Glass composition, glass fiber, and glass filler

Abstract

The present disclosure provides a glass composition having a low linear expansion coefficient and a high Young's modulus, suitable for mass production. The present disclosure provides a glass composition containing, in mass%, the following components: i) 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 substantially no TiO2; ii) 56≦SiO2≦70, 0.1≦B2O3≦8, 15≦Al2O3≦24, 4≦MgO≦14, 0≦ the glass composition containing the components CaO≦4, 0.1≦ZnO≦3, 0≦(Li2O+Na2O+K2O)≦4, and substantially free of TiO2 and ZrO2; and iii) a glass composition containing the 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] The present invention relates to a glass composition, to a glass fiber and a glass filler, and further to a product such as a molded article containing the glass fiber or the glass filler. [Background technology]

[0002] Resin compositions are widely used in electronic devices to form electrical insulating members and mechanical members. Examples of electrical insulating members include connector housings used in SMT (surface mount technology), FPC (flexible printed circuits), board-to-board, CPU (central processing unit) sockets, memory cards, card edges, optical connectors, etc., LCD (liquid crystal display) backlights, coils, flats, transformers, reactance bobbins used in magnetic heads, etc., relay cases, relay base switches, reflow dip switches, tact switches, etc., switches, sensor cases, capacitor casings, volume casings, and trimmer casings. Examples of mechanical members 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 films such as base films for FPCs and base films for copper-clad laminates. In addition, a type of printed circuit board equipped in an electronic device also has a substrate made of a resin composition. A printed wiring board before electronic components are mounted also has a substrate made of a resin composition. Hereinafter, in this specification, both printed circuit boards and printed wiring boards will be referred to as "printed boards."

[0003] The above resin composition contains a thermoplastic resin and glass fiber, and further contains a curing agent, a modifier, etc. as necessary. 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 demand for miniaturization of electronic devices and the demand for thinning for the purpose of high functionality, dimensional stability is required for the resin composition, and accordingly, a low thermal expansion coefficient and a high elastic modulus are required for the constituent materials. Patent Document 1 discloses a glass composition having a low linear thermal expansion coefficient and a high Young's modulus, and a glass fiber composed of the glass composition.

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

[0005] [Patent Document 1] JP 2011-105554 A [Patent Document 2] International Publication No. 2012 / 104999 Summary of the Invention [Problem to be solved by the invention]

[0006] As electronic devices become thinner for the purpose of miniaturization and high functionality, the resin composition constituting the electronic devices is required to have dimensional stability, and the glass fiber and glass filler constituting the electronic devices are required to have a low linear thermal expansion coefficient and a high elastic modulus. Therefore, the present invention aims to provide a new glass composition that has a low linear thermal expansion coefficient and a high Young's modulus and is suitable for mass production. [Means for solving the problem]

[0007] The present invention is characterized in that, 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 a glass composition substantially free of TiO2.

[0008] According to another aspect of the present invention, there is provided a composition comprising the following components, 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 is substantially free of TiO2 and ZrO2.

[0009] According to another aspect of the present invention, there is provided a composition comprising the following components, 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, The present invention provides a glass composition comprising the components:

[0010] The present invention can also be described as follows. The present invention is characterized in that, expressed in mass%, 56≦SiO2≦70, 0.1≦B2O3≦8, 15≦Al2O3≦24, 4≦MgO≦14, 0≦CaO≦4, Contains the components 0≦(Li2O+Na2O+K2O)≦4, The present invention provides a glass composition, wherein at least one selected from the group consisting of a) and c) or b) is satisfied. a) further containing the components 0≦ZnO≦10 and 0.1≦ZrO2≦5; Substantially free of TiO2. b) further containing a component of 0.1≦ZnO≦3; Substantially free of TiO2 and ZrO2. c) Further containing the components 0≦ZnO≦10, and 1≦ZrO2≦5. Effect of the Invention

