Glass composition, glass fiber, and glass filler

Abstract

To provide a glass composition which has a low linear expansion coefficient and a high Young's modulus, and is suitable for mass production.SOLUTION: The present disclosure provides a glass composition which contains the following components in 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, and 0.1≤ZrO2≤5, and does not substantially contain TiO2 and PbO.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a glass composition, also to glass fibers and glass fillers, and further to products such as molded articles containing glass fibers or glass fillers.

Background Art

[0002] In electronic devices, resin compositions are widely used to form electrical insulating members and mechanical members. Examples of electrical insulating members are connector housings used for SMT (surface mount technology), FPC (flexible printed circuits), between boards, CPU (central processing unit) sockets, memory cards, card edges, optical connectors, etc., reactance bobbins used for LCD (liquid crystal display) backlights, coils, flats, transformers, magnetic heads, etc., switches used for relay cases, relay base switches, reflow dip switches, tact switches, etc., sensor cases, capacitor casings, volume casings, trimmer casings. Examples of mechanical members are lens holders and pickup bases for optical pickups, insulators and terminals for micromotors, and drums for laser printers. Resin compositions are also used as films such as base films for FPCs and base films for copper-clad laminates. Also, there is a substrate composed of a resin composition as a type of printed circuit board provided in electronic devices. There is also a substrate composed of a resin composition in a printed wiring board before electronic components are mounted. Hereinafter, in this specification, both the printed circuit board and the printed wiring board are collectively referred to as "printed board".

[0003] The above resin composition contains a thermoplastic resin and glass fibers, and may further contain a curing agent, a modifier, etc. as required. The printed circuit board may further contain an inorganic filler. As the inorganic filler, a glass filler may be used. In recent years, in order to meet the requirements for miniaturization of electronic devices and the requirements for thinning for high functionality, the resin composition is required to have dimensional stability, and accordingly, its constituent materials are also required to have a low coefficient of thermal expansion and a high elastic modulus. Patent Document 1 discloses a glass composition having a low linear coefficient of thermal expansion and a high Young's modulus, and glass fibers composed of the glass composition.

[0004] The glass composition disclosed in the examples of Patent Document 1 contains titanium oxide (TiO2) in an amount of 0.7% or more and 3.0% or less on a mass basis, together with SiO2, B2O3, Al2O3, MgO, etc., and the content of zirconium dioxide (ZrO2) is limited to 0.6% or less. The glass composition disclosed in the examples of Patent Document 2 contains zinc oxide (ZnO) in an amount of 4.0% or more and 7.5% or less on a mass basis, together with SiO2, B2O3, Al2O3, MgO, etc. Patent Document 2 does not disclose a glass composition containing zirconium dioxide (ZrO2). The linear coefficient of thermal expansion of E-glass in the temperature range (50 to 200 °C) disclosed in Patent Document 2 is 53×10 -7 / °C (Comparative Example 1 of Patent Document 2), but the same coefficient of E-glass in a slightly wider temperature range (50 to 350 °C) described later is slightly larger, at 60×10 -7 / °C (Comparative Example 1 of the present application).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] With the trend towards thinner electronic devices for the purpose of miniaturization and high functionality of electronic devices, dimensional stability is required for the resin compositions that make up the electronic devices, and for the glass fibers and glass fillers that are the constituent materials, a low linear thermal expansion coefficient and a high elastic modulus are required. Therefore, an object of the present invention is to provide a new glass composition that has a low linear thermal expansion coefficient and a high Young's modulus and is also suitable for mass production.

Means for Solving the Problems

[0007] The present invention is, expressed in 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, 0.1 ≦ ZrO2 ≦ 5, and provides a glass composition containing the components of, and substantially free of TiO2.

[0008] From another aspect, the present invention is, expressed in mass%, 56 ≦ SiO2 ≦ 70, 0.1 ≦ B2O3 ≦ 8, 15 ≦ Al2O3 ≦ 24, 4 ≦ MgO ≦ 14, 0 ≦ CaO ≦ 4, 0.1 ≦ ZnO ≦ 3, 0 ≦ (Li2O + Na2O + K2O) ≦ 4, and provides a glass composition containing the components of, and substantially free of TiO2 and ZrO2.

[0009] From yet another aspect, the present invention is, expressed in 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, 1 ≤ ZrO2 ≤ 5, A glass composition containing the components is provided.

[0010] The present invention can also be described as follows. In the present invention, expressed in mass%, 56 ≤ SiO2 ≤ 70, 0.1 ≤ B2O3 ≤ 8, 15 ≤ Al2O3 ≤ 24, 4 ≤ MgO ≤ 14, 0 ≤ CaO ≤ 4, Contains the components of 0 ≤ (Li2O + Na2O + K2O) ≤ 4, A glass composition that satisfies at least one selected from the group consisting of a) and c), or b), is provided. a) Further contains the components of 0 ≤ ZnO ≤ 10 and 0.1 ≤ ZrO2 ≤ 5, Substantially does not contain TiO2. b) Further contains the component of 0.1 ≤ ZnO ≤ 3, Substantially does not contain TiO2 and ZrO2. c) Further contains the components of 0 ≤ ZnO ≤ 10 and 1 ≤ ZrO2 ≤ 5.

Advantages of the Invention

[0011] According to the present invention, a new glass composition having a low linear thermal expansion coefficient and a high Young's modulus and suitable for mass production is provided.

Modes for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described. However, the following description is not intended to limit the present invention to specific embodiments. In this specification, "substantially free of" and "substantially not contained" mean that the content rate is 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. "Substantially" is intended to allow the inclusion of trace amounts of impurities derived from glass raw materials, manufacturing equipment, forming equipment, etc. "Main component" means the component with the largest content rate based on mass. "T-Fe2O3" means total iron oxide converted to iron(III) oxide (Fe2O3). "T-SnO2" means total tin oxide converted to tin(IV) oxide (SnO2). "Alkali metal oxide" means lithium oxide (Li2O), sodium oxide (Na2O), and potassium oxide (K2O). The upper and lower limits of the content rates described below can be arbitrarily combined. Hereinafter, the glass composition may be simply referred to as glass, and the linear thermal expansion coefficient may be simply referred to as linear expansion coefficient, respectively.

[0013] [Glass Composition] <Component> (SiO2) SiO2 is a component that forms the skeleton of the glass and is the main component of the glass composition. Also, SiO2 is a component that adjusts the devitrification temperature and viscosity during glass formation and improves the water resistance of the glass. Furthermore, SiO2 is a component that lowers the linear expansion coefficient of the glass. And SiO2 has the effect of lowering the dielectric constant and dielectric tangent. The content rate of SiO2 is 56% by mass or more and 70% by mass or less. The lower limit of the content rate of SiO2 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 content rate of SiO2 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, further 61.9% by mass or less, and in some cases 61.8% by mass or less.

