Glass composition, glass fiber and glass filler

Abstract

Provided is a glass composition which has a low linear expansion coefficient and a high Young's modulus and is suitable for mass production. The present invention provides, in mass%: i) a glass composition containing 56 < = SiO2 < = 70, 0.1 < = B2O3 < = 8, 15 < = Al2O3 < = 24, 4 < = MgO < = 14, 0 < = CaO < = 4, 0 < = ZnO < = 10, 0 < = (Li2O + Na2O + K2O) < = 4, 0.1 < = ZrO2 < = 5, and substantially not containing TiO2; the present invention relates to a glass composition comprising (i) a glass composition containing 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 substantially not containing TiO2 and ZrO2, and iii) a glass composition containing 56 < = SiO2 < = 70, 0.1 < = B2O3 < = 8, 15 < = Al2O3 < = 24, 4 < = MgO < = 14, 0 < = CaO < = 4, 0 < = ZnO < = 10, 0 < = (Li2O + Na2O + K2O) < = 4, and 1 < = ZrO2 < = 5.

Description

Technical Field

[0001] The present invention relates to a glass composition, and further to glass fibers and glass fillers, and still further to articles 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 include connector housings used in SMT (surface mount technology), FPC (flexible printed circuits), board-to-board connectors, CPU (central processing unit) sockets, memory cards, card edges, optical connectors, etc., reactance bobbins used in LCD (liquid crystal display) backlights, coils, flat plates, transformers, magnetic heads, etc., open / close devices used in relay housings, relay base switches, reflow dual in-line package switches, tactile switches, etc., sensor housings, condenser housings, potentiometer housings, trimmer housings. Examples of mechanical members include lens holders and pick-up bases for optical pick-ups, insulators and terminals for micro motors, 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, there is a substrate made of a resin composition in one type of printed circuit board provided in an electronic device. There is also a substrate made of a resin composition in a printed wiring board before mounting electronic components. Hereinafter, in the present 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 further contains a curing agent, a modifier, etc. as needed. An inorganic filler is sometimes further contained in the printed board. As the inorganic filler, a glass filler is sometimes used. In recent years, in order to meet the requirements for miniaturization of electronic devices and the requirements for thinning for high functionality, dimensional stability is required for the resin composition, and accordingly, a low coefficient of thermal expansion and a high elastic modulus are required for its constituent materials. A glass composition having a low linear coefficient of thermal expansion and a high Young's modulus and glass fibers made of the glass composition are disclosed in Patent Document 1.

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

[0005] Prior art documents

[0006] Patent documents

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

[0008] Patent Document 2: International Publication No. 2012 / 104999 Summary of the invention

[0009] Problems to be solved by the invention

[0010] With the thinning for the purpose of miniaturization and high functionality of electronic devices, dimensional stability is required for the resin composition constituting the electronic device, and a low linear thermal expansion coefficient and a high elastic modulus are required for the glass fiber and glass filler as its constituent materials. Therefore, an object of the present invention is to provide a new glass composition having a low linear thermal expansion coefficient and a high Young's modulus and being suitable for mass production.

[0011] Means for solving the problems

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

[0013] 56 ≤ SiO2 ≤ 70,

[0014] 0.1 ≤ B2O3 ≤ 8,

[0015] 15 ≤ Al2O3 ≤ 24,

[0016] 4 ≤ MgO ≤ 14,

[0017] 0 ≤ CaO ≤ 4,

[0018] 0 ≤ ZnO ≤ 10,

[0019] 0 ≤ (Li2O + Na2O + K2O) ≤ 4,

[0020] a composition of 0.1 ≤ ZrO2 ≤ 5, and,

[0021] substantially free of TiO2.

[0022] On the other hand, the present invention provides the following glass composition, which contains in mass %:

[0023] 56 ≤ SiO2 ≤ 70,

[0024] 0.1 ≤ B2O3 ≤ 8,

[0025] 15 ≤ Al2O3 ≤ 24,

[0026] 4 ≤ MgO ≤ 14,

[0027] 0 ≤ CaO ≤ 4,

[0028] 0.1 ≤ ZnO ≤ 3,

[0029] a composition of 0 ≤ (Li2O + Na2O + K2O) ≤ 4, and,

[0030] substantially free of TiO2 and ZrO2.

[0031] On yet another aspect, the present invention provides the following glass composition, which contains in mass %:

[0032] 56 ≤ SiO2 ≤ 70,

[0033] 0.1 ≤ B2O3 ≤ 8,

[0034] 15 ≤ Al2O3 ≤ 24,

[0035] 4 ≤ MgO ≤ 14,

[0036] 0 ≤ CaO ≤ 4,

[0037] 0 ≤ ZnO ≤ 10,

[0038] 0 ≤ (Li2O + Na2O + K2O) ≤ 4,

[0039] a composition of 1 ≤ ZrO2 ≤ 5.

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

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

[0042] 56 ≤ SiO2 ≤ 70,

[0043] 0.1 ≤ B2O3 ≤ 8,

[0044] 15 ≤ Al2O3 ≤ 24,

[0045] 4 ≤ MgO ≤ 14,

[0046] 0 ≤ CaO ≤ 4,

[0047] a composition with 0 ≤ (Li2O + Na2O + K2O) ≤ 4, and,

[0048] at least one selected from a) and c), or b) holds.

[0049] a) further contains a composition with 0 ≤ ZnO ≤ 10 and 0.1 ≤ ZrO2 ≤ 5,

[0050] substantially does not contain TiO2.

[0051] b) further contains a composition with 0.1 ≤ ZnO ≤ 3,

[0052] substantially does not contain TiO2 and ZrO2.

[0053] c) further contains a composition with 0 ≤ ZnO ≤ 10 and 1 ≤ ZrO2 ≤ 5.

[0054] Advantages of the Invention

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

[0056] Hereinafter, embodiments of the present invention will be described. However, the gist of the following description is not to limit the present invention to a specific embodiment. In this specification, "substantially does not contain" and "substantially is 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. The gist of "substantially" is to allow the inclusion of trace impurities from glass raw materials, manufacturing apparatuses, forming apparatuses, etc. "Main component" means the component having the largest content rate on a mass basis. "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 sometimes be abbreviated as glass, and the linear thermal expansion coefficient may sometimes be abbreviated as the coefficient of linear expansion.

