions A1, A2, B, and C may be adjusted, and other components may be included.

[0157] <Characteristics>

[0158] The properties that can be obtained from the glass composition of this embodiment will be described below.

[0159] (Melting characteristics)

[0160] 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°C, dimensional deviations such as glass fiber diameter can be reduced. If the operating temperature is below 1450°C, fuel costs during glass melting can be reduced, glass manufacturing equipment is less susceptible to heat-induced corrosion, and equipment lifespan is extended. The lower limit of the operating temperature can be above 1200°C, 1300°C, 1320°C, 1330°C, 1340°C, and further above 1350°C. The upper limit of the operating temperature can be below 1420°C, 1410°C, 1400°C, 1395°C, 1390°C, 1385°C, 1382°C, and further below 1380°C.

[0161] The larger the temperature difference ΔT, obtained by subtracting the devitrification temperature from the operating temperature, the less likely devitrification will occur during glass forming, resulting in the production of homogeneous glass with a high yield rate. ΔT can be above 0°C, above 5°C, above 10°C, and further above 15°C. There is no particular upper limit to ΔT, for example, below 100°C, below 80°C, below 70°C, below 65°C, below 60°C, below 55°C, and further below 50°C. It should be noted that the devitrification temperature is the temperature at which crystals form and begin to grow in the molten glass preform, and it can be determined by the method described later.

[0162] (Coefficient of linear expansion)

[0163] The coefficient of linear expansion (CDO) is more precisely the average CDO over a temperature range of 50–350°C. The low CDO of glass contributes to improved dimensional stability of resin compositions containing glass. The lower limit of the CDO can be 20 × 10⁻⁶. -7 / ℃ or above, 25×10 -7 / ℃ or above, 26×10 -7 / ℃ or higher, and then 27×10 -7 Above / ℃. The upper limit of the linear expansion coefficient can be 35×10. -7 / ℃ below, 34×10 -7 / ℃ below, 33×10 -7 Below / ℃, and further 32×10 -7 Below / ℃, it can be 31×10 depending on the situation. -7 / ℃ below.

[0164] (Glass transition temperature)

[0165] The glass transition temperature (glass transition point) is an indicator of the heat resistance of glass. When heat-treating a glass-containing resin composition, a high glass transition temperature is desirable. The lower limit of the glass transition temperature can be above 650°C, above 700°C, above 710°C, above 720°C, and further above 730°C. The upper limit of the glass transition temperature can be below 800°C, below 790°C, below 780°C, and further below 770°C.

[0166] (Young's modulus)

[0167] A high Young's modulus in glass contributes to improved mechanical properties and dimensional stability of resin compositions containing glass fibers or glass fillers. Young's modulus can be calculated from the longitudinal and transverse wave velocities of the elastic wave propagating in the glass, determined by conventional ultrasonic methods, and the glass density, determined by the Archimedes method. The lower limit of Young's modulus can be 85 GPa or higher, 86 GPa or higher, 87 GPa or higher, 88 GPa or higher, 89 GPa or higher, and further, 90 GPa or higher. The upper limit of Young's modulus can be 100 GPa or lower, and further, 99 GPa or lower, 98 GPa or lower, 97 GPa or lower, 96 GPa or lower, and further, 95 GPa or lower.

[0168] (Dielectric constant, dielectric loss tangent)

[0169] The low dielectric constant of glass contributes to improved dielectric properties of resin compositions containing glass fibers or glass fillers. Dielectric constants measured at 1 GHz are 6.5 or less, 6.4 or less, 6.3 or less, 6.2 or less, 6.1 or less, 6.0 or less, 5.9 or less, 5.8 or less, 5.7 or less, 5.6 or less, 5.5 or less, and further 5.4 or less, and depending on the case, 5.3 or less. Strictly speaking, dielectric constant refers to relative 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). Dielectric constants can be 5.0 or greater.