[0014] (B2O3) B2O3 is a component that forms the skeleton of glass. Also, B2O3 is a component that adjusts the devitrification temperature and viscosity during glass formation. On the other hand, excessive B2O3 content decreases the Young's modulus of the glass and increases the linear expansion coefficient of the glass. Furthermore, B2O3 is a component that has the effect of lowering the dielectric constant and the dielectric loss tangent. The content rate of B2O3 is 0.1 mass% or more and 8 mass% or less. The lower limit of the content rate of B2O3 is 0.5 mass% or more, 1 mass% or more, 1.5 mass% or more, 2 mass% or more, 2.5 mass% or more, 2.6 mass% or more, 2.7 mass% or more, 2.8 mass% or more, 2.9 mass% or more, 3 mass% or more, 3.1 mass% or more, 3.2 mass% or more, 3.3 mass% or more, 3.4 mass% or more, and in some cases may be 3.5 mass% or more. The upper limit of the content rate of B2O3 is 7 mass% or less, 6 mass% or less, and further 5.8 mass% or less, 5.5 mass% or less, 5 mass% or less, 4.5 mass% or less, 4.4 mass% or less, 4.3 mass% or less, 4.2 mass% or less, 4.1 mass% or less, 4.0 mass% or less, 3.9 mass% or less, and in some cases may be 3.5 mass% or less. The content rate of B2O3 may be 0.1 mass% or more and 6 mass% or less.

[0015] (Al2O3) Al2O3 is a component that forms the glass skeleton. Also, Al2O3 is a component that adjusts the devitrification temperature and viscosity during glass formation. Furthermore, Al2O3 is a component that improves the Young's modulus of the glass and is also a component that reduces the linear expansion coefficient of the glass. And, Al2O3 is a component that adjusts the dielectric constant and dielectric loss tangent of the glass. When the content rate of Al2O3 is 15 mass% or more and 24 mass% or less, the increase in the devitrification temperature of the glass is suppressed, the melting point of the glass does not become excessively high, and the uniformity when melting the raw materials increases. The lower limit of the content rate of Al2O3 can be 16 mass% or more, 17 mass% or more, 18 mass% or more, 18.5 mass% or more, 19 mass% or more, 19.5 mass% or more, 20 mass% or more, 20.1 mass% or more, and further 20.5 mass% or more. The upper limit of the content rate of Al2O3 can be 23.5 mass% or less, 23 mass% or less, 22.5 mass% or less, 22 mass% or less, further 21.8 mass% or less, 21.5 mass% or less, and in some cases 21 mass% or less, 20.9 mass% or less, 20.8 mass% or less, 20.7 mass% or less, 20.6 mass% or less, 20.5 mass% or less.

[0016] (MgO) MgO is a component that adjusts the devitrification temperature and viscosity during glass formation and is also a component that improves the Young's modulus of the glass. Also, MgO is a component that adjusts the dielectric constant and dielectric loss tangent of the glass. The content rate of MgO is 4 mass% or more and 14 mass% or less. The lower limit of the content rate of MgO can be 5 mass% or more, 6 mass% or more, 6.5 mass% or more, 7 mass% or more, 7.5 mass% or more, 8 mass% or more, 8.5 mass% or more, and further 9 mass% or more. The upper limit of the content rate of MgO can be 13 mass% or less, 12 mass% or less, 11 mass% or less, 10 mass% or less, 9.5 mass% or less, 9 mass% or less, 8.5 mass% or less, and in some cases 8 mass% or less.

[0017] (CaO) CaO is an optional component. CaO is a component that adjusts 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 the linear expansion coefficient of the glass. The lower limit of the 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, 0.1% by mass or more. The upper limit of the 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 not be substantially contained.

[0018] (MgO + CaO) Regarding the meltability and formability of the glass, the value of the sum (MgO + CaO) of the contents of MgO and CaO may be important. From the viewpoint of obtaining meltability and formability suitable for glass production, 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. Also, 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, in some cases 8.5% by mass or less, and further 8% by mass or less.

[0019] (MgO / CaO) The value of the ratio (MgO / CaO) of the content of MgO to the content of CaO is also important in adjusting the devitrification temperature and viscosity during glass formation, and further the Young's modulus and linear expansion coefficient of the glass. Here too, the content is on a mass basis. The lower limit of (MgO / CaO) can be 30 or more, 50 or more, 80 or more, 90 or more, further 95 or more, and in some cases 100 or more. The upper limit of (MgO / CaO) is not particularly limited, but can be 10000 or less, 1000 or less, and further 500 or less.

[0020] (SrO) SrO is an optional component. SrO is a component that adjusts 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 the linear expansion coefficient of the glass. The upper limit of the SrO content can be 5 mass% or less, 4 mass% or less, 3 mass% or less, 2 mass% or less, 1 mass% or less, 0.5 mass% or less, and even 0.1 mass% or less. SrO may not be substantially contained.

[0021] (BaO) BaO is also an optional component. BaO is a component that adjusts 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 the linear expansion coefficient of the glass. The upper limit of the BaO content can be 5 mass% or less, 4 mass% or less, 3 mass% or less, 2 mass% or less, 1 mass% or less, 0.5 mass% or less, and even 0.1 mass% or less. BaO may not be substantially contained.

[0022] (MgO + CaO + SrO + BaO) Regarding the meltability and formability of the glass, the value of the total content of MgO, CaO, SrO, and BaO (MgO + CaO + SrO + BaO) may be important. From the perspective of obtaining meltability and formability suitable for glass production, the lower limit of (MgO + CaO + SrO + BaO) can be 4 mass% or more, 5 mass% or more, 6 mass% or more, 7 mass% or more, 8 mass% or more, 8.5 mass% or more, and even 9 mass% or more. Also, the upper limit of (MgO + CaO + SrO + BaO) can be 14 mass% or less, 13 mass% or less, 12 mass% or less, 11 mass% or less, 10 mass% or less, 9.5 mass% or less, 9 mass% or less, in some cases 8.5 mass% or less, and even 8 mass% or less.

[0023] (ZnO, ZrO2) ZnO and ZrO₂ are components that adjust the devitrification temperature and viscosity during glass formation. Also, ZnO and ZrO₂ are components that improve the Young's modulus of the glass and are also components that lower the linear expansion coefficient of the glass. Furthermore, ZnO and ZrO₂ are components that adjust the dielectric constant and dielectric tangent of the glass. 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 from the viewpoint of making the devitrification temperature and viscosity of the molten glass within a range suitable for glass production while suppressing an increase in the devitrification temperature. This range is also suitable from the viewpoint of ensuring a low linear expansion coefficient 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, further 1.5% by mass or more, and in some cases 2% by mass or more, 2.5% by mass or more, 3% by mass or more, and even more than 3% by mass. The upper limit of (ZnO + ZrO₂) can be 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, less than 10% by mass, 9% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, further 6.5% by mass or less, 6% by mass or less, 5.8% by mass or less, 5.5% by mass or less, 5% by mass or less, and in some cases 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, and even 2% by mass or less. Each of ZnO and ZrO₂ is an optional component. In other words, the lower limit of the content of each of these components may be 0. (ZnO + ZrO₂) may be 0.1% by mass or more and 8% by mass or less.

[0024] The lower limit of the 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 the ZnO content can be 10% by mass or less, 9% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6.5% by mass or less, 6% by mass or less, 5.5% by mass or less, 5.3% by mass or less, 5.2% by mass or less, 5.1% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.9% by mass or less, 2.8% by mass or less, 2.7% by mass or less, 2.5% by mass or less, and further 2% by mass or less. Also, ZnO may not be substantially contained.

[0025] 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. Particularly in glass substantially free of TiO2, the ZrO2 content may 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 glass containing TiO2, the ZrO2 content may be 1% by mass or more, 1.1% by mass or more, and further 1.2% by mass or more, and may also be 5% by mass or less. Also, regardless of the TiO2 content, ZrO2 may not be substantially contained. However, the ZrO2 content suitable for achieving a low dielectric tangent is 0.7% by mass or more, and further 0.8% by mass or more.

