Composition for glass fiber, glass fiber, and method for manufacturing glass fiber

Abstract

Provided are: a composition for glass fiber, the composition having exceptionally low dielectric properties; glass fiber; and a method for manufacturing glass fiber.　The composition for glass fiber is characterized by containing, as the glass composition thereof in terms of mass%, 45-70% of SiO2, 0-40% of Al2O3, 5-40% of B2O3, 0-10% of CaO, 0-10% of MgO, and 0-5% of SnO2.

Description

Composition for glass fibers, glass fibers, and method for producing glass fibers

[0001] This invention relates to a composition for glass fibers, glass fibers, and a method for producing glass fibers.

[0002] With the development of various electronic devices that support the information industry, the demand for generation AI and data servers is increasing. Circuit components for electronic devices, which are becoming increasingly high-density and high-speed, require low dielectric properties such as low dielectric constant and low dielectric loss tangent to minimize signal propagation delay due to dielectric loss (transmission loss, conduction loss, deformation loss, and vibration loss), as well as to prevent overheating of the substrate due to thermal loss. Examples of such electronic circuit boards include printed circuit boards and low-temperature fired substrates. Printed circuit boards are composite materials made by mixing glass fibers as a reinforcing material with resin and forming them into a sheet, while low-temperature fired substrates are made of SiO ２ Ya B ２ O ３ This product is made by firing a green sheet of composite powder, which is a mixture of powdered glass containing a large amount of [material name] and fillers such as silica.

[0003] Furthermore, beyond circuit boards for electronic devices, the miniaturization of electronic devices and the increase in communication speeds have led to a growing demand for low dielectric properties in resins surrounding circuit boards, components for communication equipment, and resin materials used in electronic device casings. Consequently, low dielectric properties are also required for glass fibers used as reinforcing materials for these resin materials.

[0004] Furthermore, in the automotive industry, with the development of autonomous driving systems, it is anticipated that the demand for glass fiber composite resins, which possess high strength, light weight, and low dielectric properties, will increase as components used in in-vehicle radar and cameras.

[0005] Conventionally, E-glass has been used as glass fiber for printed circuit boards and resin reinforcement, but it cannot satisfy the low dielectric properties required for circuit components in electronic devices in recent years. Therefore, glass characterized by low dielectric constant and low dielectric loss tangent, referred to as D-glass (for example, Patent Document 1), and SiO ２ -B ２ O ３ - Al ２ O ３An alkaline earth metal element is added to the glass composition system to obtain a glass (for example, Patent Document 2) that maintains low dielectric properties, aims at phase separation suppression and reduction of alkali elution amount, etc. has been proposed.

[0006] Japanese Patent Application Laid-Open No. 63-2831 Japanese Patent Application Laid-Open No. 06-219780

[0007] By the way, the above-mentioned D glass and the glass of Patent Document 2 have low dielectric properties compared to E glass, but have a high dielectric constant at 1 MHz, and there is a problem that they are insufficient as the low dielectric properties required in recent years.

[0008] An object of the present invention is to provide a glass fiber composition, a glass fiber, and a method for producing a glass fiber, which are excellent in low dielectric properties.

[0009] Hereinafter, each aspect of the glass fiber composition for solving the above problems will be described.

[0010] The glass fiber composition according to Aspect 1 of the present invention has, as a glass composition, in mass%, SiO ２ 45 to 70%, Al ２ O ３ 0 to 40%, B ２ O ３ 5 to 40%, CaO 0 to 10%, MgO 0 to 10%, SnO ２ 0 to 5%, and is characterized by containing these. By doing so, a glass fiber composition and a glass fiber excellent in low dielectric properties can be obtained.

[0011] In the glass fiber composition of Aspect 2, in Aspect 1, in mass%, SiO ２ + B ２ O ３ 50 to 90% is preferably contained. By doing so, a glass fiber composition and a glass fiber excellent in low dielectric properties can be obtained.

[0012] In the glass fiber composition of Aspect 3, in Aspect 1 or Aspect 2, in mass%, TiO ２ Less than 0 to 2% is preferably contained. By doing so, a glass fiber composition and a glass fiber excellent in low dielectric properties can be obtained.