[0170] The low dielectric loss tangent of glass also contributes to the improvement of the dielectric properties of resin compositions containing glass fibers or glass fillers. The dielectric loss tangents measured at 1 GHz were 0.0060° or less, 0.0055° or less, 0.0050° or less, 0.0045° or less, 0.0044° or less, 0.0043° or less, 0.0042° or less, 0.0041° or less, 0.0040° or less, 0.0039° or less, 0.0038° or less, 0.0037° or less, 0.0036° or less, 0.0035° or less, 0.0034° or less, 0.0033° or less, and 0.00° or less. Below 32, below 0.0031, below 0.0030, further below 0.0029, below 0.0028, below 0.0027, below 0.0026, below 0.0025, below 0.0024, below 0.0023, below 0.0022, below 0.0021, below 0.0020, and depending on the situation, below 0.0019, below 0.0018, below 0.0017, below 0.0016, below 0.0015. The dielectric loss tangent is the value at room temperature (25°C). The dielectric loss tangent can be above 0.0010.

[0171] [Glass products]

[0172] <Glass fiber>

[0173] The glass fiber of this embodiment is composed of the above-described glass composition. According to this embodiment, even when the fiber diameter is small, the occurrence of devitrification and the incorporation of bubbles in the glass fiber can be further suppressed. Therefore, the glass fiber of this embodiment can be a glass fiber with a small fiber diameter.

[0174] The average fiber diameter of the glass fiber is, for example, 0.1 to 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 further 3 μm or more; it can be less than 50 μm, less than 40 μm, less than 30 μm, less than 25 μm, less than 20 μm, less than 15 μm, less than 10 μm, less than 8 μm, less than 6 μm, less than 5 μm, less than 4.6 μm, and further less than 4.3 μm. Glass compositions having characteristic temperatures suitable for mass production are suitable for stable manufacture in the form of fine glass fibers. In a preferred embodiment, the average fiber diameter is even finer, for example, less than 3.9 μm, and further less than 3.5 μm. The glass fiber is, for example, long glass fiber (filament).

[0175] Glass fibers may have at least one shape selected from roving, roving cloth, continuous filament mat, ground fiber, flat fiber, filament mat, chopped strand, yarn, glass cloth and glass tape.

[0176] The flat fiber has a shape obtained by cutting glass fibers with a flat 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 to 25 μm. The major axis D2 is, for example, 0.6 to 300 μm. The length L of the flat fiber is, for example, 10 to 100,000 μm. The flat fiber can be obtained by known methods. The cross-sectional shape of the flat fiber can have a concave shape where the surface extending along the major axis D2 recedes towards the center compared to the ends.

[0177] Glass fibers can be manufactured by a method including a process of melting the glass composition of this embodiment and a process of forming the molten glass composition into glass fibers.

[0178] <Glass packing>

[0179] The glass filler in this embodiment is composed of the glass composition described above. The glass filler may be at least one selected from sheet glass, glass powder, glass beads, and fine flakes.

[0180] Flake glass, also known as flaky glass, has a sheet-like shape. The average particle 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 particle 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 particle size of flake glass and other glass fillers can be determined by the particle size distribution measured using laser diffraction scattering, where the cumulative volume percentage corresponds to the particle size (D50). Flake glass can be obtained using known methods such as blow molding and cupping.

[0181] Glass powder is a powdered form of 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 with the same volume as the glass powder particles. Glass powder can be obtained by known methods.

[0182] 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.

[0183] Thin sheets are sheet-like glass, specifically thin sheets of glass used for thin materials. For example, thin sheets can be composed of sheet-like glass with an average thickness of 0.1 to 2.0 μm. Alternatively, they 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. Thin sheets with such a thin average thickness and small thickness deviation provide excellent resin reinforcement and also effectively reduce the molding shrinkage rate of the resin. Thin sheets also allow for more relaxed limitations on the thickness of resin molded articles compared to conventional methods. Thin sheets are preferably composed of sheet-like glass with an average thickness of 0.1 to 1.0 μm. Preferably, thin sheets 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. Thin sheets can be obtained using the methods described for sheet-like glass.