[0011] According to the present invention, there is provided a new glass composition which has a low coefficient of linear thermal expansion and a high Young's modulus and is suitable for mass production. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the embodiments of the present invention will be described, but the following description is not intended to limit the present invention to a specific embodiment. In this specification, "substantially not contained" and "substantially not contained" mean that the content is less than 0.1 mass%, less than 0.05 mass%, less than 0.01 mass%, further less than 0.005 mass%, particularly less than 0.003 mass%, and in some cases less than 0.001 mass%. "Substantially" is intended to allow the inclusion of trace amounts of impurities derived from glass raw materials, manufacturing equipment, molding equipment, etc. "Main component" means the component with the largest content by mass. "T-Fe2O3" means the total iron oxide converted to iron trioxide (Fe2O3). "T-SnO2" means the total tin oxide converted to tin dioxide (SnO2). "Alkali metal oxide" means lithium oxide (Li2O), sodium oxide (Na2O), and potassium oxide (K2O). The upper and lower limits of the contents described below can be combined arbitrarily. Hereinafter, the glass composition may be simply referred to as glass, and the linear thermal expansion coefficient may be simply referred to as the linear expansion coefficient.

[0013] [Glass composition] <Ingredients> (SiO2) SiO2 is a component that forms the skeleton of glass and is the main component of the glass composition. SiO2 is also a component that adjusts the devitrification temperature and viscosity during glass formation and improves the water resistance of glass. SiO2 is also a component that lowers the linear expansion coefficient of glass. SiO2 is also a component that has the effect of lowering the dielectric constant and dielectric tangent. The content of SiO2 is 56% by mass or more and 70% by mass or less. The lower limit of the content 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, or even 60.1% by mass or more. The upper limit of the content 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, or even 61.9% by mass or less, or in some cases 61.8% by mass or less.

[0014] (B2O3) B2O3 is a component that forms the skeleton of glass. In addition, 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 glass and increases the linear expansion coefficient of glass. Furthermore, B2O3 is a component that has the effect of lowering 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 content of B2O3 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 in some cases 3.5% by mass or more. The upper limit of the B2O3 content may be 7% by mass or less, 6% by mass or less, further 5.8% by mass or less, 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4.4% by mass or less, 4.3% by mass or less, 4.2% by mass or less, 4.1% by mass or less, 4.0% by mass or less, 3.9% by mass or less, and in some cases 3.5% by mass or less. The B2O3 content may be 0.1% by mass or more and 6% by mass or less.

[0015] (Al2O3) Al2O3 is a component that forms the skeleton of glass. In addition, Al2O3 is also a component that adjusts the devitrification temperature and viscosity during glass formation. Furthermore, Al2O3 is a component that improves the Young's modulus of glass and also a component that reduces the linear expansion coefficient of glass. And, Al2O3 is a component that adjusts the dielectric constant and dielectric loss tangent of glass. When the content of Al2O3 is 15% by mass or more and 24% by mass or less, the increase in the devitrification temperature of glass is suppressed, and the melting point of glass does not become excessively high, and the uniformity when melting the raw materials is increased. The lower limit of the content of Al2O3 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, or even 20.5% by mass or more. The upper limit of the Al2O3 content 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, or 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 glass. MgO is also a component that adjusts the dielectric constant and dielectric tangent of glass. The content of MgO is 4% by mass or more and 14% by mass or less. The lower limit of the content of MgO 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, or even 9% by mass or more. The upper limit of the content of MgO 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, or in some cases 8% by 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 glass and increases the linear expansion coefficient of glass. The lower limit of the CaO content can be 0.05 mass% or more, 0.06 mass% or more, 0.07 mass% or more, 0.08 mass% or more, 0.09 mass% or more, or 0.1 mass% or more. The upper limit of the CaO content can be 4 mass% or less, 3 mass% or less, 2 mass% or less, 1.5 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.6 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, or even 0.15 mass% or less. CaO may not be substantially contained.

[0018] (MgO+CaO) With respect to the meltability and formability of glass, the value of the sum of the contents of MgO and CaO (MgO+CaO) may be important. From the viewpoint of obtaining meltability and formability suitable for glass production, the lower limit of (MgO+CaO) may 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, or even 9 mass% or more. The upper limit of (MgO+CaO) may 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, and in some cases, 8.5 mass% or less, or even 8 mass% or less.

[0019] (MgO / CaO) The ratio of the MgO content to the CaO content (MgO / CaO) 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. Here, the content is based on mass. The lower limit of (MgO / CaO) may be 30 or more, 50 or more, 80 or more, 90 or more, or even 95 or more, and in some cases 100 or more. The upper limit of (MgO / CaO) is not particularly limited, but may be 10,000 or less, 1,000 or less, or even 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, or 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 inclusion of BaO 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, or even 0.1 mass% or less. BaO may not be substantially contained.