[0026] (B2O3 + ZnO + ZrO2) The value of the total content of B2O3, ZnO, and ZrO2 (B2O3 + ZnO + ZrO2) may also be important in adjusting various properties. Appropriate adjustment of (B2O3 + ZnO + ZrO2) is effective in setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass production while suppressing an excessive increase in the devitrification temperature. The lower limit of (B2O3 + ZnO + ZrO2) may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 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, further 4.5% by mass or more, and in some cases 5% by mass or more. The upper limit of (B2O3 + ZnO + ZrO2) may be 18% by mass or less, 16% by mass or less, 15% by mass or less, 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 10% by mass or less, 9% by mass or less, 8% by mass or less, 7% by mass or less, and further 6% by mass or less.

[0027] (MgO + ZnO) The value of the sum of the contents of MgO and ZnO (MgO + ZnO) may also be important in adjusting various properties. Appropriate adjustment of (MgO + ZnO) is effective in setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass production while suppressing an excessive increase in the devitrification temperature. The lower limit of (MgO + ZnO) may 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, further 9% by mass or more, and in some cases 10% by mass or more. The upper limit of (MgO + ZnO) may 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.

[0028] (Li2O, Na2O, K2O) Alkali metal oxides (Li2O, Na2O, K2O) are components that adjust the devitrification temperature and viscosity during glass formation. When the total value of the content of alkali metal oxides (Li2O + Na2O + K2O) is 0 mass% or more and 4 mass% or less, the devitrification temperature and viscosity of the molten glass can be brought into a range suitable for glass production while suppressing an excessive increase in the devitrification temperature. Also, while suppressing an increase in the melting point of the glass and enabling more uniform melting of the glass raw materials, high glass heat resistance can be ensured without an excessive decrease in the glass transition temperature. The lower limit of (Li2O + Na2O + K2O) can be 0.1 mass% or more, 0.15 mass% or more, 0.2 mass% or more, 0.25 mass% or more, and further 0.3 mass% or more. The addition of a small amount of alkali metal oxide is effective in reducing bubbles in the glass. The upper limit of (Li2O + Na2O + K2O) can be 3 mass% or less, 2 mass% or less, less than 2 mass%, 1.5 mass% or less, 1 mass% or less, less than 1 mass%, 0.9 mass% or less, 0.8 mass% or less, 0.7 mass% or less, 0.6 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less. The alkali metal oxide may not be substantially contained. Each of Li2O, Na2O, and K2O is an optional component. In other words, the lower limit of the content of each of these components may be 0.

[0029] The lower limit of the content of Li2O can be 0.1 mass% or more, and further 0.2 mass% or more. The upper limit of the content of Li2O can be 4 mass% or less, 3 mass% or less, 2 mass% or less, 1.5 mass% or less, 1 mass% or less, less than 1 mass%, 0.9 mass% or less, 0.8 mass% or less, 0.7 mass% or less, 0.6 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, and further 0.2 mass% or less. Li2O may not be substantially contained.

[0030] The upper and lower limits of the Na2O and K2O contents can be the values described as the upper and lower limits of the Li2O content, respectively. The sum of the Na2O and K2O contents (Na2O + K2O) can be 4% by mass or less, 3% by mass or less, 2% by mass or less, less than 2% by mass, 1.5% by mass or less, 1% by mass or less, less than 1% by mass, 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 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, and in some cases 0.1% by mass or less. The lower limit of the (Na2O + K2O) content may be 0.1% by mass or more, and further 0.2% by mass or more. Na2O may not be substantially contained. K2O may also not be substantially contained.

[0031] (TiO2) TiO2 is a component that adjusts the devitrification temperature and viscosity during glass formation. Also, TiO2 is a component that improves the Young's modulus of the glass and is also a component that lowers the linear expansion coefficient of the glass. Furthermore, TiO2 is a component that improves the meltability and chemical durability of the glass and improves the ultraviolet absorption characteristics of the glass. The lower limit of the TiO2 content may 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 in some cases 1.2% by mass or more. However, in order to balance the Young's modulus, linear expansion coefficient, and mass production compatibility well, it is desirable not to contain TiO2 excessively. The upper limit of the 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 not be substantially contained.

[0032] (TiO2 + ZrO2) The value of the sum of the contents of TiO2 and ZrO2 (TiO2 + ZrO2) may also be important in adjusting the devitrification temperature and viscosity during glass formation, as well as the Young's modulus and linear expansion coefficient 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, further 0.4% by mass or more, and in some cases 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 in some cases 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, depending on the embodiment, neither TiO2 nor ZrO2 may be substantially contained.

[0033] (Fe) In the glass, Fe usually exists in the state of Fe 2+ or Fe 3+ . Fe 3+ is a component that enhances the ultraviolet absorption characteristics of the glass, and Fe 2+ is a component that enhances the heat ray absorption characteristics of the glass. The upper limit of the Fe 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, 0.4% by mass or less, and further 0.3% by mass or less, expressed as T-Fe2O3. The lower limit of the Fe content can be 0.1% by mass or more, 0.15% by mass or more, and further 0.2% by mass or more, expressed as T-Fe2O3. Particularly in a glass composition with a low content of alkali metal oxides, a small amount of iron oxide can promote the clarification of the glass and contribute to the reduction of bubbles. Fe may not be substantially contained.

[0034] (CeO2, SnO2) CeO2 and SnO2 are optional components. Particularly in a glass composition with a low content of alkali metal oxides, trace amounts of CeO2 and SnO2 may contribute to the promotion of glass clarification. CeO2 and SnO2 are components that adjust the devitrification temperature and viscosity during glass formation. Also, CeO2 and SnO2 are components that improve the Young's modulus of the glass and also reduce the linear expansion coefficient of the glass. The upper limit of the content of CeO2 and SnO2 may each be 0.1% by mass or more. The upper limit of the content of CeO2 and SnO2 may each 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. CeO2 may not be substantially contained. SnO2 may also not be substantially contained. Note that the content of SnO2 is the value indicated by T-SnO2.

[0035] (SO3) SO3 is also an optional component. Trace amounts of SO3 may reduce the bubbles remaining in the glass and contribute to the improvement of the mass production suitability of the glass. The lower limit of the content of SO3 may be 0.001% by mass or more, and further 0.002% by mass or more. The upper limit of the content of SO3 may be 0.5% by mass or less, 0.2% by mass or less, 0.1% by mass or less, 0.05% by mass or less, 0.04% by mass or less, 0.03% by mass or less, 0.02% by mass or less, and further 0.01% by mass or less. SO3 may not be substantially contained.

[0036] (F2, Cl2) Fluorine (F₂) and chlorine (Cl₂) are also optional components. Especially in a glass composition with a low content of alkali metal oxides, F₂ and Cl₂ can contribute to the promotion of glass clarification. However, since F₂ and Cl₂ are volatile, they may scatter during melting. The upper limits of the contents 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 not be substantially contained. The lower limit of the content of F₂ may 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 not be substantially contained.

[0037] (Total of components) The total of the above-described components, that is, the components described from SiO₂ to F₂ and Cl₂, can be 95% by mass or more, 97% by mass or more, further 99% by mass or more, and in some cases 99.5% by mass or more. The lower limit of the total content of the components represented by (SiO₂ + B₂O₃ + Al₂O₃ + MgO + CaO + ZnO) may be 75% by mass or more, 85% by mass or less, 90% by mass or more, further 95% by mass or more, and in some cases 97% by mass or more. The upper limit of the total content of the components represented by (SiO₂ + B₂O₃ + Al₂O₃ + MgO + CaO + ZnO) may be 99% by mass or less. The lower limit of the total of the components represented by (Li₂O + Na₂O + K₂O + TiO₂ + ZrO₂ + T-Fe₂O₃) may 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 represented by (Li₂O + Na₂O + K₂O + TiO₂ + ZrO₂ + T-Fe₂O₃) may be 19% by mass or less, 10% by mass or less, 5% by mass or less, and further 3% by mass or less.