[0184] Glass fillers can be manufactured by a method including a process of melting the glass composition of this embodiment and a process of shaping the molten glass composition into glass fillers.

[0185] [Articles containing glass fibers and / or glass fillers]

[0186] The glass fiber and glass filler of this embodiment can be used in various articles exemplified below. These articles are, in effect, molded bodies, filler-containing articles, resin articles, etc.

[0187] <Molded body>

[0188] The molded body of this embodiment comprises the aforementioned glass fiber and is shaped into a predetermined shape. The molded body is not limited to the following and may be at least one selected from rubber reinforcing yarn, nonwoven fabric, prepreg, reinforced plastic, printed circuit board, inorganic cured body, filter, heat insulation material, sound absorbing material, and battery spacer.

[0189] <Products containing fillers>

[0190] The filler-containing article of this embodiment includes the glass filler described above. The filler-containing article is not limited to the following: it may be at least one selected from reinforced plastics, coatings, inks, printed circuit boards, inorganic cured products, and cosmetics.

[0191] <Resin Products>

[0192] The resin article of this embodiment comprises the aforementioned glass fibers and / or glass fillers, and resin. The resin article can be an electrically 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, but may include, for example, polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyester, polyamide, polycarbonate, polybutene, polybutylene terephthalate, copolymers thereof, etc. If polybutylene terephthalate is used, the effect of warpage suppression and dimensional stability improvement of the molded article due to mixing with the glass filler is greater. Thin sheet glass, flat fibers, and thin flakes have a relatively large specific surface area, which is suitable for ensuring bonding strength with the thermoplastic resin.

[0193] [Technology provided by this embodiment]

[0194] The technology provided by this embodiment is as follows.

[0195] (Technology 1)

[0196] A glass composition, expressed in mass percent, contains:

[0197] 56≤SiO2≤70、

[0198] 0.1≤B2O3≤8

[0199] 15≤Al2O3≤24、

[0200] 4≤MgO≤14

[0201] 0≤CaO≤4、

[0202] 0≤ZnO≤10

[0203] 0≤(Li2O+Na2O+K2O)≤4,

[0204] The composition is 0.1 ≤ ZrO2 ≤ 5, and,

[0205] It does not actually contain TiO2.

[0206] (Technology 2)

[0207] A glass composition, expressed in mass percent, contains:

[0208] 56≤SiO2≤70、

[0209] 0.1≤B2O3≤8

[0210] 15≤Al2O3≤24、

[0211] 4≤MgO≤14

[0212] 0≤CaO≤4、

[0213] 0.1≤ZnO≤3、

[0214] The composition is 0 ≤ (Li₂O + Na₂O + K₂O) ≤ 4, and,

[0215] It does not actually contain TiO2 or ZrO2.

[0216] (Technology 3)

[0217] A glass composition, expressed in mass percent, contains:

[0218] 56≤SiO2≤70、

[0219] 0.1≤B2O3≤8

[0220] 15≤Al2O3≤24、

[0221] 4≤MgO≤14

[0222] 0≤CaO≤4、

[0223] 0≤ZnO≤10

[0224] 0≤(Li2O+Na2O+K2O)≤4,

[0225] The composition of ZrO2 ≤ 5.

[0226] (Technology 4)

[0227] The glass composition according to any one of Techniques 1 to 3 contains, in mass percent, 75 ≤ (SiO2 + B2O3 + Al2O3 + MgO + CaO + ZnO) ≤ 99.

[0228] (Technology 5)

[0229] The glass composition according to any one of the techniques 1 to 4 contains, in terms of mass%, 1 ≤ (ZnO + ZrO2) ≤ 15.

[0230] (Technology 6)

[0231] According to any one of the techniques 1 to 5, the glass composition contains, expressed as a percentage by mass, 1 ≤ (Li₂O + Na₂O + K₂O + TiO₂ + ZrO₂ + T-Fe₂O₃) ≤ 19. Wherein, T-Fe₂O₃ is the total iron oxide converted to Fe₂O₃.