[0022] (MgO+CaO+SrO+BaO) With respect to the meltability and formability of glass, the value of the total content of MgO, CaO, SrO and BaO (MgO+CaO+SrO+BaO) may be important. From the viewpoint of obtaining meltability and formability suitable for glass production, the lower limit of (MgO+CaO+SrO+BaO) may 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, or even 9 mass% or more. In addition, the upper limit of (MgO+CaO+SrO+BaO) may 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, and in some cases, 8.5 mass% or less, or even 8 mass% or less.

[0023] (ZnO, ZrO2) ZnO and ZrO2 are components that adjust the devitrification temperature and viscosity during glass formation. In addition, ZnO and ZrO2 are components that improve the Young's modulus of glass and also reduce the linear expansion coefficient of glass. In addition, ZnO and ZrO2 are components that adjust the dielectric constant and dielectric tangent of 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 setting the devitrification temperature and viscosity of the molten glass in 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, or even 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, or even more than 3% by mass. The upper limit of (ZnO+ZrO2) may 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 further 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 may 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, or even 3.5% by mass or more. The upper limit of the ZnO content may 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, or even 2% by mass or less. ZnO may not be substantially contained.

[0025] The lower limit of the ZrO2 content may 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, or even 0.5% by mass or more. The upper limit of the ZrO2 content may 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, or even 1% by mass or less. In particular, in a glass that does not substantially contain TiO2, the ZrO2 content may be 1% by mass or less, 0.8% by mass or less, 0.7% by mass or less, or even 0.6% by mass or less. On the other hand, in a glass that contains TiO2, the ZrO2 content may be 1% by mass or more, 1.1% by mass or more, or even 1.2% by mass or more, or may be 5% by mass or less. 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 mass % or more, and further 0.8 mass % or more.

[0026] (B2O3+ZnO+ZrO2) The total content of B2O3, ZnO, and ZrO2 (B2O3+ZnO+ZrO2) can also be important in adjusting various properties. Appropriate adjustment of (B2O3+ZnO+ZrO2) is effective in controlling the devitrification temperature and viscosity of the molten glass to a range suitable for glass production while suppressing an excessive increase in the devitrification temperature. The lower limit of (B2O3+ZnO+ZrO2) can be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 1.5 mass% or more, 2 mass% or more, 2.5 mass% or more, 3 mass% or more, 3.5 mass% or more, 4 mass% or more, or even 4.5 mass% or more, and in some cases 5 mass% or more. The upper limit of (B2O3+ZnO+ZrO2) can be 18 mass% or less, 16 mass% or less, 15 mass% or less, 14 mass% or less, 13 mass% or less, 12 mass% or less, 11 mass% or less, 10 mass% or less, 9 mass% or less, 8 mass% or less, 7 mass% or less, or even 6 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 controlling the devitrification temperature and viscosity of the molten glass to a range suitable for glass production while suppressing an excessive increase in the devitrification temperature. The lower limit of (MgO+ZnO) may be 4 mass% or more, 5 mass% or more, 6 mass% or more, 7 mass% or more, 8 mass% or more, or even 9 mass% or more, and in some cases 10 mass% or more. The upper limit of (MgO+ZnO) may be 17 mass% or less, 16.5 mass% or less, 16 mass% or less, 15.5 mass% or less, 15 mass% or less, 14.5 mass% or less, 14 mass% or less, 13.8 mass% or less, or even 13.7 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 content of alkali metal oxides (Li2O+Na2O+K2O) is 0% by mass or more and 4% by mass or less, the devitrification temperature and viscosity of the molten glass can be set in a range suitable for glass production while suppressing an excessive increase in the devitrification temperature. In addition, while suppressing an increase in the melting point of the glass and enabling more uniform melting of the glass raw materials, the glass transition temperature does not decrease excessively, and high heat resistance of the glass can be ensured. The lower limit of (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, or even 0.3% by mass or more. Addition of a small amount of alkali metal oxide is effective in reducing bubbles in the glass. The upper limit of (Li2O+Na2O+K2O) may 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, or 0.3 mass% or less. Alkali metal oxides 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 Li2O content may be 0.1 mass% or more, or even 0.2 mass% or more. The upper limit of the Li2O content may 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, or even 0.2 mass% or less. Li2O may not be substantially contained.