[0057] [Glass Composition]

[0058] <Composition>

[0059] (SiO2)

[0060] SiO2 is a component that forms the framework of the glass and is the main component of the glass composition. In addition, SiO2 is a component that adjusts the devitrification temperature and viscosity during glass formation and is a component that improves the water resistance of the glass. Furthermore, SiO2 is a component that reduces the linear expansion coefficient of the glass. Also, SiO2 is a component that has the effect of reducing the dielectric constant and the tangent of the dielectric loss angle. 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, and further 61.9% by mass or less, and can be 61.8% by mass or less depending on the circumstances.

[0061] (B2O3)

[0062] B2O3 is a component that forms the framework of the glass. In addition, B2O3 is also a component that adjusts the devitrification temperature and viscosity during glass formation. On the other hand, excessive content of B2O3 will reduce the Young's modulus of the glass and increase the linear expansion coefficient of the glass. Furthermore, B2O3 is a component that has the effect of reducing the dielectric constant and the tangent of the dielectric loss angle. The content rate of B2O3 is 0.1% by mass or more and 8% by mass or less. The lower limit of the content rate 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 can be 3.5% by mass or more depending on the circumstances. The upper limit of the content rate of B2O3 can be 7% by mass or less, 6% by mass or less, and 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 can be 3.5% by mass or less depending on the circumstances. The content rate of B2O3 can also be 0.1% by mass or more and 6% by mass or less.

[0063] (Al2O3)

[0064] Al2O3 is a component that forms the framework of the glass. Additionally, Al2O3 is also a component that adjusts the devitrification temperature and viscosity during glass formation. Furthermore, Al2O3 is a component that increases the Young's modulus of the glass and also a component that decreases the linear expansion coefficient of the glass. Moreover, Al2O3 is a component that adjusts the dielectric constant and the tangent of the dielectric loss angle of the glass. If the content rate of Al2O3 is 15 mass% or more and 24 mass% or less, the increase in the devitrification temperature of the glass can be suppressed, and the melting point of the glass will not become too high, and the uniformity during melting of the raw materials will increase. 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, and further 21.8 mass% or less, 21.5 mass% or less, and depending on the situation, it can be 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.

[0065] (MgO)

[0066] MgO is a component that adjusts the devitrification temperature and viscosity during glass formation, and is also a component that increases the Young's modulus of the glass. Additionally, MgO is a component that adjusts the dielectric constant and the tangent of the dielectric loss angle 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 depending on the situation, it can be 8 mass% or less.

[0067] (CaO)

[0068] CaO is an optional component. CaO is a component that adjusts the devitrification temperature and viscosity during glass formation. On the other hand, excessive inclusion of CaO reduces the Young's modulus of the glass and increases the linear expansion coefficient of the glass. The lower limit of the content rate of CaO 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, 0.1 mass% or more. The upper limit of the content rate of CaO 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, and further 0.15 mass% or less. CaO may also be substantially not contained.

[0069] (MgO + CaO)

[0070] Regarding the meltability and formability of the glass, the value of the sum of the content rates of MgO and CaO (MgO + CaO) is sometimes important. From the viewpoint of obtaining meltability and formability suitable for glass manufacturing, the lower limit of (MgO + CaO) can be 4 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 further 9 mass% or more. In addition, the upper limit of (MgO + CaO) 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, and can be 8.5 mass% or less, and further 8 mass% or less depending on the situation.

[0071] (MgO / CaO)

[0072] The value of the ratio of the content rate of MgO to the content rate of CaO (MgO / CaO) is sometimes also important in terms of 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 rate is also based on mass. The lower limit of (MgO / CaO) can be 30 or more, 50 or more, 80 or more, 90 or more, and further 95 or more, and can be 100 or more depending on the situation. The upper limit of (MgO / CaO) is not particularly limited and can be 10000 or less, 1000 or less, and further 500 or less.

[0073] (SrO)

[0074] SrO is an optional component. SrO is a component that adjusts the devitrification temperature and viscosity during glass formation. On the other hand, excessive inclusion of SrO reduces the Young's modulus of the glass and increases the linear expansion coefficient of the glass. The upper limit of the inclusion rate of SrO can be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, and further 0.1% by mass or less. SrO may also be substantially not included.

[0075] (BaO)

[0076] 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 inclusion rate of BaO can be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, and further 0.1% by mass or less. BaO may also be substantially not included.

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

[0078] Regarding the meltability and formability of the glass, the value of the total inclusion rate of MgO, CaO, SrO, and BaO (MgO+CaO+SrO+BaO) is sometimes important. From the viewpoint of obtaining meltability and formability suitable for glass manufacturing, the lower limit of (MgO+CaO+SrO+BaO) can be 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 8.5% by mass or more, and further 9% by mass or more. In addition, the upper limit of (MgO+CaO+SrO+BaO) can be 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 10% by mass or less, 9.5% by mass or less, 9% by mass or less, and can be 8.5% by mass or less, and further 8% by mass or less depending on the situation.

[0079] (ZnO、ZrO2)

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

[0081] The lower limit of the content of ZnO can be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 1.1 mass% or more, 1.3 mass% or more, 1.5 mass% or more, 2 mass% or more, 2.1 mass% or more, 2.5 mass% or more, 3 mass% or more, and further 3.5 mass% or more. The upper limit of the content of ZnO can be 10 mass% or less, 9 mass% or less, 8 mass% or less, 7.5 mass% or less, 7 mass% or less, 6.5 mass% or less, 6 mass% or less, 5.5 mass% or less, 5.3 mass% or less, 5.2 mass% or less, 5.1 mass% or less, 5 mass% or less, 4.5 mass% or less, 4 mass% or less, 3.5 mass% or less, 3 mass% or less, 2.9 mass% or less, 2.8 mass% or less, 2.7 mass% or less, 2.5 mass% or less, and further 2 mass% or less. Additionally, ZnO may also be substantially not contained.