[0232] (Technology 7)

[0233] The glass composition according to any one of the techniques 1 to 6 contains an amount of 2 ≤ B2O3 ≤ 6, expressed as a percentage by mass.

[0234] (Technology 8)

[0235] The glass composition according to any one of the techniques 1 to 7 contains 5 ≤ ​​MgO ≤ 13% by mass.

[0236] (Technology 9)

[0237] According to the glass composition described in Technique 8, it contains 0 ≤ CaO ≤ 1% by mass.

[0238] (Technology 10)

[0239] The glass composition described in any one of Techniques 1 to 9 does not substantially contain SrO.

[0240] (Technology 11)

[0241] The glass composition described in any one of Artificial Intelligence 1 to Artificial Intelligence 10 does not substantially contain BaO.

[0242] (Technology 12)

[0243] The glass composition according to any one of Art 1 to Art 11 contains an amount of 0 ≤ ZnO ≤ 8% by mass.

[0244] (Technology 13)

[0245] The glass composition according to any one of Art 1 to Art 12 contains, in mass percent, 4 ≤ (MgO + ZnO) ≤ 17.

[0246] (Technology 14)

[0247] The glass composition according to any one of Art 1 to Art 13 contains, in terms of mass%, 0 ≤ (Li2O + Na2O + K2O) ≤ 1.

[0248] (Technology 15)

[0249] According to the glass composition described in Technique 14, it contains an amount of 0.1 ≤ (Li2O + Na2O + K2O) ≤ 1, expressed as a percentage by mass.

[0250] (Technology 16)

[0251] The glass composition according to any one of Art 1 to Art 15 contains, in terms of mass%, 0 ≤ (Na2O + K2O) ≤ 1.

[0252] (Technology 17)

[0253] The glass composition according to any one of Art 1 to Art 16 contains, in mass % 0 ≤ (TiO2 + ZrO2) ≤ 4.

[0254] (Technology 18)

[0255] The glass composition according to any one of Artificial Intelligence 1 to Artificial Intelligence 17 contains, expressed as a percentage by mass, 0 ≤ T-Fe2O3 ≤ 5. Wherein, T-Fe2O3 is the total iron oxide converted to Fe2O3.

[0256] (Technology 19)

[0257] The glass composition according to any one of Art 1 to Art 18 contains an amount of 0 ≤ Y2O3 ≤ 3% by mass.

[0258] (Technology 20)

[0259] The glass composition according to any one of Artificial Intelligence 1 to Artificial Intelligence 19 contains, expressed as a percentage by mass, an amount of 0 ≤ T-SnO2 ≤ 2. Wherein, T-SnO2 is the total tin oxide converted to SnO2.

[0260] (Technology 21)

[0261] The glass composition according to any one of Art 1 to Art 20 contains, in mass % 0 ≤ CeO2 ≤ 2.

[0262] (Technology 22)

[0263] The glass composition according to any one of Art 1 to Art 21 contains an amount of 0 ≤ F2 ≤ 5, expressed as a percentage by mass.

[0264] (Technology 23)

[0265] The glass composition according to any one of Art 1 to Art 22 contains an amount of 0 ≤ SO3 ≤ 0.5% by mass.

[0266] (Technology 24)

[0267] According to any one of the technologies 1 to 23, the glass composition wherein, when the temperature at which the viscosity is 1000 dPa·sec is set as the operating temperature, the operating temperature is 1450°C or less.

[0268] (Technology 25)

[0269] According to any one of the technologies 1 to 24, the glass composition wherein, when the temperature at which the viscosity is 1000 dPa·sec is set as the operating temperature, the temperature difference ΔT obtained by subtracting the devitrification temperature from the operating temperature is 0°C or higher.