[0038] (Other components) Examples of other optional components include at least one selected from the group consisting of 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, the other optional components are not necessarily limited to these. The other optional components may each be contained at a content rate of 3% by mass or less. The allowable content rate of each of the 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, or even 0.1% by mass or less. Each of the other optional components may not be substantially contained. Y2O3 and La2O3 are components that adjust the devitrification temperature and viscosity during glass formation. Also, Y2O3 and La2O3 are components that improve the Young's modulus of the glass. For example, the sum of the content rates of Y2O3 and La2O3 (Y2O3 + La2O3) may be 5% by mass or less, 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, or even 0.1% by mass or less. For example, from the perspective of environmental protection, it is desirable that As2O3 and Sb2O3 are not substantially contained respectively. The total of the content rates of the other optional components listed above may be 5% by mass or less, less than 3% by mass, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, or even 0.1% by mass or less.

[0039] <Preferred Composition> Preferred compositions are exemplified below. The ranges noted in parentheses for each component are more preferred ranges. (Composition A1) Expressed in mass%, 58 ≦ SiO2 ≦ 64 (58.5 ≦ SiO2 ≦ 63), 1 ≦ B2O3 ≦ 6 (1.5 ≦ B2O3 ≦ 5), 17 ≦ Al2O3 ≦ 23 (18 ≦ Al2O3 ≦ 22), 4 ≦ MgO ≦ 13 (7 ≦ MgO ≦ 12), 0 ≦ CaO ≦ 3 (0 ≦ CaO ≦ 1), 1 ≦ ZnO ≦ 8 (1.1 ≦ ZnO ≦ 7), 0 ≦ (Li2O + Na2O + K2O) ≦ 3 (0 ≦ (Li2O + Na2O + K2O) ≦ 2), 0.2 ≦ ZrO2 ≦ 4 (0.3 ≦ ZrO2 ≦ 3), and contains no substantial amount of TiO2.

[0040] Composition A1 has a low linear thermal expansion coefficient and a high Young's modulus, and is also excellent in mass production compatibility. An example of excellent mass production compatibility is that ΔT obtained by subtracting the devitrification temperature from the working temperature is a positive value.

[0041] (Composition A2) Expressed in mass%, 58.5 ≦ SiO2 ≦ 62 1.5 ≦ B2O3 ≦ 5, 18 ≦ Al2O3 ≦ 22, 7 ≦ MgO ≦ 12, 0 ≦ CaO ≦ 1, 1.1 ≦ ZnO ≦ 7, 0.1 ≦ (Li2O + Na2O + K2O) ≦ 2, 0.3 ≦ ZrO2 ≦ 3, and contains no substantial amount of TiO2, satisfying 9 ≦ (MgO + ZnO) ≦ 13.8.

[0042] Composition A2 has a low linear thermal expansion coefficient and a high Young's modulus, and is also excellent in mass production compatibility. An example of excellent mass production compatibility is a low working temperature and a large ΔT. Here, the low working temperature is, for example, 1395 °C or lower, and the large ΔT is, for example, 10 °C or higher.

[0043] (Composition B) Expressed in mass%, 58 ≦ SiO2 ≦ 64 (58.5 ≦ SiO2 ≦ 63), 1 ≦ B2O3 ≦ 6 (1.5 ≦ B2O3 ≦ 5), 17 ≦ Al2O3 ≦ 23 (18 ≦ Al2O3 ≦ 22), 4 ≦ MgO ≦ 13 (7 ≦ MgO ≦ 12), 0 ≦ CaO ≦ 3 (0 ≦ CaO ≦ 1), 0.5 ≦ ZnO ≦ 2.8 (1.1 ≦ ZnO ≦ 2.8), 0 ≦ (Li2O + Na2O + K2O) ≦ 3 (0 ≦ (Li2O + Na2O + K2O) ≦ 2), A glass composition containing the components of and substantially not containing TiO2 and ZrO2.

[0044] Composition B is different from Compositions A1 - A2 and C in that it substantially does not contain ZrO2. Composition B has a low linear thermal expansion coefficient and a high Young's modulus, and is also excellent in mass - production compatibility.

[0045] (Composition C) Expressed in mass%, 58 ≦ SiO2 ≦ 64 (58.5 ≦ SiO2 ≦ 63), 1 ≦ B2O3 ≦ 6 (1.5 ≦ B2O3 ≦ 5), 17 ≦ Al2O3 ≦ 23 (18 ≦ Al2O3 ≦ 22), 4 ≦ MgO ≦ 13 (7 ≦ MgO ≦ 12), 0 ≦ CaO ≦ 3 (0 ≦ CaO ≦ 1), 1 ≦ ZnO ≦ 8 (1.1 ≦ ZnO ≦ 7), 0 ≦ (Li2O + Na2O + K2O) ≦ 3 (0 ≦ (Li2O + Na2O + K2O) ≦ 2), 0.1 ≦ TiO2 ≦ 4 (0.3 ≦ TiO2 ≦ 3), 1.1 ≦ ZrO2 ≦ 4 (1.1 ≦ ZrO2 ≦ 3), A glass composition containing the components of.

[0046] Composition C is different from Compositions A1 - A2 and B in that it contains both TiO2 and ZrO2. Composition C has a low linear thermal expansion coefficient and a high Young's modulus, and is also excellent in mass - production compatibility. Also, Composition C is suitable for achieving a low dielectric tangent.

[0047] Compositions A1, A2, B, and C may further contain 0.1 ≦ T-Fe2O3 ≦ 3 (more preferably 0.1 ≦ T-Fe2O3 ≦ 2), and together with T-Fe2O3 in this range, may further contain 0.001 ≦ SO3 ≦ 0.5 (more preferably 0.002 ≦ SO3 ≦ 0.3). Also, as described in the <components> column, the upper and / or lower limits of the content of each component in Compositions A1, A2, B, and C can be changed. Furthermore, as described in the <components> column, the total of the components in Compositions A1, A2, B, and C may be adjusted, and they may contain other components.

[0048] <Properties> The properties that the glass composition of this embodiment can have will be described below. (Melting properties) The temperature at which the viscosity of the molten glass becomes 1000 dPa·sec (1000 poise) is called the working temperature of the glass and is a temperature suitable for glass forming. If the working temperature of the glass is 1100 °C or higher, variations in dimensions such as the glass fiber diameter can be reduced. If the working temperature is 1450 °C or lower, the fuel cost for melting the glass can be reduced, the glass manufacturing apparatus is less likely to be corroded by heat, and the apparatus life is extended. The lower limit of the working temperature can be 1200 °C or higher, 1300 °C or higher, 1320 °C or higher, 1330 °C or higher, 1340 °C or higher, and further 1350 °C or higher. The upper limit of the working temperature can be 1420 °C or lower, 1410 °C or lower, 1400 °C or lower, 1395 °C or lower, 1390 °C or lower, 1385 °C or lower, 1382 °C or lower, and further 1380 °C or lower.