[0030] The upper and lower limits of the content of Na2O and K2O may be the values ​​stated as the upper and lower limits of the content of Li2O, respectively. The sum of the content of Na2O and K2O (Na2O+K2O) may be 4 mass% or less, 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, 0.2 mass% or less, or even 0.15 mass% or less, and in some cases 0.1 mass% or less. The lower limit of the content of (Na2O+K2O) may be 0.1 mass% or more, or even 0.2 mass% or more. Na2O may not be substantially contained. K2O may not be substantially contained.

[0031] (TiO2) TiO2 is a component that adjusts the devitrification temperature and viscosity during glass formation. TiO2 is also a component that improves the Young's modulus of glass and reduces the linear expansion coefficient of glass. TiO2 is also a component that improves the meltability and chemical durability of glass and improves the ultraviolet absorption characteristics of glass. The lower limit of the TiO2 content may be 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 1 mass% or more, or in some cases 1.2 mass% or more. However, in order to adjust the Young's modulus, linear expansion coefficient, and mass production suitability in a well-balanced manner, it is desirable not to contain an excessive amount of TiO2. The upper limit of the TiO2 content may be 5 mass% or less, 4 mass% or less, 3 mass% or less, 2 mass% or less, 1.5 mass% or less, 1.4 mass% or less, 1.3 mass% or less, 1 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, or even 0.1 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) may be 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, or even 0.4 mass% or more, and in some cases 0.5 mass% or more. The upper limit of (TiO2+ZrO2) may be 5 mass% or less, 4 mass% or less, 3.5 mass% or less, 3.3 mass% or less, 3 mass% or less, 2.5 mass% or less, and in some cases 2 mass% or less, 1.5 mass% or less, 1.2 mass% or less, 1 mass% or less, 0.7 mass% or less, and even 0.6 mass% or less. However, depending on the embodiment, TiO2 and ZrO2 may not be substantially contained.

[0033] (Fe) In glass, Fe is usually 2+ or Fe 3+ It exists in the state of Fe 3+ is a component that enhances the ultraviolet absorbing properties of glass, and Fe 2+ is a component that enhances the heat ray absorption properties of glass. The upper limit of the Fe content may 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, 0.4 mass% or less, or even 0.3 mass% or less, expressed by T-Fe2O3. The lower limit of the Fe content may be 0.1 mass% or more, 0.15 mass% or more, or even 0.2 mass% or more, expressed by T-Fe2O3. In particular, in glass compositions with a low content of alkali metal oxides, a trace amount of iron oxide can promote fining of the glass and contribute to reducing bubbles. Fe may not be substantially contained.

[0034] (CeO2, SnO2) CeO2 and SnO2 are optional components. In particular, in glass compositions with a low content of alkali metal oxides, trace amounts of CeO2 and SnO2 may contribute to promoting clarification of the glass. CeO2 and SnO2 are components that adjust the devitrification temperature and viscosity during glass formation. CeO2 and SnO2 are also components that improve the Young's modulus of glass and reduce the linear expansion coefficient of glass. The upper limits of the CeO2 and SnO2 contents may be 0.1 mass% or more. The upper limits of the CeO2 and SnO2 contents may be 2 mass% or less, 1 mass% or less, 0.5 mass% or less, 0.3 mass% or less, or even 0.2 mass% or less. CeO2 may not be substantially contained. SnO2 may not be substantially contained. The SnO2 content is a value expressed by T-SnO2.

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

[0036] (F2, Cl2) Fluorine (F2) and chlorine (Cl2) are also optional components. In particular, in glass compositions with a low content of alkali metal oxides, F2 and Cl2 can contribute to the promotion of fining of the glass. However, since F2 and Cl2 are easily volatile, there is a possibility that they may scatter during melting. The upper limits of the contents of F2 and Cl2 may 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, 0.2 mass% or less, or even 0.1 mass% or less, respectively. F2 may not be substantially contained. The lower limit of the content of F2 may be 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.35 mass% or more, or even 0.4 mass% or more. Cl2 may not be substantially contained either.

[0037] (sum of ingredients) The total of the above-mentioned components, i.e., the components described from SiO2 to F2 and Cl2, may 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 content 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 even 1% by mass or more. The upper limit of the total amount of each component represented by (Li2O+Na2O+K2O+TiO2+ZrO2+T-Fe2O3) may be 19 mass % or less, 10 mass % or less, 5 mass % or less, or even 3 mass % or less.