[0270] (Technology 26)

[0271] The glass composition described in any one of Techniques 1 to 25 has a Young's modulus of 85 to 100 GPa.

[0272] (Technology 27)

[0273] According to any one of Artificial 1 to Artificial 26, the glass composition has an average coefficient of linear expansion of 20 to 35 × 10⁻⁶ at 50 to 350°C. -7 / ℃.

[0274] (Technology 28)

[0275] The glass composition according to any one of Artificial Intelligence 1 to 27 has a dielectric constant of 6.5 or less at a frequency of 1 GHz.

[0276] (Technology 29)

[0277] The glass composition described in any one of Artificial 1 to 28 has a dielectric loss tangent of 0.0060 or less at a frequency of 1 GHz.

[0278] (Technology 30)

[0279] A glass fiber comprising the glass composition described in any one of techniques 1 to 29.

[0280] (Technology 31)

[0281] According to the glass fiber described in Technique 30, it has at least one shape selected from roving, roving cloth, continuous filament mat, ground fiber, flat fiber, filament mat, chopped filament, yarn, glass cloth and glass tape.

[0282] (Technology 32)

[0283] A glass filler comprising the glass composition described in any one of techniques 1 to 29.

[0284] (Technology 33)

[0285] According to Technique 32, the glass filler is selected from at least one of sheet glass, glass powder, glass beads, and thin flakes.

[0286] (Technology 34)

[0287] A molded body comprising the glass fiber described in Technique 30, and being at least one selected from rubber reinforcing yarn, nonwoven fabric, prepreg, reinforced plastic, printed substrate, inorganic cured body, filter, heat insulation material, sound absorbing material, and battery spacer.

[0288] (Technology 35)

[0289] An article containing filler comprising the glass filler described in Technique 32, and being at least one selected from reinforced plastics, coatings, inks, printed circuit boards, inorganic cured bodies, and cosmetics.

[0290] (Technology 36)

[0291] A method for manufacturing glass fiber includes a step of melting a glass composition as described in any one of techniques 1 to 29, and a step of forming the molten glass composition into glass fiber.

[0292] (Technology 37)

[0293] A method for manufacturing a glass filler includes a step of melting a glass composition as described in any one of techniques 1 to 29, and a step of shaping the molten glass composition into a glass filler.

[0294] Example

[0295] The following examples and comparative examples further illustrate the implementation of the present invention.

[0296] (Examples and Comparative Examples)

[0297] Common glass raw materials such as silica sand were prepared in accordance with the compositions shown in Tables 1-4, and glass raw material batches were prepared in the Examples and Comparative Examples respectively. Each batch was heated to 1500-1600°C in an electric furnace to melt it, and this process was maintained for approximately 4 hours until the composition became homogeneous. Then, a portion of the molten glass (glass melt) was allowed to flow onto an iron plate and slowly cooled to room temperature in the electric furnace to obtain a bulk glass composition (plate-shaped object, glass sample). It should be noted that in Examples 16, 28, 35-37 and Comparative Example 3, tin(IV) oxide (SnO2) was used as the SnO2 source. In Examples 17, 19, 38, and 39, cerium(IV) oxide (CeO2) was used as the CeO2 source. In Examples 19-23, 29, 31-36, and 38-42, sodium sulfate was used as the SO3 source, and in Examples 26 and 37, lithium sulfate monohydrate was used as the SO3 source.

[0298] The evaluation methods for these characteristics are explained below.

[0299] (Operating temperature)

[0300] 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 based on the results. Here, the platinum ball pulling method refers to the following method: immersing a platinum ball in molten glass, and applying the Stokes equation, which describes the relationship between viscosity and falling velocity when a small particle settles in a fluid, to determine the viscosity by pulling the platinum ball at a constant speed using the load (resistance) and the forces acting on the platinum ball, such as gravity and buoyancy.