[0049] The larger the temperature difference ΔT obtained by subtracting the devitrification temperature from the working temperature, the less likely devitrification occurs during glass forming, and a homogeneous glass can be produced with a high yield. ΔT can be 0 °C or higher, 5 °C or higher, 10 °C or higher, and further 15 °C or higher. The upper limit of ΔT is not particularly limited, but for example, it can be 100 °C or lower, 80 °C or lower, 70 °C or lower, 65 °C or lower, 60 °C or lower, 55 °C or lower, and further 50 °C or lower. The devitrification temperature is the temperature at which crystals start to form and grow in the molten glass substrate and can be measured by the method described later.

[0050] (Coefficient of linear expansion) The coefficient of linear expansion is precisely the average coefficient of linear expansion at 50 to 350 °C. The low coefficient of linear expansion of the glass contributes to improving the dimensional stability of the resin composition containing the glass. The lower limit of the coefficient of linear expansion is 20×10 -7 / °C or more, 25×10 -7 / °C or more, 26×10 -7 / °C or more, and furthermore can be 27×10 -7 / °C or more. The upper limit of the coefficient of linear expansion is 35×10 -7 / °C or less, 34×10 -7 / °C or less, 33×10 -7 / °C or less, and furthermore can be 32×10 -7 / °C or less, and in some cases can be 31×10 -7 / °C or less.

[0051] (Glass transition temperature) The glass transition temperature (glass transition point) serves as an indicator of the heat resistance of the glass. When the resin composition containing the glass is subjected to heat treatment, a high glass transition temperature is desired. The lower limit of the glass transition temperature can be 650 °C or more, 700 °C or more, 710 °C or more, 720 °C or more, and furthermore 730 °C or more. The upper limit of the glass transition temperature can be 800 °C or less, 790 °C or less, 780 °C or less, and furthermore 770 °C or less.

[0052] (Young's modulus) The high Young's modulus of the glass contributes to improving the mechanical properties and dimensional stability of the resin composition containing glass fibers or glass fillers. Young's modulus can be calculated from the longitudinal wave velocity and transverse wave velocity of elastic waves propagating in the glass measured by the ordinary ultrasonic method and the density of the glass measured by the Archimedes method. The lower limit of Young's modulus can be 85 GPa or more, 86 GPa or more, 87 GPa or more, 88 GPa or more, 89 GPa or more, and furthermore 90 GPa or more. The upper limit of Young's modulus can be 100 GPa or less, or can be 99 GPa or less, 98 GPa or less, 97 GPa or less, 96 GPa or less, and furthermore 95 GPa or less.

[0053] (Dielectric constant, dielectric loss tangent) The low dielectric constant of the glass contributes to the improvement of the dielectric properties of the resin composition containing glass fibers or glass fillers. The dielectric constant at a measurement frequency of 1 GHz is 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 in some cases 5.3 or less. The dielectric constant strictly means the relative dielectric constant, but in this specification, it is simply referred to as the dielectric constant according to convention. The dielectric constant is the value at room temperature (25 °C). The dielectric constant may be 5.0 or more.

[0054] The low dielectric tangent of the glass also contributes to the improvement of the dielectric properties of the resin composition containing glass fibers or glass fillers. The dielectric tangent at a measurement frequency of 1 GHz is 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, 0.0032 or less, 0.0031 or less, 0.0030 or less, and further 0.0029 or less, 0.0028 or less, 0.0027 or less, 0.0026 or less, 0.0025 or less, 0.0024 or less, 0.0023 or less, 0.0022 or less, 0.0021 or less, 0.0020 or less, and in some cases 0.0019 or less, 0.0018 or less, 0.0017 or less, 0.0016 or less, 0.0015 or less. The dielectric tangent is the value at room temperature (25 °C). The dielectric tangent may be 0.0010 or more.

[0055] [Glass product] <Glass fiber> The glass fiber of the present embodiment is composed of the above-described glass composition. According to the present embodiment, even when the fiber diameter is small, the occurrence of devitrification and the inclusion of bubbles in the glass fiber can be further suppressed. Therefore, the glass fiber of the present embodiment can be a glass fiber having a small fiber diameter.

[0056] The average fiber diameter of the glass fiber is, for example, 0.1 to 50 μm. The average fiber diameter may 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, and may 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. The glass composition having a characteristic temperature suitable for mass production is suitable for being stably manufactured as thin glass fibers. In a preferred embodiment, the average fiber diameter is even thinner, for example, 3.9 μm or less, and even 3.5 μm or less. The glass fiber is, for example, a glass long fiber (filament).

[0057] The glass fiber may have at least one shape selected from the group consisting of roving, roving cloth, continuous strand mat, milled fiber, flat fiber, filament mat, chopped strand, yarn, glass cloth, and glass tape.

[0058] The flat fiber has a shape obtained by cutting glass fibers having a flat cross-sectional shape such as an ellipse. The major axis D2 is larger than the minor axis D1 of the cross-section of the flat fiber, and D2 / D1 is, 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 100000 μm. The flat fiber can be obtained by a known method. The cross-sectional shape of the flat fiber may have a concave shape in which the surface extending along the major axis D2 recedes at the central part rather than at the end part.

[0059] The glass fiber can be manufactured by a method including a step of melting the glass composition of the present embodiment and a step of forming the molten glass composition into glass fibers.

[0060] <Glass filler> The glass filler of this embodiment is composed of the glass composition described above. The glass filler can be at least one selected from the group consisting of flake glass, glass powder, glass beads, and fine flakes.

[0061] Flake glass, also called scaly glass, has a flake-like shape. The average particle size of the flake glass is, for example, 0.2 to 15000 μm. The aspect ratio of the flake glass is, for example, 2 to 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 100 or more flake glasses using a scanning electron microscope (SEM) and calculating the average value. The average particle size of the flake glass and other glass fillers can be determined by the particle size (D50) corresponding to a cumulative volume percentage of 50% in the particle size distribution measured by the laser diffraction scattering method. Flake glass can be obtained by known blowing methods, cup methods, etc.

[0062] Glass powder is powdery glass and is manufactured by pulverizing glass. The average particle size of the glass powder is, for example, 1 to 500 μm. The particle size of the glass powder is defined as the diameter of a sphere having the same volume as the particles of the glass powder. Glass powder can be obtained by known methods.

[0063] Glass beads have a spherical or substantially spherical shape. The average particle size of the glass beads is, for example, 1 to 500 μm. The particle size of the glass beads is defined as the diameter of a sphere having the same volume as the particles of the glass beads. Glass beads can be obtained by known methods.

[0064] Fine flakes are thin glass flakes. The fine flakes are flaky glass of a thin material. The fine flakes may be composed of, for example, flaky glass having an average thickness of 0.1 to 2.0 μm, or may contain, for example, flaky glass in the range of 0.01 to 2.0 μm in thickness at a ratio of 90% by mass or more. The fine flakes having such a small average thickness and small variation in thickness have a high effect of reinforcing the resin and are also excellent in the effect of reducing the molding shrinkage rate of the resin. The fine flakes are also suitable for relaxing the restrictions on the thickness of the resin molded body and the like more than before. The fine flakes are preferably composed of flaky glass having an average thickness of 0.1 to 1.0 μm. The fine flakes preferably contain flaky glass in the range of 0.05 to 1.0 μm in thickness at a ratio of 90% by mass or more. The fine flakes can be obtained by the method described for the flaky glass.

[0065] The glass filler can be manufactured by a method including a step of melting the glass composition of the present embodiment and a step of molding the melted glass composition into the glass filler.

[0066] [Product containing glass fiber and / or glass filler] The glass fiber and glass filler of the present embodiment can be used in various products exemplified below. The various products have aspects as molded bodies, filler-containing products, resin products, and the like.