[0038] (Other Ingredients) 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 limited to these. Each of the other optional components may be contained at a content of 3 mass% or less. The allowable content 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. The other optional components may not be substantially contained. Y2O3 and La2O3 are components that adjust the devitrification temperature and viscosity during glass formation. In addition, Y2O3 and La2O3 are components that improve the Young's modulus of glass. For example, the sum of the contents 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, 0.9% by mass or less, less than 0.5% by mass, or even 0.1% by mass or less. For example, it is desirable that As2O3 and Sb2O3 are not substantially contained from the viewpoint of environmental protection. The total content 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> A preferred composition is shown below. The ranges shown 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), A glass composition comprising the components above and substantially no TiO2.

[0040] Composition A1 has a low linear thermal expansion coefficient and a high Young's modulus, and is also excellent in mass production suitability. One example of excellent mass production suitability is that ΔT, which is the working temperature minus the devitrification 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, The glass composition contains the above components, satisfies 9≦(MgO+ZnO)≦13.8, and is substantially free of TiO2.

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

[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 comprising the components above and substantially free of TiO2 and ZrO2.

[0044] Composition B does not substantially contain ZrO2, unlike compositions A1-A2 and C. Composition B has a low linear thermal expansion coefficient and a high Young's modulus, and is also excellent in suitability for mass production.

[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 comprising the components:

[0046] Composition C, unlike compositions A1-A2 and B, 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 suitability. Composition C is also suitable for achieving a low dielectric tangent.

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

[0048] <Characteristics> Possible properties of the glass composition of this embodiment will be described below. (melting characteristics) The temperature at which the viscosity of the molten glass is 1000 dPa·sec (1000 poise) is called the working temperature of the glass, and is the temperature suitable for forming the glass. If the working temperature of the glass is 1100°C or higher, the variation in dimensions such as the diameter of the glass fiber 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 equipment is less susceptible to corrosion due to heat, and the equipment life can be 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, or even 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, or even 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 molding, and homogeneous glass can be produced with a high yield. ΔT can be 0°C or more, 5°C or more, 10°C or more, or even 15°C or more. There is no particular upper limit for ΔT, but it can be, for example, 100°C or less, 80°C or less, 70°C or less, 65°C or less, 60°C or less, 55°C or less, or even 50°C or less. The devitrification temperature is the temperature at which crystals form in the molten glass base and begin to grow, and can be measured by the method described below.

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

[0051] (glass transition temperature) The glass transition temperature (glass transition point) is an index of the heat resistance of glass. When a resin composition containing 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, or even 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, or even 770°C or less.

[0052] (Young's Modulus) The high Young's modulus of glass contributes to improving the mechanical properties and dimensional stability of a resin composition containing glass fiber or glass filler. The Young's modulus can be calculated from the longitudinal wave velocity and transverse wave velocity of elastic waves propagating through glass measured by a normal ultrasonic method and the density of the glass measured by the Archimedes method. The lower limit of the 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, or even 90 GPa or more. The upper limit of the Young's modulus can be 100 GPa or less, 99 GPa or less, 98 GPa or less, 97 GPa or less, 96 GPa or less, or even 95 GPa or less.

[0053] (Dielectric constant, dielectric tangent) The low dielectric constant of glass contributes to improving the dielectric properties of a resin composition containing glass fiber or glass filler. 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, or even 5.4 or less, and in some cases 5.3 or less. Strictly speaking, the dielectric constant 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 a value at room temperature (25°C). The dielectric constant may be 5.0 or more.

[0054] The low dielectric tangent of glass also contributes to improving the dielectric properties of a resin composition containing glass fiber or glass filler. 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, The dielectric tangent is 0.0031 or less, 0.0030 or less, 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 a value at room temperature (25°C). The dielectric tangent may be 0.0010 or more.

[0055] [Glass products] <Glass fiber> The glass fiber of the present embodiment is composed of the above-mentioned 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, so that 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 fibers 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, or 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, or even 4.3 μm or less. A glass composition having a characteristic temperature suitable for mass production is suitable for stable production as a thin glass fiber. In a preferred embodiment, the average fiber diameter is even thinner, for example, 3.9 μm or less, or even 3.5 μm or less. The glass fibers are, for example, long glass fibers (filaments).