[0082] The lower limit of the content rate of ZrO2 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, and further 0.5% by mass or more. The upper limit of the content rate of ZrO2 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, and further 1% by mass or less. Especially in the glass substantially free of TiO2, the content rate of ZrO2 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 the glass containing TiO2, the content rate of ZrO2 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. In addition, regardless of the content rate of TiO2, ZrO2 may also be substantially not contained. However, the content rate of ZrO2 suitable for achieving a low dielectric loss tangent is 0.7% by mass or more, and further 0.8% by mass or more.

[0083] (B2O3 + ZnO + ZrO2)

[0084] The total value of the content rates of B2O3, ZnO, and ZrO2 (B2O3 + ZnO + ZrO2) is sometimes also important in terms of adjusting various properties. The appropriate adjustment of (B2O3 + ZnO + ZrO2) is effective in the aspect of suppressing an excessive rise in the devitrification temperature while setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass manufacturing. 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, and further 4.5% by mass or more, and may be 5% by mass or more depending on the situation. 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.

[0085] (MgO + ZnO)

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

[0087] (Li2O, Na2O, K2O)

[0088] Alkali metal oxides (Li2O, Na2O, K2O) are components that adjust the devitrification temperature and viscosity during glass formation. If the sum of the contents of the alkali metal oxides (Li2O + Na2O + K2O) is 0% by mass or more and 4% by mass or less, it is possible to suppress an excessive increase in the devitrification temperature while setting the devitrification temperature and viscosity of the molten glass within a range suitable for glass production. In addition, an increase in the melting point of the glass can be suppressed, and more uniform melting of the glass raw materials can be achieved. However, 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, and further 0.3% by mass or more. The addition of a small amount of alkali metal oxides is effective in reducing bubbles in the glass. The upper limit of (Li2O + Na2O + K2O) can be 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. The alkali metal oxides may also be substantially not contained. Li2O, Na2O, and K2O are each optional components. In other words, the lower limit of the content of each of these components can be 0.

[0089] The lower limit of the Li₂O content can be 0.1% by mass or more, and further 0.2% by mass or more. The upper limit of the Li₂O content can be 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, 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, and further 0.2% by mass or less. Li₂O may also be substantially not contained.

[0090] 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 can be 0.1% by mass or less depending on the situation. The lower limit of the (Na₂O + K₂O) content can be 0.1% by mass or more, and further 0.2% by mass or more. Na₂O may also be substantially not contained. K₂O may also be substantially not contained.

[0091] (TiO₂)

[0092] TiO₂ is a component that adjusts the devitrification temperature and viscosity during glass formation. In addition, TiO₂ is a component that increases the Young's modulus of the glass and is also a component that decreases the linear expansion coefficient of the glass. Furthermore, TiO₂ is a component that improves the meltability and chemical durability of the glass and enhances the ultraviolet absorption characteristics of the glass. The lower limit of the TiO₂ content can be 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, and can be 1.2% by mass or more depending on the situation. However, in terms of well-balanced adjustment of the Young's modulus, linear expansion coefficient, and mass production adaptability, it is desirable not to contain TiO₂ in excess. 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 also be substantially not contained.

[0093] (TiO₂+ZrO₂)

[0094] The sum of the contents of TiO2 and ZrO2 (TiO2 + ZrO2) may also be important in terms of 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 mass% or more, 0.2 mass% or more, 0.3 mass% or more, and further 0.4 mass% or more, and can be 0.5 mass% or more depending on the situation. The upper limit of (TiO2 + ZrO2) can 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 can be 2 mass% or less, 1.5 mass% or less, 1.2 mass% or less, 1 mass% or less, 0.7 mass% or less, and further 0.6 mass% or less depending on the situation. However, according to the embodiment, neither TiO2 nor ZrO2 may be substantially contained.

[0095] (Fe)

[0096] In the glass, Fe usually exists in the state of Fe 2+ or Fe 3+ . Fe 3+ is a component that improves the ultraviolet absorption characteristics of the glass, and Fe 2+ is a component that improves the heat ray absorption characteristics of the glass. The upper limit of the content of Fe 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, 0.4 mass% or less, and further 0.3 mass% or less, expressed as T-Fe2O3. The lower limit of the content of Fe can be 0.1 mass% or more, 0.15 mass% or more, and further 0.2 mass% or more, expressed as T-Fe2O3. Especially in the 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 also not be substantially contained.

[0097] (CeO2, SnO2)

[0098] CeO2 and SnO2 are optional components. Especially in a glass composition with a low content rate of alkali metal oxides, trace amounts of CeO2 and SnO2 sometimes help promote the clarification of the glass. CeO2 and SnO2 are components that adjust the devitrification temperature and viscosity during glass formation. In addition, CeO2 and SnO2 are components that increase the Young's modulus of the glass and also components that reduce the linear expansion coefficient of the glass. The upper limit of the content rate of CeO2 and SnO2 can be 0.1 mass% or more, respectively. The upper limit of the content rate of CeO2 and SnO2 can be 2 mass% or less, 1 mass% or less, 0.5 mass% or less, 0.3 mass% or less, and further 0.2 mass% or less, respectively. CeO2 may also be substantially not contained. SnO2 may also be substantially not contained. It should be noted that the content rate of SnO2 is the value represented by T-SnO2.

[0099] (SO3)

[0100] SO3 is also an optional component. Trace amounts of SO3 can reduce the bubbles remaining in the glass and help improve the mass production adaptability of the glass. The lower limit of the content rate of SO3 can be 0.001 mass% or more, and further 0.002 mass% or more. The upper limit of the content rate of SO3 can 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 further 0.01 mass% or less. SO3 may also be substantially not contained.

[0101] (F2、Cl2)

[0102] Fluorine (F2) and chlorine (Cl2) are also optional components. Especially in a glass composition with a low content rate of alkali metal oxides, F2 and Cl2 can help promote the clarification of the glass. However, F2 and Cl2 are volatile and may scatter during melting. The upper limit of the content rate of F2 and Cl2 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, 0.2 mass% or less, and further 0.1 mass% or less, respectively. F2 may also be substantially not contained. The lower limit of the content rate of F2 can be 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.35 mass% or more, and further 0.4 mass% or more. Cl2 may also be substantially not contained.