[0067] [Molded body] The molded body of the present embodiment contains the glass fiber described above and is molded into a predetermined shape. The molded body is not limited to the following, but can be at least one selected from the group consisting of rubber reinforcing cords, non-woven fabrics, prepregs, reinforced plastics, printed circuit boards, inorganic cured bodies, filters, heat insulating materials, sound absorbing materials, and battery separators.

[0068] [Filler-containing product] The filler-containing product of this embodiment contains the glass filler described above. The filler-containing product can be at least one selected from the group consisting of, but not limited to, reinforced plastics, paints, inks, printed circuit boards, inorganic hardened bodies, and cosmetics.

[0069] <Resin product> The resin product of this embodiment contains the glass fiber and / or glass filler described above and a resin. The resin product can be an electrical insulating member or a mechanical member. Examples of these members are as described above. The resin may be a thermoplastic resin. The thermoplastic resin is not particularly limited, and examples thereof include polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyester, polyamide, polycarbonate, polybutylene, polybutylene terephthalate, and copolymers thereof. When using polybutylene terephthalate, the effect of suppressing warping of the molded product and improving dimensional stability by mixing with the glass filler becomes greater. Flake glass, flat fiber, and fine flake have a relatively large specific surface area and are suitable for ensuring the bonding force with the thermoplastic resin.

[0070] [Technology provided by this embodiment] The technology provided by this embodiment is as follows. (Technology 1) Expressed in 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, 0.1 ≦ ZrO2 ≦ 5, A glass composition containing the components of and substantially free of TiO2.

[0071] (Technology 2) Expressed in mass%, 56 ≦ SiO2 ≦ 70, 0.1 ≦ B2O3 ≦ 8, 15 ≤ Al2O3 ≤ 24, 4 ≤ MgO ≤ 14, 0 ≤ CaO ≤ 4, 0.1 ≤ ZnO ≤ 3, 0 ≤ (Li2O + Na2O + K2O) ≤ 4, A glass composition containing the components and substantially free of TiO2 and ZrO2.

[0072] (Technology 3) Expressed in 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, 1 ≤ ZrO2 ≤ 5, A glass composition containing the components.

[0073] (Technology 4) Expressed in mass%, a glass composition containing the components of 75 ≤ (SiO2 + B2O3 + Al2O3 + MgO + CaO + ZnO) ≤ 99, described in any one of Technologies 1 to 3.

[0074] (Technology 5) Expressed in mass%, a glass composition containing the components of 1 ≤ (ZnO + ZrO2) ≤ 15, described in any one of Technologies 1 to 4.

[0075] (Technology 6) Expressed in mass%, a glass composition containing the components of 1 ≤ (Li2O + Na2O + K2O + TiO2 + ZrO2 + T-Fe2O3) ≤ 19, described in any one of Technologies 1 to 5. However, T-Fe2O3 is the total iron oxide converted to Fe2O3.

[0076] (Technology 7) Expressed in mass%, a glass composition containing the components of 2 ≤ B2O3 ≤ 6, described in any one of Technologies 1 to 6.

[0077] (Technology 8) A glass composition according to any one of Technologies 1 to 7, containing components expressed in mass % such that 5 ≦ MgO ≦ 13.

[0078] (Technology 9) A glass composition according to Technology 8, containing components expressed in mass % such that 0 ≦ CaO ≦ 1.

[0079] (Technology 10) A glass composition according to any one of Technologies 1 to 9, substantially not containing SrO.

[0080] (Technology 11) A glass composition according to any one of Technologies 1 to 10, substantially not containing BaO.

[0081] (Technology 12) A glass composition according to any one of Technologies 1 to 11, containing components expressed in mass % such that 0 ≦ ZnO ≦ 8.

[0082] (Technology 13) A glass composition according to any one of Technologies 1 to 12, containing components expressed in mass % such that 4 ≦ (MgO + ZnO) ≦ 17.

[0083] (Technology 14) A glass composition according to any one of Technologies 1 to 13, containing components expressed in mass % such that 0 ≦ (Li2O + Na2O + K2O) ≦ 1.

[0084] (Technology 15) A glass composition according to Technology 14, containing components expressed in mass % such that 0.1 ≦ (Li2O + Na2O + K2O) ≦ 1.

[0085] (Technology 16) A glass composition according to any one of Technologies 1 to 15, containing components expressed in mass % such that 0 ≦ (Na2O + K2O) ≦ 1.

[0086] (Technology 17) A glass composition according to any one of Technologies 1 to 16, containing components expressed in mass% such that 0 ≦ (TiO2 + ZrO2) ≦ 4.

[0087] (Technology 18) A glass composition according to any one of Technologies 1 to 17, containing components expressed in mass% such that 0 ≦ T-Fe2O3 ≦ 5, where T-Fe2O3 is total iron oxide converted to Fe2O3.

[0088] (Technology 19) A glass composition according to any one of Technologies 1 to 18, containing components expressed in mass% such that 0 ≦ Y2O3 ≦ 3.

[0089] (Technology 20) A glass composition according to any one of Technologies 1 to 19, containing components expressed in mass% such that 0 ≦ T-SnO2 ≦ 2, where T-SnO2 is total tin oxide converted to SnO2.

[0090] (Technology 21) A glass composition according to any one of Technologies 1 to 20, containing components expressed in mass% such that 0 ≦ CeO2 ≦ 2.

[0091] (Technology 22) A glass composition according to any one of Technologies 1 to 21, containing components expressed in mass% such that 0 ≦ F2 ≦ 5.

[0092] (Technology 23) A glass composition according to any one of Technologies 1 to 22, containing components expressed in mass% such that 0 ≦ SO3 ≦ 0.5.

[0093] (Technology 24) When the temperature at which the viscosity is 1000 dPa·sec is defined as the working temperature, a glass composition according to any one of Technologies 1 to 23, wherein the working temperature is 1450°C or lower.

[0094] (Technology 25) When the temperature at a viscosity of 1000 dPa·sec is defined as the working temperature, the temperature difference ΔT obtained by subtracting the devitrification temperature from the working temperature is 0°C or higher, and the glass composition according to any one of Technologies 1 to 24.

[0095] (Technology 26) The glass composition according to any one of Technologies 1 to 25, having a Young's modulus of 85 to 100 GPa.

[0096] (Technology 27) The average linear expansion coefficient at 50 to 350°C is 20 to 35×10 -7 / °C, and the glass composition according to any one of Technologies 1 to 26.

[0097] (Technology 28) The glass composition according to any one of Technologies 1 to 27, having a dielectric constant at a frequency of 1 GHz of 6.5 or less.

[0098] (Technology 29) The glass composition according to any one of Technologies 1 to 28, having a dielectric tangent at a frequency of 1 GHz of 0.0060 or less.

[0099] (Technology 30) Glass fiber containing the glass composition according to any one of Technologies 1 to 29.

[0100] (Technology 31) The glass fiber according to Technology 30, having at least one shape selected from the group consisting of roving, roving cloth, continuous strand mat, milled fiber, flat fiber, filament mat, chopped strand, yarn, glass cloth, and glass tape.

[0101] (Technology 32) Glass filler containing the glass composition according to any one of Technologies 1 to 29.

[0102] (Technology 33) The glass filler according to Technology 32, which is at least one selected from the group consisting of flaky glass, glass powder, glass beads, and fine flakes.