[0013] In the glass fiber composition of Embodiment 4, in any one embodiment of Embodiments 1 to 3, the mass ratio of SiO ２ / SnO ２ The value of is preferably between 10 and 10000. In this way, a glass fiber composition and glass fibers with excellent low dielectric properties can be obtained.

[0014] In the glass fiber composition of Embodiment 5, in any one embodiment of Embodiments 1 to 4, the mass ratio Al ２ O ３ The value of / MgO is preferably between 10 and 500. In this way, a glass fiber composition and glass fibers with excellent low dielectric properties can be obtained.

[0015] In the glass fiber composition of embodiment 6, in any one embodiment of embodiments 1 to 5, Li is present in mass%. ２ O + Na ２ O+K ２ O+SrO+BaO+ZnO+P ２ O ５ It is preferable that the content be 0.002 to 3%. By doing so, a glass fiber composition and glass fibers with excellent low dielectric properties can be obtained.

[0016] In the glass fiber composition of Embodiment 7, it is preferable that in any one embodiment of Embodiments 1 to 6, the dielectric constant ε at 25°C and 10 GHz is 6 or less, and the dielectric loss tangent tanδ is 0.0080 or less. By doing so, a glass fiber composition and glass fibers with excellent low dielectric properties can be obtained.

[0017] In the glass fiber composition of Embodiment 8, it is preferable that in any one embodiment of Embodiments 1 to 7, the dielectric constant ε at 25°C and 40 GHz is 6 or less, and the dielectric loss tangent tanδ is 0.0100 or less. By doing so, a glass fiber composition and glass fibers with excellent low dielectric properties can be obtained.

[0018] In the glass fiber composition of Embodiment 9, it is preferable that the spinning temperature Tx is 1500°C or less in any one embodiment of Embodiments 1 to 8. By doing so, glass fibers with excellent productivity can be obtained.

[0019] In the glass fiber composition of embodiment 10, it is preferable that the Young's modulus E at 25°C is 30 GPa or more in any one embodiment of embodiments 1 to 9. By doing so, sufficient strength can be obtained in the glass fiber reinforced resin.

[0020] In the glass fiber composition of embodiment 11, in any one embodiment of embodiments 1 to 10, the coefficient of thermal expansion α at 50 to 200°C is 40 × 10 －７ It is preferable that the temperature be below / °C. By doing so, damage due to temperature changes can be suppressed in the glass fiber reinforced resin.

[0021] The glass fiber according to embodiment 12 of the present invention is characterized by comprising glass made from a glass fiber composition according to any one embodiment of embodiments 1 to 11.

[0022] The glass fiber reinforced product according to aspect 13 of the present invention is characterized by containing glass fibers according to aspect 12.

[0023] A method for producing glass fibers according to embodiment 14 of the present invention is characterized by comprising the steps of: preparing a glass raw material batch so as to obtain a glass fiber composition according to any embodiment 1 to 11; melting the glass raw material batch to obtain molten glass; and forming the molten glass into fibers. In this way, glass fibers with excellent low dielectric properties can be obtained.

[0024] According to the present invention, it is possible to provide a glass fiber composition with excellent low dielectric properties, as well as glass fibers, a glass fiber composition, and a method for producing glass fibers.

[0025] The glass fiber composition of this embodiment has a glass composition of SiO2 by mass. ２ 45-70%, Al ２ O ３ 0-40%, B ２ O ３ 5-40%, CaO 0-10%, MgO 0-10%, SnO ２It is characterized by containing 0-5% of the component. The reason for limiting the glass composition as described above is explained below. In the following explanation of the content of each component, unless otherwise specified, "%" means "mass percent".