[0301] (Devitrification temperature)

[0302] 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. If the glass becomes cloudy and crystals are not observed, the highest temperature of the furnace corresponding to the location where cloudiness occurs is taken as the devitrification temperature. Here, the particle size is determined by sieving. It should be noted that the temperature distribution within the furnace (different temperatures depending on the location within the furnace) is predetermined, and the glass composition placed at a predetermined location within the furnace is heated at the predetermined temperature of that location. The temperature difference ΔT is obtained by subtracting the devitrification temperature from the operating temperature.

[0303] (Coefficient of linear expansion)

[0304] The average linear expansion coefficient of the obtained glass composition was measured from 50 to 350°C using a commercially available dilatometer (Rigaku Corporation, Thermomechanical Analysis Apparatus, TMA8510). Furthermore, the glass transition temperature Tglass was obtained based on the thermal expansion curves obtained from the TMA apparatus. g .

[0305] (Young's modulus)

[0306] Young's modulus E is determined as follows: The longitudinal wave velocity vl and transverse wave velocity vt of the elastic wave propagating in the glass are measured using the conventional ultrasonic method. The density ρ of the glass is then determined using the Archimedes method, and E = 3ρ·vt. t 2 ·(v l 2 -4 / 3·v t 2 ) / (v l 2 -v t 2 Find the expression for ).

[0307] (Dielectric constant, dielectric loss tangent)

[0308] The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured using a dielectric constant measuring device based on the cavity resonator perturbation method. The measurement temperature was set to 25℃, and the sample size was set to a cuboid with a base of 1.5 mm on each side and a height of 100 mm.

[0309] (Number of bubbles)

[0310] Common glass raw materials such as silica sand were prepared into batches for both the examples and comparative examples. Using an electric furnace, 150g of each batch was heated to 1600°C (the test temperature) to melt it, and this process was maintained for 2 hours until the composition became homogeneous. Then, a portion of the molten glass (glass melt) was allowed to flow onto an iron plate and slowly cooled to room temperature in the electric furnace to obtain a glass sample. The number of bubbles in the glass sample was observed using an optical microscope, and the number of bubbles per 100g of glass was calculated. Case A was defined as having fewer than 400 bubbles per 100g of glass; case B as having more than 400 but less than 2000 bubbles; case C as having more than 2000 but less than 10000 bubbles; and case D as having more than 10000 bubbles.

[0311] The measurement results are shown in Tables 1-4. It should be noted that all glass compositions in the tables are expressed as mass % (%). Additionally, Fe2O3 and SnO2 in the tables represent T-Fe2O3 and T-SnO2, respectively.

[0312] [Table 1]

[0313]

[0314] [Table 2]

[0315]

[0316] [Table 3]

[0317]

[0318] [Table 4]

[0319]

[0320] According to the various embodiments, the coefficient of linear expansion was obtained to be 29–32 × 10⁻⁶. -7 The results are given at / ℃, Young's modulus of 90~92GPa, operating temperature of 1324~1410℃, and difference ΔT (operating temperature - devitrification temperature) of 0~54℃.

[0321] The glass composition of Comparative Example 1 has an E-glass composition. E-glass has a poor average coefficient of linear expansion and Young's modulus at 50–350°C. 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 productionability. The glass composition of Comparative Example 3 has the glass composition of Example 2 of Patent Document 1. This glass has a poor Young's modulus and a slightly higher operating temperature. 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. It should be noted that the coefficient of linear expansion of Comparative Example 4 (33 × 10⁻⁶) is... -7 ( / ℃) compared to the measured value in Patent Document 2 (29×10) -7 The reason for the higher ( / ℃) depends on the different temperature ranges measured. Furthermore, the inventors conducted additional experiments, and the results showed that ΔT in Comparative Example 4 was negative, resulting in poor mass production. At least one of the average coefficient of linear expansion, Young's modulus, and difference ΔT in the glass compositions of Comparative Examples 5-16 was also insufficient.

Claims

1. A glass composition comprising, in weight percent: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0≤ZnO≤10 0.1≤(Li2O+Na2O+K2O)≤1, The composition is 0.25 ≤ ZrO2 ≤ 5, and, It does not actually contain BaO, TiO2, or PbO.