[0103] (Total of components)

[0104] The total of the above-described components, that is, the components described from SiO2 to F2 and Cl2, may be 95% by mass or more, 97% by mass or more, and further 99% by mass or more, and may be 99.5% by mass or more depending on circumstances. The lower limit of the total content of the components shown by (SiO2 + B2O3 + Al2O3 + MgO + CaO + ZnO) may be 75% by mass or more, 85% by mass or less, 90% by mass or more, and further 95% by mass or more, and may be 97% by mass or more depending on circumstances. The upper limit of the total content of the components shown by (SiO2 + B2O3 + Al2O3 + MgO + CaO + ZnO) may be 99% by mass or less. The lower limit of the total of the components shown 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 shown 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.

[0105] (Other components)

[0106] As other optional components, at least one selected from P2O5, HfO2, Ga2O3, La2O3, Pr2O3, Nd2O3, Pm2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, WO3, Nb2O5, Sc2O3, Y2O3, MoO3, Ta2O5, MnO2, Cr2O3, CuO, CoO, PbO, Bi2O3, Br2, I2, As2O3, and Sb2O3 can be cited. However, the other optional components are not limited to these. The other optional components can each be contained at a content rate of 3% by mass or less. The allowable content rate of each of the other optional components can be 2% by mass or less, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, and further 0.1% by mass or less. The other optional components can also each be substantially not contained. Y2O3 and La2O3 are components that adjust the devitrification temperature and viscosity during glass formation. In addition, Y2O3 and La2O3 are components that increase the Young's modulus of the glass. For example, the sum of the content rates of Y2O3 and La2O3 (Y2O3 + La2O3) can 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, and further 0.1% by mass or less. For example, from the viewpoint of environmental protection, As2O3 and Sb2O3 are desirably each substantially not contained. The total of the content rates of the other optional components listed above can 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, and further 0.1% by mass or less.

[0107] <Preferred Composition>

[0108] Preferred composition examples are shown below. For each component, the range indicated in parentheses is the more preferred range.

[0109] (Composition A1)

[0110] A glass composition containing, in mass%:

[0111] 58 ≤ SiO2 ≤ 64 (58.5 ≤ SiO2 ≤ 63),

[0112] 1 ≤ B2O3 ≤ 6 (1.5 ≤ B2O3 ≤ 5),

[0113] 17 ≤ Al2O3 ≤ 23 (18 ≤ Al2O3 ≤ 22),

[0114] 4 ≤ MgO ≤ 13 (7 ≤ MgO ≤ 12),

[0115] 0 ≤ CaO ≤ 3 (0 ≤ CaO ≤ 1),

[0116] 1 ≤ ZnO ≤ 8 (1.1 ≤ ZnO ≤ 7),

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

[0118] a composition with 0.2 ≤ ZrO2 ≤ 4 (0.3 ≤ ZrO2 ≤ 3), and,

[0119] substantially free of TiO2.

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

[0121] (Composition A2)

[0122] A glass composition containing, by mass%:

[0123] 58.5 ≤ SiO2 ≤ 62,

[0124] 1.5 ≤ B2O3 ≤ 5,

[0125] 18 ≤ Al2O3 ≤ 22,

[0126] 7 ≤ MgO ≤ 12,

[0127] 0 ≤ CaO ≤ 1,

[0128] 1.1 ≤ ZnO ≤ 7,

[0129] 0.1 ≤ (Li2O + Na2O + K2O) ≤ 2,

[0130] a composition with 0.3 ≤ ZrO2 ≤ 3, and,

[0131] satisfying 9 ≤ (MgO + ZnO) ≤ 13.8, substantially free of TiO2.

[0132] Composition A2 has a low linear thermal expansion coefficient and a high Young's modulus, and also has excellent mass production adaptability. An example of excellent mass production adaptability is a low operating temperature and a large ΔT. Here, the low operating temperature is, for example, 1395 °C or lower, and the large ΔT is, for example, 10 °C or higher.

[0133] (Composition B)

[0134] A glass composition containing, by mass%:

[0135] 58 ≤ SiO2 ≤ 64 (58.5 ≤ SiO2 ≤ 63),

[0136] 1 ≤ B2O3 ≤ 6 (1.5 ≤ B2O3 ≤ 5),

[0137] 17 ≤ Al2O3 ≤ 23 (18 ≤ Al2O3 ≤ 22),

[0138] 4 ≤ MgO ≤ 13 (7 ≤ MgO ≤ 12),

[0139] 0 ≤ CaO ≤ 3 (0 ≤ CaO ≤ 1),

[0140] 0.5 ≤ ZnO ≤ 2.8 (1.1 ≤ ZnO ≤ 2.8),

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

[0142] substantially free of TiO2 and ZrO2.

[0143] Composition B is different from Compositions A1 - A2 and C and is substantially free of ZrO2. Composition B has a low linear thermal expansion coefficient and a high Young's modulus, and also has excellent mass production adaptability.

[0144] (Composition C)

[0145] A glass composition containing, in mass%:

[0146] 58 ≤ SiO2 ≤ 64 (58.5 ≤ SiO2 ≤ 63),

[0147] 1 ≤ B2O3 ≤ 6 (1.5 ≤ B2O3 ≤ 5),

[0148] 17 ≤ Al2O3 ≤ 23 (18 ≤ Al2O3 ≤ 22),

[0149] 4 ≤ MgO ≤ 13 (7 ≤ MgO ≤ 12),

[0150] 0 ≤ CaO ≤ 3 (0 ≤ CaO ≤ 1),

[0151] 1 ≤ ZnO ≤ 8 (1.1 ≤ ZnO ≤ 7),

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

[0153] 0.1 ≤ TiO2 ≤ 4 (0.3 ≤ TiO2 ≤ 3),

[0154] a composition of 1.1 ≤ ZrO2 ≤ 4 (1.1 ≤ ZrO2 ≤ 3).

[0155] Component C is different from components A1 - A2 and B, and contains both TiO2 and ZrO2 simultaneously. Component C has a low linear thermal expansion coefficient and a high Young's modulus, and also has excellent mass - production adaptability. In addition, component C is also suitable for achieving a low dielectric loss tangent.