[0026] (SiO ２ ) SiO ２ It is a component that forms the framework of the mesh-like structure of glass. It is also a component that reduces the dielectric constant ε and dielectric loss tangent tanδ of glass. SiO ２ If the content is too low, it becomes difficult to obtain the effect of lowering the dielectric constant ε and dielectric loss tangent tanδ. Therefore, SiO ２ The lower limit of the allowable amount is preferably 45% or more, 46% or more, 47% or more, 48% or more, 49% or more, 50% or more, more than 50%, 51% or more, 52% or more, 53% or more, more than 53%, and especially 53.5% or more. On the other hand, SiO ２ If the content is too high, the solubility of the raw material decreases, making it difficult to obtain homogeneous glass. In addition, the spinning temperature Tx increases, reducing productivity. Furthermore, in order to improve productivity, it is necessary to include components that improve melting, and these components tend to increase the dielectric constant ε and dielectric loss tangent tanδ. Therefore, SiO ２ The upper limit of the content is 70% or less, 69% or less, 68% or less, 67% or less, 66% or less, 65% or less, 64% or less, 63% or less, 62% or less, 61% or less, 60% or less, 59% or less, less than 59%, 58% or less, less than 58%, 57% or less, and especially less than 57%.

[0027] (Al ２ O ３ ) Al ２ O ３ It forms the framework of the glass's network structure and is a component that suppresses the phase separation of glass. Also, SiO ２ -B ２ O ３ - Al ２ O ３ In glass compositions, it is a component that reduces high-temperature viscosity. Al ２ O ３The lower limit of the content is 0% or more, 0.1% or more, 0.5% or more, 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, more than 8%, 8.5% or more, 9% or more, 9.5% or more, more than 9.5%, 10% or more, more than 10%, 10.5% or more, and more than 10.5% is particularly preferred. On the other hand, Al ２ O ３ If the content is too high, the difference in electronegativity between aluminum atoms and oxygen atoms becomes large, which tends to increase the dielectric constant ε and dielectric loss tangent tanδ. Also, the liquidus temperature Ty increases, and productivity decreases. Therefore, Al ２ O ３ The upper limit of the content is 40% or less, 35% or less, 30% or less, 25% or less, 24% or less, 23% or less, 22% or less, 21% or less, less than 21%, 20% or less, 19% or less, 18% or less, less than 18%, 17% or less, 16% or less, 15% or less, less than 15%, 14.5% or less, less than 14.5%, 14% or less, less than 14%, 13.5% or less, less than 13.5%, 13% or less, less than 13%, less than 12.5%, with less than 12% being particularly preferable.

[0028] (B ２ O ３ ) B ２ O ３ is SiO ２ Similarly, it is a component that forms the framework of the glass's mesh-like structure. It is also a component that reduces the dielectric constant ε and dielectric loss tangent tanδ of glass. B ２ O ３ If the content is too low, it becomes difficult to obtain the effect of lowering the dielectric constant ε and dielectric loss tangent tanδ of the glass. Therefore, B ２ O ３ The lower limit of the allowance is preferably 5% or more, 10% or more, 13% or more, 14% or more, 15% or more, 16% or more, more than 16%, 17% or more, 18% or more, 19% or more, 20% or more, 21% or more, 22% or more, 23% or more, 24% or more, 25% or more, more than 25%, 25.5% or more, more than 25.5%, 26% or more, more than 26%, and especially preferably 27% or more. On the other hand, B ２ O ３ If the content of B is too high, the glass may become more prone to phase separation. Also, if B is present on the glass surface... ２ O ３When a rich layer is formed, borate spraying makes the glass surface prone to crack formation, thus making spinning liable to become unstable. Therefore, B ２ O ３ The upper limit of the content is preferably 40% or less, 39% or less, 38% or less, 37% or less, 36% or less, 35% or less, 34% or less, 33% or less, 32% or less, 31% or less, less than 31%, 30% or less, less than 30%, 29.9% or less, 29.5% or less, particularly less than 29.5%.

[0029] (SiO ２ + B ２ O ３ ) SiO ２ and B ２ O ３ are both components that lower the dielectric constant ε and dielectric loss tangent tanδ of the glass. If the content of SiO ２ + B ２ O ３ is too low, the dielectric constant ε and dielectric loss tangent tanδ of the glass tend to increase. Therefore, the lower limit of the content of SiO ２ + B ２ O ３ is preferably 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, more than 75%, 76% or more, 77% or more, 78% or more, 79% or more, 80% or more, particularly more than 80%. On the other hand, if the content of SiO ２ + B ２ O ３ is too high, it may lead to a decrease in the melting property of the glass and a decrease in productivity. Therefore, the upper limit of the content of SiO ２ + B ２ O ３ is preferably 90% or less, less than 90%, 89% or less, less than 89%, 88% or less, less than 88%, 87% or less, less than 87%, 86% or less, less than 86%, 85% or less, particularly less than 85%. Note that SiO ２ + B ２ O ３ means the total content of SiO ２ and B ２ O ３ .