2. A glass composition, comprising, in percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0.1≤ZnO≤2.9 The composition is 0.1 ≤ (Li₂O + Na₂O + K₂O) ≤ 1, and, It does not actually contain TiO2, ZrO2, or PbO.

3. The glass composition according to claim 1 or 2, wherein the composition contains 75 ≤ (SiO2 + B2O3 + Al2O3 + MgO + CaO + ZnO) ≤ 99% by mass.

4. A glass composition, comprising, in percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0≤ZnO≤10 0.1≤(Li2O+Na2O+K2O)≤1, 0.25≤ZrO2≤5、 The composition is 1 ≤ (ZnO + ZrO2) ≤ 15, and, It does not actually contain TiO2 and PbO.

5. The glass composition according to any one of claims 1, 2, and 4, wherein the composition contains, expressed as a percentage by mass, 1 ≤ (Li₂O + Na₂O + K₂O + TiO₂ + ZrO₂ + T-Fe₂O₃) ≤ 19. in, T-Fe2O3 is the total iron oxide converted to Fe2O3.

6. A glass composition comprising, in percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 5≤MgO≤13 0≤CaO≤4、 0≤ZnO≤10 0.1≤(Li2O+Na2O+K2O)≤1, The composition is 0.25 ≤ ZrO2 ≤ 5, and, It does not actually contain TiO2 and PbO.

7. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the component contains 0 ≤ CaO ≤ 1 in mass%.

8. The glass composition according to any one of claims 1, 2, 4 and 6, substantially free of SrO.

9. The glass composition according to any one of claims 2, 4 and 6, substantially free of BaO.

10. The glass composition according to any one of claims 1, 4, and 6, wherein it contains 0.1 ≤ ZnO ≤ 8% by mass.

11. The glass composition according to any one of claims 1, 2, 4 and 6, wherein it contains 4 ≤ (MgO + ZnO) ≤ 17 by mass%.

12. The glass composition according to any one of claims 1, 2, 4 and 6, wherein it contains 0 ≤ (Na2O + K2O) ≤ 1 in mass%.

13. The glass composition according to any one of claims 1, 2, 4 and 6, wherein it contains, expressed as a percentage by mass, 0 ≤ T - Fe₂O₃ ≤ 5. in, T-Fe2O3 is the total iron oxide converted to Fe2O3.

14. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the composition contains 0 ≤ Y₂O₃ ≤ 3% by mass.

15. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the component containing 0 ≤ T - SnO2 ≤ 2 is expressed as a percentage by mass. in, T-SnO2 is the total tin oxide converted to SnO2.

16. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the component contains 0 ≤ CeO2 ≤ 2 in mass %.

17. The glass composition according to any one of claims 1, 2, 4 and 6, wherein it contains 0 ≤ F2 ≤ 5 in mass % 18. The glass composition according to any one of claims 1, 2, 4 and 6, wherein it contains 0 ≤ SO3 ≤ 0.5% by mass.

19. The glass composition according to any one of claims 1, 2, 4 and 6, wherein, When the temperature at which the viscosity is 1000 dPa·sec is set as the operating temperature, the operating temperature is below 1450°C.

20. The glass composition according to any one of claims 1, 2, 4 and 6, wherein, When the operating temperature is set to the temperature at which the viscosity is 1000 dPa·sec, the temperature difference ΔT obtained by subtracting the devitrification temperature from the operating temperature is above 0°C.

21. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the Young's modulus is 85 GPa to 100 GPa.

22. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the average coefficient of linear expansion at 50°C to 350°C is 20 × 10⁻⁶. -7 / ℃~35×10 -7 / ℃.

23. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the dielectric constant at a frequency of 1 GHz is 6.5 or less.

24. The glass composition according to any one of claims 1, 2, 4 and 6, wherein the dielectric loss tangent at a frequency of 1 GHz is less than 0.0060°.