[0103] (Technology 34) A molded article containing the glass fiber according to Technology 30 and being at least one selected from the group consisting of a rubber-reinforcing cord, a nonwoven fabric, a prepreg, a reinforced plastic, a printed circuit board, an inorganic cured body, a filter, a heat insulating material, a sound absorbing material, and a battery separator.

[0104] (Technology 35) A filler-containing product containing the glass filler according to Technology 32 and being at least one selected from the group consisting of a reinforced plastic, a paint, an ink, a printed circuit board, an inorganic cured body, and a cosmetic.

[0105] (Technology 36) A method for manufacturing glass fibers, comprising a step of melting the glass composition according to any one of Technologies 1 to 29 and a step of forming the melted glass composition into glass fibers.

[0106] (Technology 37) A method for manufacturing a glass filler, comprising a step of melting the glass composition according to any one of Technologies 1 to 29 and a step of forming the melted glass composition into a glass filler.

Examples

[0107] Hereinafter, embodiments of the present invention will be described more specifically with reference to Examples and Comparative Examples. (Examples and Comparative Examples) Ordinary glass raw materials such as silica sand were formulated so as to have the compositions shown in Tables 1 to 4, and batches of the glass raw materials were prepared for each of the examples and comparative examples. Using an electric furnace, each batch was heated to 1500 to 1600 °C and melted, and maintained for about 4 hours until the composition became uniform. Thereafter, a part of the molten glass (glass melt) was poured out onto an iron plate and slowly cooled to room temperature in the electric furnace to obtain a glass composition as a bulk (plate-like object, glass sample). In Examples 16, 28, 35 to 37 and Comparative Example 3, tin(IV) oxide (SnO2) was used as the SnO2 source. In Examples 17, 19, 38, 39, cerium(IV) oxide (CeO2) was used as the CeO2 source. In Examples 19 to 23, 29, 31 to 36, 38 to 42, sodium sulfate was used as the SO3 source, and in Examples 26, 37, lithium sulfate monohydrate was used as the SO3 source.

[0108] The method for evaluating the properties will be described below. (Working temperature) Regarding the obtained glass composition, the relationship between viscosity and temperature was examined by the ordinary platinum ball pulling-up method, and the working temperature was determined from the results. Here, the platinum ball pulling-up method is a method of measuring viscosity by applying the relationship between the load (resistance) when pulling up the platinum ball at a constant speed in molten glass, the gravity and buoyancy acting on the platinum ball, etc., to Stokes' law showing the relationship between the viscosity and the falling speed when minute particles settle in a fluid.

[0109] (Devitrification temperature) The glass composition crushed to a size of 1.0 to 2.8 mm in particle diameter was placed in a platinum boat and held in an electric furnace with a temperature gradient (900 to 1500 °C) for 2 hours, and the devitrification temperature was determined from the maximum temperature of the electric furnace corresponding to the position where crystals appeared. When the glass became turbid and no crystals could be observed, the maximum temperature of the electric furnace corresponding to the position where turbidity appeared was taken as the devitrification temperature. Here, the particle diameter is a value measured by the sieving method. The temperature difference (temperature distribution in the electric furnace) varying depending on the location in the electric furnace was measured in advance, and the glass composition placed at a predetermined location in the electric furnace was heated at the temperature of the predetermined location measured in advance. The temperature difference ΔT is the temperature difference obtained by subtracting the devitrification temperature from the working temperature.

[0110] (Coefficient of linear expansion) For the obtained glass composition, the average coefficient of linear expansion at 50 to 350 °C was measured using a commercially available dilatometer [Rigaku Corporation, Thermomechanical Analyzer, TMA8510]. Also, based on the thermal expansion curve obtained from the TMA apparatus, the glass transition temperature T g was obtained.

[0111] (Young's modulus) Young's modulus E was measured by the normal ultrasonic method by measuring the longitudinal wave velocity vl and the transverse wave velocity vt of the elastic wave propagating in the glass, and from the density ρ of the glass measured separately by the Archimedes method, E = 3ρ·v t 2 ·(v l 2 - 4 / 3·v t 2 ) / (v l 2 - v t 2 ) was obtained from the formula.

[0112] (Dielectric constant, dielectric loss tangent) The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured using a dielectric constant measuring device by the cavity resonator perturbation method. The measurement temperature was 25 °C, and the dimensions of the sample for measurement were a rectangular parallelepiped with a height of 100 mm and a bottom surface being a square with a side length of 1.5 mm.

[0113] (Number of bubbles) Ordinary glass raw materials such as silica sand were formulated, and batches of glass raw materials were prepared for each of the examples and comparative examples. Using an electric furnace, each 150 g batch was heated and melted at the test temperature of 1600 °C and maintained for 2 hours until the composition became uniform. Thereafter, a part of the molten glass (glass melt) was poured out onto an iron plate and slowly cooled to room temperature in the electric furnace to obtain a glass sample. The number of bubbles in this glass sample was observed with an optical microscope, and the number of bubbles per 100 g of glass was calculated. Those with less than 400 bubbles per 100 g of glass were designated as A, those with 400 or more and less than 2000 as B, those with 2000 or more and less than 10000 as C, and those with 10000 or more as D.

[0114] The measurement results are shown in Tables 1 to 4. Note that all the glass compositions in the tables are values expressed in mass %. Also, Fe2O3 and SnO2 in the tables represent T-Fe2O3 and T-SnO2, respectively.

[0115] [Table 1]

[0116] [Table 2]

[0117] [Table 3]

[0118] [Table 4]

[0119] From each of the examples, results of a linear expansion coefficient of 29 - 32×10 -7 / °C, a Young's modulus of 90 - 92 GPa, a working temperature of 1324 - 1410 °C, and a difference ΔT (working temperature - devitrification temperature) of 0 - 54 °C were obtained.

[0120] The glass composition of Comparative Example 1 has an E glass composition. E glass is inferior in average linear expansion coefficient and Young's modulus at 50 to 350°C. The glass composition of Comparative Example 2 has an S glass composition. S glass has a high working temperature, a negative ΔT, and is inferior in mass productivity. The glass composition of Comparative Example 3 has the glass composition of Example 2 of Patent Document 1. This glass is inferior in Young's modulus and has a slightly high working temperature. The glass composition of Comparative Example 4 has the glass composition of Example 2 of Patent Document 2. This glass is inferior in average linear expansion coefficient at 50 to 350°C. Note that the reason why the linear expansion coefficient of Comparative Example 4 is higher (33×10 -7 / °C) than the measured value (29×10 -7 / °C) in Patent Document 2 is due to the difference in the measured temperature range. Further, when the present inventors conducted a follow-up test, Comparative Example 4 had a negative ΔT and was inferior in mass productivity. The glass compositions of Comparative Examples 5-16 also had at least one of the average linear expansion coefficient, Young's modulus, and the difference ΔT that was not sufficient.

Claims

1. Expressed in mass %, 56≦SiO 2 ≦70、 0.1≦B 2 O 3 ≦8、 15≦Al 2 O 3 ≦24、 4≦MgO≦14, 0≦CaO≦4, 0≦ZnO≦10, 0.1≦(L- 2 O+1 2 O+K 2 O)≦1、 0.1≦ZrO 2 ≦5、 Contains TiO 2 and a glass composition substantially free of PbO.

2. Expressed in mass %, 56≦SiO 2 ≦70、 0.1≦B 2 O 3 ≦8、 15≦Al 2 O 3 ≦24、 4≦MgO≦14, 0≦CaO≦4, 0.1≦ZnO≦3, 0.1≦(L- 2 O+1 2 O+K 2 O)≦1、 Contains TiO 2 , ZrO 2 and a glass composition substantially free of PbO.