[0030] (MgO) MgO is a component that reduces the viscosity of glass. It is not necessary to contain MgO, but from the perspective of reducing the viscosity of glass, the lower limit of the MgO content is 0% or more, more than 0%, 0.001% or more, 0.002% or more, 0.003% or more, 0.004% or more, 0.005% or more, 0.006% or more, 0.007% or more, 0.008% or more, 0.009% or more, 0.01% or more, and particularly more than 0.01% is preferable. On the other hand, if the MgO content is too high, the thermal expansion coefficient α, dielectric constant ε, and dielectric loss tangent tanδ tend to increase. Also, due to crystal precipitation, the transparency of the glass tends to decrease. Therefore, the upper limit of the MgO content is 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5.5% or less, 5% or less, 4.1% or less, less than 4.1%, 4% or less, 3% or less, 2.8% or less, 2.6% or less, 2.4% or less, 2.2% or less, 2% or less, 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1% or less, less than 1%, 0.9% or less, less than 0.9%, 0.8% or less, less than 0.8%, 0.7% or less, and particularly less than 0.7% is preferable.

[0031] (Al ２ O ３ / MgO) In a glass composition system containing a large amount of Al ２ O ３ MgO tends to promote phase separation and crystal precipitation of the glass, and there is a risk that production will become difficult. Therefore, when MgO is contained in this embodiment, it is preferable to control the value of the mass ratio Al ２ O ３ / MgO. If the value of the mass ratio Al ２ O ３ / MgO is too small, production will become difficult due to phase separation and crystal precipitation of the glass. Therefore, the mass ratio Al ２ O ３The lower limit of the MgO value is 10 or more, greater than 10, 11 or more, 12 or more, 13 or more, 14 or more, 15 or more, greater than 15, 16 or more, 17 or more, 18 or more, 19 or more, 20 or more, greater than 20, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, greater than 100, 110 or more, 120 or more, 130 or more, 140 or more, 150 or more, 160 or more, 170 or more, 180 or more, 190 or more, 200 or more, 210 or more, 220 or more, 230 or more, 240 or more, 250 or more, 260 or more, 270 or more, 280 or more, 290 or more, 300 or more, with a particularly preferred value greater than 300. On the other hand, the mass ratio Al ２ O ３ If the value of / MgO is too large, Al ２ O ３ The crystals derived from this material are more likely to precipitate. Therefore, the mass ratio Al ２ O ３ The upper limit for / MgO is 500 or less, less than 500, 490 or less, 480 or less, 470 or less, 460 or less, 450 or less, 440 or less, 430 or less, 420 or less, 410 or less, 400 or less, with less than 400 being particularly preferred.

[0032] (CaO) CaO is a component that reduces the viscosity of glass. Although it is not necessary to contain CaO, from the viewpoint of reducing the viscosity of glass, the lower limit of the CaO content is preferably 0% or more, greater than 0%, 0.001% or more, 0.005% or more, 0.01% or more, 0.05% or more, 0.1% or more, greater than 0.1%, 0.5% or more, greater than 0.5%, 1% or more, greater than 1%, 1.5% or more, greater than 1.5%, 2% or more, greater than 2%, 2.5% or more, greater than 2.5%, 3% or more, greater than 3%, 3.5% or more, greater than 3.5%, 4% or more, greater than 4%, 4.1% or more, 4.2% or more, 4.3% or more, 4.4% or more, 4.5% or more, greater than 4.5%, and especially 5% or more. On the other hand, if the CaO content is too high, the thermal expansion coefficient α, dielectric constant ε, and dielectric loss tangent tanδ tend to increase. Therefore, the upper limits for the CaO content are preferably 10% or less, 9% or less, 8% or less, 7% or less, 6.6% or less, 6.5% or less, less than 6.5%, 6% or less, less than 6%, 5.9% or less, 5.8% or less, 5.7% or less, 5.6% or less, 5.5% or less, and especially less than 5.5%.