[0156] Components A1, A2, B, and C may further contain 0.1 ≤ T - Fe2O3 ≤ 3 (for a more preferred range, 0.1 ≤ T - Fe2O3 ≤ 2), and may further contain 0.001 ≤ SO3 ≤ 0.5 (for a more preferred range, 0.002 ≤ SO3 ≤ 0.3) together with T - Fe2O3 in this range. In addition, as described in the <Composition> column, components A1, A2, B, and C can change the upper limit and / or lower limit of the content rate of each component. Furthermore, as described in the <Composition> column, components A1, A2, B, and C can adjust the total of the components and can also contain other components.

[0157] <Properties>

[0158] Hereinafter, the properties that can be obtained by the glass composition of the present embodiment will be described.

[0159] (Melting characteristics)

[0160] The temperature at which the viscosity of molten glass is 1000 dPa·sec (1000 poise) is called the working temperature of the glass, which is a temperature suitable for the forming of the glass. If the working temperature of the glass is 1100 °C or higher, the deviation of dimensions such as the diameter of glass fibers 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 not easily 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.

[0161] 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 homogeneous glass can be manufactured with a high qualified rate. 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, for example, it is 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. It should be noted that the devitrification temperature is the temperature at which crystals are formed and begin to grow in the molten glass blank, and can be measured by the method described later.

[0162] (Coefficient of linear expansion)

[0163] 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 helps to improve the dimensional stability of the resin composition containing the glass. The lower limit of the coefficient of linear expansion can be 20×10 -7 / °C or more, 25×10 -7 / °C or more, 26×10 -7 / °C or more, and further 27×10 -7 / °C or more. The upper limit of the coefficient of linear expansion can be 35×10 -7 / °C or less, 34×10 -7 / °C or less, 33×10 -7 / °C or less, and further 32×10 -7 / °C or less, and can be 31×10 -7 / °C or less according to circumstances.

[0164] (Glass transition temperature)

[0165] The glass transition temperature (glass transition point) is an index of the heat resistance of the glass. In the case of subjecting the resin composition containing the glass 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 further 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 further 770 °C or less.

[0166] (Young's modulus)

[0167] The high Young's modulus of the glass helps to improve 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 the elastic wave propagating in the glass measured by the usual 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 further 90 GPa or more. The upper limit of Young's modulus can be 100 GPa or less, can be 99 GPa or less, 98 GPa or less, 97 GPa or less, 96 GPa or less, and further 95 GPa or less.

[0168] (Dielectric constant, tangent of dielectric loss angle)

[0169] The low dielectric constant of the glass contributes to improving the dielectric properties of a 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. Strictly speaking, the dielectric constant refers to the relative dielectric constant, but in this specification, it is only denoted as the dielectric constant as a convention. The dielectric constant is a value at room temperature (25°C). The dielectric constant can be 5.0 or more.

[0170] The low dielectric loss tangent of the glass also contributes to improving the dielectric properties of a resin composition containing glass fibers or glass fillers. The dielectric loss 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 loss tangent is a value at room temperature (25°C). The dielectric loss tangent can be 0.0010 or more.

[0171] [Glass article]

[0172] <Glass fiber>

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

[0174] The average fiber diameter of the glass fiber is, for example, 0.1 to 50 μm. The average fiber diameter can be 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 1 μm or more, 2 μm or more, and further 3 μm or more, and can be 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 8 μm or less, 6 μm or less, 5 μm or less, 4.6 μm or less, and further 4.3 μm or less. The glass composition having a characteristic temperature suitable for mass production is suitable for stably manufacturing in the form of fine glass fibers. In a preferred mode, the average fiber diameter is finer, for example, 3.9 μm or less, and further 3.5 μm or less. The glass fiber is, for example, a glass long fiber (filament).

[0175] The glass fiber can have at least one shape selected from rovings, roving cloths, continuous strand mats, chopped fibers, flat fibers, filament mats, chopped strands, yarns, glass cloths, and glass tapes.

[0176] 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 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 can have a concave shape in which the surface extending along the major axis D2 recedes at the central part compared to the end part.

[0177] 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 melted glass composition into a glass fiber.

[0178] <Glass filler>

[0179] The glass filler of the present embodiment is composed of the above glass composition. The glass filler can be at least one selected from flaky glass, glass powder, glass beads, and fine flakes.

[0180] Flaky glass, also known as scaly glass, has a flaky shape. The average particle size of the flaky glass is, for example, 0.2 to 15,000 μm. The aspect ratio of the flaky 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 determined by measuring the thickness t of 100 or more pieces of flaky glass using a scanning electron microscope (SEM) and calculating the average value. The average particle size of the flaky glass and other glass fillers can be determined by the particle size (D50) at which the cumulative volume percentage in the particle size distribution measured by the laser diffraction scattering method is 50%. The flaky glass can be obtained by known blow molding methods, cup methods, etc.

[0181] Glass powder is powdered 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. The glass powder can be obtained by known methods.

[0182] 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 the particles of the glass beads. The glass beads can be obtained by known methods.

[0183] A fine flake is flaky glass, which is a thin flaky glass. The fine flake can be composed of, for example, flaky glass with an average thickness of 0.1 to 2.0 μm. Additionally, for example, it can contain flaky glass with a thickness in the range of 0.01 to 2.0 μm in a proportion of 90 mass% or more. The fine flake with such a thin average thickness and small deviation in thickness has a high effect of reinforcing the resin and is also excellent in the effect of reducing the molding shrinkage rate of the resin. The fine flake is also suitable for relaxing the restrictions on the thickness of the resin molded body compared to the past. The fine flake is preferably composed of flaky glass with an average thickness of 0.1 to 1.0 μm. The fine flake preferably contains flaky glass with a thickness in the range of 0.05 to 1.0 μm in a proportion of 90 mass% or more. The fine flake can be obtained by the methods described for flaky glass.

[0184] 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 shaping the melted glass composition into a glass filler.

[0185] [Articles Containing Glass Fibers and / or Glass Fillers]

[0186] The glass fibers and glass fillers of the present embodiment can be used in various articles exemplified below. The various articles have aspects such as a molded body, a filler-containing article, a resin article, etc.

[0187] <Molded Body>

[0188] The molded article of this embodiment contains the above glass fiber and is molded into a specified shape. The molded article is not limited to the following and can be at least one selected from a wire for rubber reinforcement, a nonwoven fabric, a prepreg, a reinforced plastic, a printed circuit board, an inorganic solidified body, a filter, a heat insulating material, a sound absorbing material, and a battery spacer.