[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 a glass fiber having a flat cross section such as an ellipse. The major axis D2 of the cross section of the flat fiber is larger than the minor axis D1, 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 100,000 μm. The flat fiber can be obtained by a known method. The cross section of the flat fiber may have a concave shape in which the surface extending along the major axis D2 is recessed in the center from the ends.

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

[0060] <Glass filler> The glass filler of the present embodiment is composed of the above-mentioned glass composition. The glass filler may be at least one selected from the group consisting of glass flakes, glass powder, glass beads, and fine flakes.

[0061] Flake glass is also called scale glass and has a flake 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 pieces of flake glass 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 a laser diffraction scattering method. The flake glass can be obtained by a known blow method, cup method, etc.

[0062] The glass powder is a powdered glass and is produced by crushing 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 a particle of the glass powder. The glass powder can be obtained by a known method.

[0063] The glass beads have a spherical or nearly 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 a particle of the glass beads. The glass beads can be obtained by a known method.

[0064] Fine flakes are thin flake glass. Fine flakes may be composed of flake glass having an average thickness of 0.1 to 2.0 μm, or may contain 90% by mass or more of flake glass having a thickness in the range of 0.01 to 2.0 μm. Fine flakes having such a small average thickness and small thickness variation are highly effective in reinforcing resin and are also excellent in reducing the molding shrinkage rate of resin. Fine flakes are also suitable for relaxing the restrictions on the thickness of resin molded bodies compared to conventional methods. Fine flakes are preferably composed of flake glass having an average thickness of 0.1 to 1.0 μm. Fine flakes preferably contain 90% by mass or more of flake glass having a thickness in the range of 0.05 to 1.0 μm. Fine flakes can be obtained by the method described for flake glass.

[0065] The glass filler can be produced 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 a glass filler.

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

[0067] <Molded body> The molded article of the present embodiment contains the above-mentioned glass fiber and is molded into a predetermined shape. The molded article may be at least one selected from the group consisting of, but not limited to, 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.

[0068] <Products containing fillers> The filler-containing product of the present embodiment contains the above-mentioned glass filler. The filler-containing product may be at least one selected from the group consisting of, but not limited to, reinforced plastics, paints, inks, printed circuit boards, inorganic cured bodies, and cosmetics.

[0069] <Resin products> The resin product of the present embodiment includes the above-mentioned glass fiber and / or glass filler, and a resin. The resin product may 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, but may be, for example, polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyester, polyamide, polycarbonate, polybutylene, polybutylene terephthalate, or a copolymer thereof. When polybutylene terephthalate is used, the effect of suppressing warping of the molded product and improving the dimensional stability by mixing with the glass filler is increased. Flake-like glass, flat fiber, and fine flakes have a relatively large specific surface area and are suitable for ensuring the bonding force between the thermoplastic resin and the glass filler.

[0070] [Technology provided by the present embodiment] The techniques provided by this embodiment are 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 comprising the components above and substantially no 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 comprising the components above 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 comprising the components:

[0073] (Technology 4) The glass composition according to any one of the techniques 1 to 3, containing components in the range of 75≦(SiO2+B2O3+Al2O3+MgO+CaO+ZnO)≦99, expressed in mass%,

[0074] (Technology 5) The glass composition according to any one of the first to fourth aspects of the present invention, comprising components in the range of 1≦(ZnO+ZrO2)≦15, expressed in mass%,

[0075] (Technology 6) The glass composition according to any one of the techniques 1 to 5, containing, in mass%, 1≦(Li2O+Na2O+K2O+TiO2+ZrO2+T-Fe2O3)≦19, where T-Fe2O3 is total iron oxide calculated as Fe2O3.

[0076] (Technology 7) The glass composition according to any one of the first to sixth techniques, comprising a component satisfying the following relationship: 2≦B2O3≦6, expressed in mass%.

[0077] (Technology 8) The glass composition according to any one of the first to seventh aspects, comprising a component in the range of 5≦MgO≦13, expressed in mass%,

[0078] (Technology 9) The glass composition according to claim 8, containing a component in the range of 0≦CaO≦1, expressed in mass%.

[0079] (Technology 10) The glass composition according to any one of the first to ninth aspects of the present invention, which is substantially free of SrO.