[0033] (SnO ２ ) SnO２ SnO is a component that releases oxygen gas at temperatures above 1500°C due to the change in the valence of Sn in response to the temperature of the glass melt, resulting in a clarifying effect. ２ Because it releases gas at a high temperature, it can be used as a clarifying agent in glass where the content of alkali metal components and alkaline earth metal components in the glass is low, and the viscosity of the glass melt tends to be high. ２ The lower limit of the content is 0% or more, greater than 0%, 0.001% or more, 0.005% or more, 0.01% or more, 0.05% or more, 0.1% or more, 0.11% or more, 0.12% or more, 0.13% or more, 0.14% or more, 0.15% or more, 0.16% or more, 0.17% or more, 0.18% or more, with a particularly preferred amount being greater than 0.18%. On the other hand, SnO ２ If the content is too high, it may cause discoloration of the glass or crystal precipitation. Therefore, SnO ２ The upper limits for the content are 5% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, 0.45% or less, 0.4% or less, 0.35% or less, 0.3% or less, 0.29% or less, 0.28% or less, 0.27% or less, 0.26% or less, 0.25% or less, with less than 0.25% being particularly preferable.

[0034] (SiO ２ / SnO ２ ) SnO ２ When using as a clarifying agent, SnO ２ Considering the balance between suppressing crystal precipitation and the clarification effect, the mass ratio of SiO ２ / SnO ２ It is preferable to control the value of SiO. ２ / SnO ２ If the value is too small, SnO ２ Crystals mainly composed of SiO are more likely to precipitate. Therefore, the mass ratio SiO ２ / SnO ２The lower limit of the value is 10 or more, greater than 10, 11 or more, 12 or more, 13 or more, 14 or more, 15 or more, 16 or more, 17 or more, 18 or more, 19 or more, 20 or more, greater than 20, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 110 or more, 120 or more, 130 or more, 140 or more, 150 or more, 160 or more, 170 or more, 180 or more, 190 or more, 200 or more, 210 or more, 220 or more, 230 or more, 240 or more, and especially greater than 240. On the other hand, the mass ratio SiO ２ / SnO ２ If the value is too large, it becomes difficult to obtain sufficient clarification. Therefore, the mass ratio SiO ２ / SnO ２ The upper limits of the value are 10000 or less, less than 10000, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, less than 5000, 4000 or less, 3000 or less, 2000 or less, 1000 or less, less than 1000, 900 or less, 800 or less, 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, less than 500, 490 or less, 480 or less, 470 or less, 460 or less, 450 or less, less than 450, 440 or less, 430 or less, 420 or less, 410 or less, 400 or less, less than 400, 390 or less, 380 or less, 370 or less, 360 or less, 350 or less, 340 or less, 330 or less, 320 or less, 310 or less, 300 or less, especially less than 300.

[0035] In addition to the above components, the glass fiber composition of this embodiment also contains, for example, Li ２ O, Na ２ O, K ２ O, SrO, BaO, ZnO, P ２ O ５ Fe ２ O ３ , TiO ２ , ZrO ２ It may contain ingredients such as the following.

[0036] (Li ２ O) Li ２O is a component that reduces the viscosity of glass. On the other hand, because the difference in electronegativity between lithium atoms and oxygen atoms is large and polarization is easily achieved, it is a component that easily increases the dielectric constant ε and dielectric loss tangent tanδ of glass. In addition, H contained in water adhering to glass in high temperature and high humidity environments... ＋ Li ＋ It is prone to leaching. Therefore, the adhesion between glass and resin tends to decrease, making it difficult to maintain sufficient strength as a glass fiber composite resin. In addition, there is a risk that raw material costs will rise due to concerns about the supply of raw materials. Therefore, Li ２ It is preferable to keep the O content as low as possible. Therefore, Li ２ The upper limit for the O content is preferably 0.1% or less, less than 0.1%, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, and especially preferably less than 0.05%.