[0189] <Article Containing Filler>

[0190] The article containing filler of this embodiment contains the above glass filler. The article containing filler is not limited to the following and can be at least one selected from a reinforced plastic, a coating, an ink, a printed circuit board, an inorganic solidified body, and a cosmetic.

[0191] <Resin Article>

[0192] The resin article of this embodiment contains the above glass fiber and / or glass filler, and a resin. The resin article can be an electrical insulating member or a mechanical member. Examples of these members are as described above. The resin can be a thermoplastic resin. The thermoplastic resin is not particularly limited and is, for example, polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyester, polyamide, polycarbonate, polybutene, polybutylene terephthalate, a copolymer thereof, etc. If polybutylene terephthalate is used, the effect of suppressing warping of the molded article and improving dimensional stability due to mixing with the glass filler becomes greater. The specific surface area of flaky glass, flat fibers, and thin flakes is relatively large, which is suitable for ensuring the bonding force with the thermoplastic resin.

[0193] [Technology Provided by this Embodiment]

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

[0195] (Technology 1)

[0196] A glass composition containing, in mass%:

[0197] 56 ≤ SiO2 ≤ 70,

[0198] 0.1 ≤ B2O3 ≤ 8,

[0199] 15 ≤ Al2O3 ≤ 24,

[0200] 4 ≤ MgO ≤ 14,

[0201] 0 ≤ CaO ≤ 4,

[0202] 0 ≤ ZnO ≤ 10,

[0203] 0 ≤ (Li2O + Na2O + K2O) ≤ 4,

[0204] a component of 0.1 ≤ ZrO2 ≤ 5, and,

[0205] Substantially does not contain TiO2.

[0206] (Technology 2)

[0207] A glass composition containing, in mass %:

[0208] 56 ≤ SiO2 ≤ 70,

[0209] 0.1 ≤ B2O3 ≤ 8,

[0210] 15 ≤ Al2O3 ≤ 24,

[0211] 4 ≤ MgO ≤ 14,

[0212] 0 ≤ CaO ≤ 4,

[0213] 0.1 ≤ ZnO ≤ 3,

[0214] Components of 0 ≤ (Li2O + Na2O + K2O) ≤ 4, and

[0215] Substantially does not contain TiO2 and ZrO2.

[0216] (Technology 3)

[0217] A glass composition containing, in mass %:

[0218] 56 ≤ SiO2 ≤ 70,

[0219] 0.1 ≤ B2O3 ≤ 8,

[0220] 15 ≤ Al2O3 ≤ 24,

[0221] 4 ≤ MgO ≤ 14,

[0222] 0 ≤ CaO ≤ 4,

[0223] 0 ≤ ZnO ≤ 10,

[0224] 0 ≤ (Li2O + Na2O + K2O) ≤ 4,

[0225] Components of 1 ≤ ZrO2 ≤ 5.

[0226] (Technology 4)

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

[0228] (Technology 5)

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

[0230] (Technology 6)

[0231] The glass composition according to any one of Technologies 1 to 5 contains a component of 1 ≤ (Li2O + Na2O + K2O + TiO2 + ZrO2 + T-Fe2O3) ≤ 19 in terms of mass%. Here, T-Fe2O3 is the total iron oxide converted to Fe2O3.

[0232] (Technology 7)

[0233] The glass composition according to any one of Technologies 1 to 6 contains a component of 2 ≤ B2O3 ≤ 6 in terms of mass%.

[0234] (Technology 8)

[0235] The glass composition according to any one of Technologies 1 to 7 contains a component of 5 ≤ MgO ≤ 13 in terms of mass%.

[0236] (Technology 9)

[0237] The glass composition according to Technology 8 contains a component of 0 ≤ CaO ≤ 1 in terms of mass%.

[0238] (Technology 10)

[0239] The glass composition according to any one of Technologies 1 to 9 substantially does not contain SrO.

[0240] (Technology 11)

[0241] The glass composition according to any one of Technologies 1 to 10 substantially does not contain BaO.

[0242] (Technology 12)

[0243] The glass composition according to any one of Technologies 1 to 11 contains a component of 0 ≤ ZnO ≤ 8 in terms of mass%.

[0244] (Technology 13)

[0245] The glass composition according to any one of Technologies 1 to 12 contains a component of 4 ≤ (MgO + ZnO) ≤ 17 in terms of mass%.

[0246] (Technology 14)

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

[0248] (Technology 15)

[0249] The glass composition according to Technology 14 contains a component of 0.1 ≤ (Li2O + Na2O + K2O) ≤ 1 in terms of mass%.

[0250] (Technology 16)

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

[0252] (Technology 17)

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

[0254] (Technology 18)

[0255] The glass composition according to any one of Technologies 1 to 17 contains a component of 0 ≤ T-Fe2O3 ≤ 5 in terms of mass%. Herein, T-Fe2O3 is the total iron oxide converted into Fe2O3.

[0256] (Technology 19)

[0257] The glass composition according to any one of Technologies 1 to 18 contains a component of 0 ≤ Y2O3 ≤ 3 in terms of mass%.

[0258] (Technology 20)

[0259] The glass composition according to any one of Technologies 1 to 19 contains a component of 0 ≤ T-SnO2 ≤ 2 in terms of mass%. Herein, T-SnO2 is the total tin oxide converted into SnO2.

[0260] (Technology 21)

[0261] The glass composition according to any one of Technologies 1 to 20 contains a component of 0 ≤ CeO2 ≤ 2 in terms of mass%.

[0262] (Technology 22)

[0263] The glass composition according to any one of Technologies 1 to 21 contains a component of 0 ≤ F2 ≤ 5 in terms of mass%.

[0264] (Technology 23)

[0265] The glass composition according to any one of Technologies 1 to 22 contains a component of 0 ≤ SO3 ≤ 0.5 in terms of mass%.

[0266] (Technology 24)

[0267] The glass composition according to any one of Technologies 1 to 23, wherein when the temperature at a viscosity of 1000 dPa·sec is set as the working temperature, the above working temperature is 1450°C or lower.