3. Expressed in mass %, 56≦SiO 2 ≦70、 0.1≦B 2 O 3 ≦8、 15≦Al 2 O 3 ≦24、 4≦MgO≦14, 0≦CaO≦4, 0≦ZnO≦10, 0.1≦(L- 2 O+1 2 O+K 2 O)≦1、 1≦ZrO 2 ≦4、 Contains TiO 2 and ZrO 2 The sum of the contents of PbO and HfO is 4 mass% or less, 2 A glass composition that is substantially free of:

4. Expressed in mass %, 56≦SiO 2 ≦70、 0.1≦B 2 O 3 ≦8、 15≦Al 2 O 3 ≦24、 4≦MgO≦14, 0≦CaO≦4, 0≦ZnO≦10, 0.1≦(L- 2 O+1 2 O+K 2 O)≦1、 1≦ZrO 2 ≦5、 Contains PbO, P 2 O 5 and HfO 2 A glass composition that is substantially free of:

5. Expressed in mass%, 75≦(SiO 2 +B 2 O 3 +Al 2 O 3 The glass composition according to claim 1 , further comprising the component (CuO+MgO+CaO+ZnO)≦99.

6. Expressed in mass%, 1≦(ZnO+ZrO 2 2. The glass composition according to claim 1, comprising:

7. Expressed in mass%, 1≦(Li 2 O+Na 2 O+K 2 O+TiO 2 + ZrO 2 +T-Fe 2 O 3 5. The glass composition according to claim 1 , wherein the components are: However, T-Fe 2 O 3 is Fe 2 O 3 This is the total iron oxide converted to

8. Expressed in mass%, 2≦B 2 O 3 5. The glass composition according to claim 1, further comprising:

9. The glass composition according to claim 1 , containing components in the range of 5≦MgO≦13, expressed in mass %.

10. The glass composition according to claim 1 , containing components satisfying the following relationship, expressed in mass %: 0≦CaO≦1.

11. The glass composition according to claim 1 , which is substantially free of SrO.

12. The glass composition according to claim 1 , which is substantially free of BaO.

13. 5. The glass composition according to claim 1, 3 or 4, containing a component in the range of 0≦ZnO≦8, expressed in mass %.

14. The glass composition according to claim 1 , containing components in the range of 4≦(MgO+ZnO)≦17, expressed in mass %.

15. Expressed in mass%, 0≦(Na 2 O+K 2 5. The glass composition according to claim 1, further comprising a component satisfying the following formula:

16. Expressed in mass%, 0≦T-Fe 2 O 3 5. The glass composition according to claim 1 , wherein the composition is selected from the group consisting of tungsten, tungsten, niobium, tungsten ... However, T-Fe 2 O 3 is Fe 2 O 3 This is the total iron oxide converted to

17. Expressed in mass%, 0≦Y 2 O 3 5. The glass composition according to claim 1, further comprising: ≦3.

18. Expressed in mass%, 0≦T-SnO 2 5. The glass composition according to claim 1, further comprising: ≦2. However, T-SnO 2 is SnO 2 This is the total tin oxide converted to

19. Expressed in mass%, 0≦CeO 2 5. The glass composition according to claim 1, further comprising: ≦2.

20. Expressed in mass%, 0≦F 2 5. The glass composition according to claim 1 , wherein the composition is selected from the group consisting of tungsten, tungsten, niobium, tungsten ...

21. Expressed in mass%, 0≦SO 3 5. The glass composition according to claim 1 , further comprising a component of ≦0.

5.

22. 5. The glass composition according to claim 1, wherein the working temperature is 1450°C or less, when the temperature at which the viscosity is 1000 dPa·sec is defined as the working temperature.

23. 5. The glass composition according to claim 1, wherein, when a temperature at which a viscosity is 1000 dPa·sec is defined as a working temperature, a temperature difference ΔT obtained by subtracting a devitrification temperature from the working temperature is 0° C. or more.

24. 5. The glass composition according to claim 1, having a Young's modulus of 85 to 100 GPa.

25. Average linear expansion coefficient at 50 to 350°C is 20 to 35 x 10 -7 The glass composition according to claim 1 , wherein the temperature is 100° C. / ° C.

26. 5. The glass composition according to claim 1, having a dielectric constant of 6.5 or less at a frequency of 1 GHz.

27. 5. The glass composition according to claim 1, having a dielectric loss tangent of 0.0060 or less at a frequency of 1 GHz.

28. A glass fiber comprising the glass composition according to any one of claims 1 to 4.

29. The glass fiber according to claim 28, having at least one shape selected from the group consisting of roving, roving cloth, continuous strand mat, milled fiber, flat fiber, filament mat, chopped strand, yarn, glass cloth and glass tape.

30. Expressed in mass %, 56≦SiO 2 ≦70、 0.1≦B 2 O 3 ≦8、 15≦Al 2 O 3 ≦24、 4≦MgO≦14, 0≦CaO≦4, 0≦ZnO≦10, 0≦(L) 2 O+1 2 O+K 2 O)≦4、 0.1≦ZrO 2 ≦5、 Contains TiO 2 1. A glass fiber comprising a glass composition that is substantially free of:

31. Expressed in mass %, 56≦SiO 2 ≦70、 0.1≦B 2 O 3 ≦8、 15≦Al 2 O 3 ≦24、 4≦MgO≦14, 0≦CaO≦4, 0.1≦ZnO≦3, 0≦(L) 2 O+1 2 O+K 2 O)≦4、 Contains TiO 2 and ZrO 2 1. A glass fiber comprising a glass composition that is substantially free of:

32. Expressed in mass %, 56≦SiO 2 ≦70、 0.1≦B 2 O 3 ≦8、 15≦Al 2 O 3 ≦24、 4≦MgO≦14, 0≦CaO≦4, 0≦ZnO≦10, 0≦(L) 2 O+1 2 O+K 2 O)≦4、 1≦ZrO 2 ≦5、 Contains the component HfO 2 1. A glass fiber comprising a glass composition that is substantially free of:

33. The glass fiber according to any one of claims 30 to 32, having at least one shape selected from the group consisting of roving, roving cloth, continuous strand mat, milled fiber, flat fiber, filament mat, chopped strand, yarn, glass cloth and glass tape.

34. A glass filler comprising the glass composition according to claim 1 .

35. The glass filler according to claim 34, which is at least one selected from the group consisting of flake glass, glass powder, glass beads, and fine flakes.

36. 29. A molded article comprising the glass fiber according to claim 28, which is at least one selected from the group consisting of a rubber reinforcing cord, a nonwoven fabric, a prepreg, a reinforced plastic, a printed circuit board, an inorganic cured material, a filter, a heat insulating material, a sound absorbing material, and a battery separator.

37. A filler-containing product comprising the glass filler according to claim 34, which is at least one product selected from the group consisting of reinforced plastics, paints, inks, printed circuit boards, inorganic cured materials, and cosmetics.

38. A molded article comprising the glass fiber according to any one of claims 30 to 32, which is at least one selected from the group consisting of a rubber reinforcement cord, a nonwoven fabric, a prepreg, a reinforced plastic, a printed circuit board, an inorganic cured body, a filter, a heat insulating material, a sound absorbing material, and a battery separator.

39. A method for producing a glass fiber, comprising the steps of melting the glass composition according to claim 1 , and forming the molten glass composition into a glass fiber.

40. A method for producing a glass filler, comprising: melting the glass composition according to claim 1 ; and forming the molten glass composition into a glass filler.

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