[0080] (Technology 11) The glass composition according to any one of the first to tenth embodiments, which is substantially free of BaO.

[0081] (Technology 12) The glass composition according to any one of the techniques 1 to 11, containing a component in which, expressed in mass%, 0≦ZnO≦8.

[0082] (Technology 13) The glass composition according to any one of the first to third aspects of the present invention, comprising a component in the range of 4≦(MgO+ZnO)≦17, expressed in mass%,

[0083] (Technology 14) The glass composition according to any one of the techniques 1 to 13, containing components in the range of 0≦(Li2O+Na2O+K2O)≦1, expressed in mass%,

[0084] (Technology 15) The glass composition according to claim 14, containing components in the range of 0.1≦(Li2O+Na2O+K2O)≦1, expressed in mass%,

[0085] (Technology 16) The glass composition according to any one of the techniques 1 to 15, containing components in the range of 0≦(Na2O+K2O)≦1, expressed in mass%,

[0086] (Technology 17) The glass composition according to any one of the techniques 1 to 16, containing components in the range of 0≦(TiO2+ZrO2)≦4, expressed in mass%,

[0087] (Technology 18) The glass composition according to any one of the techniques 1 to 17, containing a component in the range of 0≦T-Fe2O3≦5, expressed in mass%, where T-Fe2O3 is total iron oxide calculated as Fe2O3.

[0088] (Technology 19) The glass composition according to any one of the techniques 1 to 18, containing a component, expressed in mass%, of 0≦Y2O3≦3.

[0089] (Technology 20) The glass composition according to any one of the techniques 1 to 19, containing a component in a range of 0≦T-SnO2≦2, expressed in mass%, where T-SnO2 is total tin oxide converted to SnO2.

[0090] (Technology 21) The glass composition according to any one of the techniques 1 to 20, containing a component, expressed in mass%, of 0≦CeO2≦2.

[0091] (Technology 22) The glass composition according to any one of the techniques 1 to 21, containing a component, expressed in mass%, of 0≦F2≦5.

[0092] (Technology 23) The glass composition according to any one of the techniques 1 to 22, containing a component in the range of 0≦SO3≦0.5, expressed in mass%,

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

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

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

[0096] (Technology 27) Average linear expansion coefficient at 50 to 350°C is 20 to 35 x 10 -7 The glass composition according to any one of the techniques 1 to 26, wherein the glass composition has a viscosity of 1000:1 / °C.

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

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

[0099] (Technology 30) A glass fiber comprising the glass composition according to any one of claims 1 to 29.

[0100] (Technology 31) The glass fiber according to the technique 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) A glass filler comprising the glass composition according to any one of claims 1 to 29.

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

[0103] (Technology 34) A molded article comprising the glass fiber according to claim 30, 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 material, a filter, a heat insulating material, a sound absorbing material, and a battery separator.

[0104] (Technology 35) A filler-containing product comprising the glass filler according to Technical 32, which is at least one selected from the group consisting of reinforced plastics, paints, inks, printed circuit boards, inorganic cured materials, and cosmetics.

[0105] (Technology 36) 30. A method for producing a glass fiber, comprising: melting the glass composition according to any one of claims 1 to 29; and forming the molten glass composition into a glass fiber.

[0106] (Technology 37) A method for producing a glass filler, comprising: melting the glass composition according to any one of techniques 1 to 29; and forming the molten glass composition into a glass filler. EXAMPLES

[0107] Hereinafter, the 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 mixed to obtain the compositions shown in Tables 1 to 4, and batches of 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 to melt, and was maintained as such for about 4 hours until the composition became uniform. Then, a part of the molten glass (glass melt) was poured onto an iron plate and slowly cooled to room temperature in an electric furnace to obtain a bulk glass composition (plate-shaped material, 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, and 39, cerium (IV) oxide (CeO2) was used as the CeO2 source. In Examples 19 to 23, 29, 31 to 36, and 38 to 42, sodium sulfate was used as the SO3 source, and in Examples 26 and 37, lithium sulfate monohydrate was used as the SO3 source.

[0108] The methods for evaluating the characteristics are described below. (working temperature) The relationship between viscosity and temperature of the obtained glass composition was examined by a conventional platinum ball pulling method, and the working temperature was calculated from the results. Here, the platinum ball pulling method is a method of measuring viscosity by applying the relationship between the load (resistance) applied when a platinum ball is immersed in molten glass and pulled up at a uniform speed, and the gravity and buoyancy acting on the platinum ball, to Stokes' law, which shows the relationship between the viscosity and the falling speed when a minute particle sinks in a fluid.