[0037] (Na ２ O) Na ２ O is a component that reduces the viscosity of glass. On the other hand, because the difference in electronegativity between sodium atoms and oxygen atoms is large and polarization is easily achieved, it is a component that easily increases the dielectric constant ε and dielectric loss tangent tanδ of glass. In addition, in high temperature and high humidity environments, H contained in water adhering to glass... ＋ Na ＋ It is prone to leaching. Therefore, the adhesion between the glass and the resin is likely to decrease, making it difficult to maintain sufficient strength as a glass fiber composite resin. Hence, Na ２ It is preferable to keep the O content as low as possible. Therefore, Na ２ The upper limits for the O content are 1% or less, 0.5% or less, 0.1% or less, less than 0.1%, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, and especially less than 0.05%. On the other hand, Na ２ O is present as an impurity in the glass raw material, and Na is derived from the above raw material. ２ Completely removing O may increase manufacturing costs. Therefore, Na is used within a range that does not affect the dielectric constant ε and dielectric loss tangent tanδ of the glass. ２ It may contain oxygen. For example, Na ２The content of O may be 0.001% or more, 0.002% or more, or 0.003% or more.

[0038] (K ２ O) K ２ O is a component that reduces the viscosity of glass. On the other hand, because the difference in electronegativity between potassium atoms and oxygen atoms is large and polarization is easily achieved, it is a component that easily increases the dielectric constant ε and dielectric loss tangent tanδ of glass. In addition, in high temperature and high humidity environments, H contained in water adhering to glass... ＋ K ＋ It is prone to leaching. Therefore, the adhesion between the glass and the resin is likely to decrease, making it difficult to maintain sufficient strength as a glass fiber composite resin. Hence, K ２ It is preferable to keep the O content as low as possible. Therefore, K ２ The upper limit for the O content is 1% or less, 0.5% or less, 0.1% or less, less than 0.1%, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, and especially less than 0.05%. On the other hand, K ２ O is present as an impurity in the glass raw material, and K is derived from the above raw material. ２ Completely removing O may increase manufacturing costs. Therefore, K is used within a range that does not affect the dielectric constant ε and dielectric loss tangent tanδ of the glass. ２ It may contain O. For example, K ２ The content of O may be 0.001% or more, 0.002% or more, or 0.003% or more.

[0039] (Li ２ O + Na ２ O+K ２ O) Li ２ O, Na ２ O and K ２ Alkali metal components such as oxygen tend to increase the dielectric constant ε and dielectric loss tangent tanδ of glass. Furthermore, there is a risk of causing glass erosion due to alkali leaching. Therefore, Li ２ O + Na ２ O+K ２ It is preferable to keep the O content as low as possible. Therefore, Li ２ O + Na ２ O+K ２The upper limits for the O content are 1% or less, 0.5% or less, 0.3% or less, less than 0.3%, 0.2% or less, less than 0.2%, 0.15% or less, less than 0.15%, 0.1% or less, less than 0.1%, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, and especially less than 0.05%. On the other hand, alkali metal components are contained as impurities in the glass raw materials, and if alkali metal components are completely removed from the above raw materials, manufacturing costs may increase. Therefore, alkali metal components may be included in a range that does not affect the dielectric constant ε and dielectric loss tangent tanδ of the glass. For example, Li ２ O + Na ２ O+K ２ The content of O may be 0.001% or more, 0.002% or more, or 0.003% or more.

[0040] (SrO) SrO is a component that reduces the viscosity of glass. On the other hand, Al ２ O ３ In glass compositions containing a large amount of SrO, SrO may promote phase separation and crystal precipitation of the glass. In addition, the thermal expansion coefficient α, dielectric constant ε, and dielectric loss tangent tanδ of the glass tend to increase. Therefore, it is preferable to keep the SrO content as low as possible. Accordingly, the upper limits of the SrO content are preferably 3% or less, 2.8% or less, 2.6% or less, 2.4% or less, 2.2% or less, 2% or less, 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2% or less, 0.1% or less, less than 0.1%, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, and especially less than 0.05%. On the other hand, SrO can be present as an impurity in glass raw materials, and completely removing SrO from the raw materials may increase manufacturing costs. Therefore, SrO may be included in a range that does not affect the dielectric constant ε and dielectric loss tangent tanδ of the glass. For example, the SrO content may be 0.001% or more, 0.002% or more, 0.003% or more, 0.004% or more, or 0.005% or more.