[0268] (Technology 25)

[0269] The glass composition according to any one of Technologies 1 to 24, wherein when the temperature at a viscosity of 1000 dPa·sec is set as the working temperature, the temperature difference ΔT obtained by subtracting the devitrification temperature from the above working temperature is 0°C or higher.

[0270] (Technology 26)

[0271] The glass composition according to any one of Technologies 1 to 25, having a Young's modulus of 85 to 100 GPa.

[0272] (Technology 27)

[0273] The glass composition according to any one of Technologies 1 to 26, having an average linear expansion coefficient of 20 to 35×10 -7 / °C at 50 to 350°C.

[0274] (Technology 28)

[0275] The glass composition according to any one of Technologies 1 to 27, having a dielectric constant of 6.5 or lower at a frequency of 1 GHz.

[0276] (Technology 29)

[0277] The glass composition according to any one of Technologies 1 to 28, having a dielectric loss tangent of 0.0060 or lower at a frequency of 1 GHz.

[0278] (Technology 30)

[0279] A glass fiber comprising the glass composition according to any one of Technologies 1 to 29.

[0280] (Technology 31)

[0281] The glass fiber according to Technology 30, having at least one shape selected from rovings, roving fabrics, continuous strand mats, milled fibers, flattened fibers, filament mats, chopped strands, yarns, glass fabrics, and glass tapes.

[0282] (Technology 32)

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

[0284] (Technique 33)

[0285] The glass filler according to Technique 32, which is at least one selected from flaky glass, glass powder, glass beads, and flakes.

[0286] (Technique 34)

[0287] A shaped body comprising the glass fiber described in Technique 30 and being at least one selected from rubber reinforcing cords, non-woven fabrics, prepregs, reinforced plastics, printed circuit boards, inorganic solidified bodies, filters, heat insulating materials, sound absorbing materials, and battery spacers.

[0288] (Technique 35)

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

[0290] (Technique 36)

[0291] A method for manufacturing glass fiber, which includes a step of melting the glass composition described in any one of Techniques 1 to 29 and a step of shaping the melted glass composition into glass fiber.

[0292] (Technique 37)

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

[0294] Examples

[0295] Hereinafter, examples and comparative examples are given to further specifically illustrate the embodiments of the present invention.

[0296] (Examples and Comparative Examples)

[0297] Common glass raw materials such as silica sand were formulated to have the compositions shown in Tables 1 to 4, and batch materials of the glass raw materials were prepared in the examples and comparative examples, respectively. Using an electric furnace, each batch material was heated to 1500 to 1600 °C to be melted and maintained for about 4 hours until the composition became uniform. Then, a part of the molten glass (glass melt) was made to flow out onto an iron plate and slowly cooled to room temperature in the electric furnace to obtain a glass composition (plate-like object, glass specimen) as a block. It should be noted that 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.

[0298] The evaluation methods for the properties are described below.

[0299] (Operating temperature)

[0300] For the obtained glass composition, the relationship between viscosity and temperature was investigated by the usual platinum ball pulling method, and the operating temperature was determined from the results. Here, the platinum ball pulling method refers to the following method: A platinum ball is immersed in the molten glass, and the relationship between the load (resistance) when pulling the platinum ball at a constant speed and the gravity and buoyancy acting on the platinum ball is applied to the Stokes formula representing the relationship between the viscosity and the falling speed when minute particles settle in a fluid, thereby measuring the viscosity.

[0301] (Devitrification temperature)

[0302] 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 having 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. In the case where the glass became cloudy and crystals could not be observed, the maximum temperature of the electric furnace corresponding to the position where cloudiness appeared was taken as the devitrification temperature. Here, the particle diameter is a value measured by the sieving method. It should be noted that the temperature (temperature distribution in the electric furnace) varying depending on the position in the electric furnace was measured in advance, and the glass composition placed at a specified position in the electric furnace was heated at the temperature of the specified position measured in advance. The temperature difference ΔT is the temperature difference obtained by subtracting the devitrification temperature from the operating temperature.

[0303] (Coefficient of linear expansion)

[0304] For the obtained glass composition, the average linear expansion coefficient at 50 to 350 °C was measured using a commercially available dilatometer [Rigaku Corporation, thermomechanical analyzer, TMA8510]. In addition, based on the thermal expansion curve obtained by the TMA apparatus, the glass transition temperature T g .

[0305] (Young's modulus)

[0306] Young's modulus E was determined as follows: The longitudinal wave velocity vl and the transverse wave velocity vt of the elastic wave propagating in the glass were measured using the ordinary ultrasonic method, and based on the density ρ of the glass measured by the Archimedes method, E = 3ρ·v t 2 ·(v l 2 - 4 / 3·v t 2 ) / (v l 2 - v t 2 ) was calculated from the formula.

[0307] (Dielectric constant, dielectric loss tangent)

[0308] The dielectric constant and the dielectric loss tangent at a frequency of 1 GHz were measured using a dielectric constant measuring apparatus based on the cavity resonator perturbation method. The measurement temperature was set to 25 °C, and the size of the sample for measurement was set to a rectangular parallelepiped with a square bottom side of 1.5 mm and a height of 100 mm.

[0309] (Number of bubbles)

[0310] Usual glass raw materials such as silica sand were blended, and batches of glass raw materials were prepared in Examples and Comparative Examples, respectively. Using an electric furnace, 150 g of each batch was heated and melted at a temperature of 1600 °C as the test temperature, and maintained for 2 hours until the composition became uniform. Then, 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 specimen. The number of bubbles in the glass specimen was observed with an optical microscope, and the number of bubbles per 100 g of glass was calculated. The case where the number of bubbles in 100 g of glass was less than 400 was designated as A, the case where it was 400 or more and less than 2000 was designated as B, the case where it was 2000 or more and less than 10000 was designated as C, and the case where it was 10000 or more was designated as D.

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

[0312] [Table 1]

[0313]

[0314] [Table 2]

[0315]

[0316] [Table 3]

[0317]

[0318] [Table 4]

[0319]

[0320] According to each embodiment, the coefficient of linear expansion is 29 - 32×10 -7 / °C, the Young's modulus is 90 - 92 GPa, the operating temperature is 1324 - 1410 °C, and the difference ΔT (operating temperature - devitrification temperature) is 0 - 54 °C.