[0109] (devitrification temperature) The glass composition crushed to a particle size of 1.0 to 2.8 mm was placed in a platinum boat and held for 2 hours in an electric furnace with a temperature gradient (900 to 1500°C), and the devitrification temperature was determined from the maximum temperature of the electric furnace corresponding to the position where crystals appeared. When the glass was opaque and crystals could not be observed, the maximum temperature of the electric furnace corresponding to the position where opacity appeared was taken as the devitrification temperature. Here, the particle size is a value measured by a sieving method. The temperature (temperature distribution in the electric furnace) which differs depending on the location in the electric furnace is measured in advance, and the glass composition placed in a predetermined location in the electric furnace is 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] (Linear expansion coefficient) The average linear expansion coefficient of the obtained glass composition at 50 to 350°C was measured using a commercially available dilatometer (Rigaku Corporation, thermomechanical analyzer, TMA8510). In addition, the glass transition temperature T g obtained.

[0111] (Young's Modulus) Young's modulus E is calculated by measuring the longitudinal wave velocity vl and the transverse wave velocity vt of the elastic wave propagating through the glass using a conventional ultrasonic method, and then calculating the glass density ρ using the Archimedes method: E=3ρ·v t 2 ·(v l 2 -4 / 3·v t 2 ) / (v l 2 -v t 2 ) was calculated using the formula:

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

[0113] (Number of bubbles) Ordinary glass raw materials such as silica sand were mixed to prepare batches of glass raw materials for each of the examples and comparative examples. Using an electric furnace, 150g of each batch was heated and melted at the test temperature of 1600°C, and maintained for 2 hours until the composition became uniform. Then, a part of the molten glass (glass melt) was poured 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 100g of glass was calculated. Glass samples with less than 400 bubbles per 100g of glass were rated as A, those with 400 to 2000 bubbles were rated as B, those with 2000 to 10000 bubbles were rated as C, and those with 10000 bubbles or more were rated as D.

[0114] The measurement results are shown in Tables 1 to 4. The glass compositions in the tables are all expressed in mass %. 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 example, the linear expansion coefficient is 29 to 32 × 10 -7 / ℃, Young's modulus 90~92GPa, working temperature 1324~1410℃, and difference ΔT (working temperature - devitrification temperature) 0~54℃ 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 and 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. The linear expansion coefficient of Comparative Example 4 is the measured value in Patent Document 2 (29×10 -7 / ℃) higher than (33×10 -7 / °C) is due to the difference in the temperature range in which it was measured. In addition, when the inventors performed additional tests, Comparative Example 4 had a negative ΔT, which indicated poor mass productivity. The glass compositions of Comparative Examples 5-16 also had insufficient average linear expansion coefficient, Young's modulus, and difference ΔT in at least one of them.

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、 The glass composition contains the above components, the sum of the contents of TiO 2 and ZrO 2 being 4 mass % or less, and is substantially free of PbO and HfO 2 .

4. Expressed in mass %, 56≦SiO2≦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≦(Li 2 O+Na 2 O+K 2 O)≦1, 1≦ZrO2≦5, and is substantially free of PbO, P 2 O 5 and HfO 2 .

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≦SiO2≦70, 0.1≦B 2 O 3 ≦8, 15≦Al 2 O 3 ≦24, 4≦MgO≦14, 0≦CaO≦4, 0≦ZnO≦10, 0≦(Li2O+Na2O+K2O)≦4, 0.1≦ZrO2≦5, and is substantially free of TiO 2 .

31. Expressed in mass %, 56≦SiO2≦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≦(Li2O+Na2O+K2O)≦4, and is substantially free of TiO 2 and ZrO 2 .

32. Expressed in mass %, 56≦SiO2≦70, 0.1≦B 2 O 3 ≦8, 15≦Al 2 O 3 ≦24, 4≦MgO≦14, 0≦CaO≦4, 0≦ZnO≦10, 0≦(Li2O+Na2O+K2O)≦4, 1≦ZrO2≦5, and is substantially free of HfO 2 .

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, the molded article being 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 material, 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.