[0041] (BaO) BaO is a component that reduces the viscosity of glass. On the other hand, Al ２ O３ In glass compositions containing a large amount of BaO, BaO may promote phase separation and crystal precipitation of the glass. In addition, the thermal expansion coefficient α, dielectric constant ε, and dielectric loss tangent tanδ of the glass tend to increase. Therefore, it is preferable to keep the BaO content as low as possible. Accordingly, the upper limits of the BaO content are preferably 3% or less, 2.8% or less, 2.6% or less, 2.4% or less, 2.2% or less, 2% or less, 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2% or less, 0.1% or less, less than 0.1%, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, and especially less than 0.05%. On the other hand, BaO can be present as an impurity in glass raw materials, and completely removing BaO from the raw materials may increase manufacturing costs. Therefore, BaO may be included in a range that does not affect the dielectric constant ε and dielectric loss tangent tanδ of the glass. For example, the BaO content may be 0.001% or more, 0.002% or more, 0.003% or more, 0.004% or more, or 0.005% or more.

[0042] (MgO + CaO + SrO + BaO) Alkaline earth metals such as MgO, CaO, SrO, and BaO tend to decrease the viscosity of glass while increasing the dielectric constant ε and dielectric loss tangent tanδ of glass. Therefore, it is preferable to control the content of MgO + CaO + SrO + BaO in consideration of the balance between the viscosity and dielectric properties of the glass. The lower limit of the MgO + CaO + SrO + BaO content is preferably 0% or more, greater than 0%, 0.001% or more, 0.002% or more, 0.003% or more, 0.004% or more, 0.005% or more, 0.01% or more, greater than 0.01%, 0.02% or more, 0.03% or more, 0.04% or more, 0.05% or more, 0.06% or more, 0.07% or more, 0.08% or more, 0.09% or more, with 0.10% or more being particularly preferable. On the other hand, if the MgO + CaO + SrO + BaO content is too high, the dielectric constant ε and dielectric loss tangent tanδ of the glass tend to increase. Therefore, the upper limit of the MgO + CaO + SrO + BaO content is preferably 10% or less, 9% or less, 8% or less, 7% or less, 6.5% or less, 6.4% or less, 6.3% or less, 6.2% or less, 6.1% or less, and especially preferably 6% or less.

[0043] (ZnO) ZnO is a component that reduces the viscosity of glass. On the other hand, Al ２ O ３ In glass compositions containing a large amount of ZnO, ZnO may promote glass layering and crystal precipitation. In addition, the thermal expansion coefficient α, dielectric constant ε, and dielectric loss tangent tanδ of the glass tend to increase. Therefore, it is preferable to keep the ZnO content as low as possible. Accordingly, the upper limits of the ZnO content are preferably 3% or less, 2.8% or less, 2.6% or less, 2.4% or less, 2.2% or less, 2% or less, 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2% or less, 0.1% or less, less than 0.1%, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, and especially less than 0.05%. On the other hand, ZnO can be present as an impurity in glass raw materials, and completely removing ZnO from the raw materials may increase manufacturing costs. Therefore, ZnO may be included in a range that does not affect the dielectric constant ε and dielectric loss tangent tanδ of the glass. For example, the ZnO content may be 0.001% or more, 0.002% or more, 0.003% or more, 0.004% or more, or 0.005% or more.