[0321] The glass composition of Comparative Example 1 has an E - glass composition. The average coefficient of linear expansion and the difference in Young's modulus of E - glass at 50 - 350 °C. The glass composition of Comparative Example 2 has an S - glass composition. The operating temperature of S - glass is high, ΔT is negative, and the mass - productivity is poor. The glass composition of Comparative Example 3 has the glass composition of Example 2 of Patent Document 1. The difference in Young's modulus of this glass is such that the operating temperature is slightly high. The glass composition of Comparative Example 4 has the glass composition of Example 2 of Patent Document 2. The difference in the average coefficient of linear expansion of this glass at 50 - 350 °C. It should be noted that the reason for the higher coefficient of linear expansion (33×10 -7 / °C) of Comparative Example 4 than the measured value (29×10 -7 / °C) in Patent Document 2 depends on the difference in the measured temperature range. In addition, the present inventors conducted additional tests, and as a result, ΔT of Comparative Example 4 is negative and the mass - productivity is poor. At least one of the average coefficient of linear expansion, Young's modulus, and the difference ΔT of the glass compositions of Comparative Examples 5 - 16 is also insufficient.

Claims

1. A glass composition comprising, 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 Contains virtually no TiO2.

2. A glass composition comprising, 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 It contains virtually no TiO2 and ZrO2.

3. A glass composition comprising, 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, Composition: 1≤ZrO2≤5. 4 . The glass composition according to claim 1 , comprising, expressed in mass %, components in an amount of 75 ≤ (SiO 2 + B 2 O 3 + Al 2 O 3 + MgO + CaO + ZnO) ≤ 99. 5 . The glass composition according to claim 1 , comprising components expressed in mass % such that 1≤(ZnO+ZrO 2 )≤15.

6. The glass composition according to any one of claims 1 to 3, comprising, expressed in mass %, 1 ≤ (Li2O + Na2O + K2O + TiO2 + ZrO2 + T-Fe2O3) ≤ 19 components, in, T-Fe2O3 is the total iron oxide converted to Fe2O3. 7 . The glass composition according to claim 1 , comprising, expressed in mass %, components of 2≤B 2 O 3 ≤6. 8 . The glass composition according to claim 1 , comprising, in terms of mass %, components of 5 ≤ MgO ≤ 13. 9 . The glass composition according to claim 1 , comprising a component of 0≤CaO≤1 expressed in mass %. 10 . The glass composition according to claim 1 , which contains substantially no SrO. 11 . The glass composition according to claim 1 , which contains substantially no BaO. 12 . The glass composition according to claim 1 , comprising, expressed in mass %, 0≤ZnO≤8. 13 . The glass composition according to claim 1 , comprising, in terms of mass %, components of 4≤(MgO+ZnO)≤17. 14 . The glass composition according to claim 1 , comprising components expressed in mass % such that 0≤(Li 2 O+Na 2 O+K 2 O)≤1. 15 . The glass composition according to claim 1 , comprising, expressed in mass %, components such that 0.1≤(Li 2 O+Na 2 O+K 2 O)≤1. 16 . The glass composition according to claim 1 , comprising components expressed in mass % such that 0≤(Na 2 O+K 2 O)≤1. 17 . The glass composition according to claim 1 , comprising components expressed in mass % such that 0≤(TiO 2 +ZrO 2 )≤4.

18. The glass composition according to any one of claims 1 to 3, comprising, expressed in mass %, components of 0 ≤ T-Fe2O3 ≤ 5, in, T-Fe2O3 is the total iron oxide converted to Fe2O3.

19. The glass composition according to any one of claims 1 to 3, comprising, expressed in mass %, components of 0≤Y2O3≤3.

20. The glass composition according to any one of claims 1 to 3, comprising, expressed in mass %, a component of 0 ≤ T-SnO2 ≤ 2, in, T-SnO2 is the total tin oxide converted to SnO2. 21 . The glass composition according to claim 1 , comprising a component of 0≤CeO 2 ≤2 expressed in mass %. 22 . The glass composition according to claim 1 , comprising components of 0≤F2≤5 expressed in mass %. 23 . The glass composition according to claim 1 , comprising, expressed in mass %, a component of 0≤SO 3 ≤0.

5.

24. The glass composition according to any one of claims 1 to 3, wherein When the temperature at which the viscosity reaches 1000 dPa·sec is defined as the working temperature, the working temperature is 1450° C. or lower.

25. The glass composition according to any one of claims 1 to 3, wherein When the temperature at which the viscosity is 1000 dPa·sec is defined as the working temperature, the temperature difference ΔT obtained by subtracting the devitrification temperature from the working temperature is 0° C. or more. 26 . The glass composition according to claim 1 , which has a Young's modulus of 85 GPa to 100 GPa.

27. The glass composition according to any one of claims 1 to 3, wherein the average linear expansion coefficient at 50°C to 350°C is 20×10 -7 / ℃~35×10 -7 / ℃.

28. The glass composition according to any one of claims 1 to 3, which has a dielectric constant of 6.5 or less at a frequency of 1 GHz.

29. The glass composition according to any one of claims 1 to 3, which has a dielectric loss tangent of 0.0060 or less at a frequency of 1 GHz.

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

31. The glass fiber of claim 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.

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

33. The glass filler according to claim 32, which is at least one selected from the group consisting of flaky glass, glass powder, glass beads and fine flakes.

34. A molded body comprising the glass fiber according to claim 30 and being at least one selected from the group consisting of rubber reinforcing threads, nonwoven fabrics, prepregs, reinforced plastics, printed circuit boards, inorganic solid bodies, filters, heat insulating materials, sound absorbing materials, and battery spacers.

35. A filler-containing product, comprising the glass filler according to claim 32 and being at least one selected from reinforced plastics, coatings, inks, printed substrates, inorganic solids and cosmetics. 36 . A method for producing glass fibers, comprising the steps of melting the glass composition according to claim 1 , and forming the molten glass composition into glass fibers. 37 . A method for producing a glass filler, comprising the steps of melting the glass composition according to claim 1 , and forming the molten glass composition into a glass filler.

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