25. A glass fiber comprising the glass composition described in composition 1 or composition 2 below. Composition 1 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0≤ZnO≤10 0.1≤(Li2O+Na2O+K2O)≤1, The composition is 0.25 ≤ ZrO2 ≤ 5, and, It does not actually contain TiO2 and PbO; Composition 2 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0.1≤ZnO≤2.9 The composition is 0.1 ≤ (Li₂O + Na₂O + K₂O) ≤ 1, and, It does not actually contain TiO2, ZrO2, or PbO.

26. A glass fiber comprising a glass composition, said glass composition containing, expressed in percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0≤ZnO≤10 0≤(Li2O+Na2O+K2O)≤4, The composition is 0.25 ≤ ZrO2 ≤ 5, and, It does not actually contain TiO2.

27. A glass fiber comprising a glass composition, said glass composition containing, expressed in percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0.1≤ZnO≤2.9 The composition is 0 ≤ (Li₂O + Na₂O + K₂O) ≤ 4, and, It does not actually contain TiO2 or ZrO2.

28. The glass fiber according to any one of claims 25 to 27, having at least one shape selected from roving, roving cloth, continuous filament mat, ground fiber, flat fiber, filament mat, chopped strand, glass cloth, and glass tape.

29. The glass fiber according to any one of claims 25 to 27, having the shape of a yarn.

30. A glass filler comprising the glass composition described in composition 1 or composition 2 below. Composition 1 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0≤ZnO≤10 0.1≤(Li2O+Na2O+K2O)≤1, The composition is 0.25 ≤ ZrO2 ≤ 5, and, It does not actually contain TiO2 and PbO; Composition 2 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0.1≤ZnO≤2.9 The composition is 0.1 ≤ (Li₂O + Na₂O + K₂O) ≤ 1, and, It does not actually contain TiO2, ZrO2, or PbO.

31. The glass filler according to claim 30, wherein it is selected from at least one of sheet glass, glass powder and glass beads.

32. A filler-containing article comprising the glass filler of claim 30, and being at least one selected from reinforced plastics, coatings, printed circuit boards, inorganic cured bodies, and cosmetics.

33. An article containing filler, which is an ink and comprises the glass filler as described in claim 30.

34. A molded body comprising glass fiber according to any one of claims 25 to 27, and being at least one selected from rubber reinforcing yarn, nonwoven fabric, prepreg, reinforced plastic, printed circuit board, inorganic cured body, filter, thermal insulation material, sound absorbing material and battery spacer.

35. A method for manufacturing glass fiber, comprising a step of melting a glass composition described in composition 1 or composition 2, and a step of forming the molten glass composition into glass fiber. Composition 1 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0≤ZnO≤10 0.1≤(Li2O+Na2O+K2O)≤1, The composition is 0.25 ≤ ZrO2 ≤ 5, and, It does not actually contain TiO2 and PbO; Composition 2 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0.1≤ZnO≤2.9 The composition is 0.1 ≤ (Li₂O + Na₂O + K₂O) ≤ 1, and, It does not actually contain TiO2, ZrO2, or PbO.

36. A method for manufacturing a glass filler, comprising a step of melting a glass composition described in composition 1 or composition 2, and a step of shaping the molten glass composition into a glass filler. Composition 1 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0≤ZnO≤10 0.1≤(Li2O+Na2O+K2O)≤1, The composition is 0.25 ≤ ZrO2 ≤ 5, and, It does not actually contain TiO2 and PbO; Composition 2 is a glass composition containing, expressed as a percentage by mass: 56≤SiO2≤70、 0.1≤B2O3≤8 15≤Al2O3≤24、 4≤MgO≤14 0≤CaO≤4、 0.1≤ZnO≤2.9 The composition is 0.1 ≤ (Li₂O + Na₂O + K₂O) ≤ 1, and, It does not actually contain TiO2, ZrO2, or PbO.

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