[0044] (P ２ O ５ ) P ２ O ５ Al ２ O ３ Ya B ２ O ３ Along with it, it is a component that forms the framework of the glass's mesh-like structure. On the other hand, P ２ O ５ Glass containing P is prone to reduced chemical resistance, and in chemical treatment processes such as Cu foil etching, if the chemical solution penetrates the glass from the substrate cross-section, there is a risk of the glass being corroded. Therefore, P ２ O ５ It is preferable to keep the content of as little as possible. Therefore, P ２ O ５The upper limit of the content is preferably 3% or less, less than 3%, 2% or less, 1% or less, less than 1%, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, and especially less than 0.5%. On the other hand, P ２ O ５ P is included as an impurity in the glass raw material, and P is derived from the above raw material. ２ O ５ Completely removing it could increase manufacturing costs. Therefore, to the extent that it does not affect the chemical resistance of the glass, P ２ O ５ It may contain P. ２ O ５ The content may be 0.001% or more, and may exceed 0.001%.

[0045] (LiO ２ +Na ２ O+K ２ O+SrO+BaO+ZnO+P ２ O ５ ) LiO ２ Na ２ O, K ２ O, SrO, BaO, ZnO and P ２ O ５ The presence of these components tends to increase the thermal expansion coefficient α, dielectric constant ε, and dielectric loss tangent tanδ of the glass. Therefore, LiO ２ +Na ２ O+K ２ O+SrO+BaO+ZnO+P ２ O ５ The upper limit of the content is preferably 3% or less, less than 3%, 2% or less, 1% or less, less than 1%, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, and especially less than 0.5%. On the other hand, LiO ２ Na ２ O, K ２ O, SrO, BaO, ZnO and P ２ O ５ These components are present as impurities in the glass raw materials, and completely removing them from the raw materials may increase manufacturing costs. Therefore, these components may be included to the extent that they do not affect the dielectric or chemical properties of the glass. For example, LiO ２ +Na ２ O+K ２O+SrO+BaO+ZnO+P ２ O ５ The content may be 0.002% or more, greater than 0.002%, 0.003% or more, greater than 0.003%, 0.004% or more, greater than 0.004%, or 0.005% or more.

[0046] (Fe ２ O ３ ) Fe ２ O ３ These are components that increase the dielectric constant ε and dielectric loss tangent tanδ of glass. Therefore, Fe ２ O ３ It is preferable to keep the content of as little as possible. Therefore, Fe ２ O ３ The upper limit of the content is preferably 0.1% or less, 0.09% or less, and especially preferably 0.08% or less. On the other hand, Fe ２ O ３ Fe is a component that can be introduced from natural raw materials or melting equipment, and using high-purity raw materials or expensive melting equipment may increase manufacturing costs. Therefore, Fe is used within a range that does not affect the dielectric constant ε and dielectric loss tangent tanδ of the glass. ２ O ３ It may contain, for example, Fe ２ O ３ The content may be 0.001% or more, greater than 0.001%, or 0.005% or more.

[0047] (TiO ２ ) TiO ２ This component reduces the viscosity of glass and improves its chemical resistance. It also easily increases the dielectric constant ε, while making it difficult to increase the dielectric loss tangent tanδ. (TiO) ２ If the content of TiO is too high, the liquidus temperature Ty of the glass will rise, potentially causing crystals to precipitate in the glass and reducing productivity. In addition, the dielectric constant ε of the glass will tend to increase. Therefore, TiO ２ The upper limits of the content are less than 2%, 1.5% or less, less than 1.5%, 1% or less, less than 1%, 0.5% or less, less than 0.5%, 0.49% or less, 0.4% or less, 0.3% or less, less than 0.3%, 0.2% or less, less than 0.2%, 0.1% or less, 0.08% or less, 0.06% or less, and especially preferably 0.05% or less. On the other hand, TiO ２It may be present as an impurity in the natural raw materials, and TiO ２ If TiO is completely removed, manufacturing costs may increase. Therefore, TiO is used within a range that does not affect the liquidus temperature Ty or dielectric constant ε of the glass. ２ It may contain TiO. ２ The content may be 0.001% or more, and may exceed 0.001%.

[0048] (ZrO ２ ) ZrO ２ It is a component that suppresses crystal precipitation in glass even in small amounts. On the other hand, ZrO ２ If it contains an excess of ZrO, the viscosity of the glass increases, and in addition, it becomes easier to promote phase separation of the glass. Therefore, ZrO ２ The upper limits for the content are 1.5% or less, 1.3% or less, 1% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2% or less, 0.1% or less, 0.08% or less, 0.06% or less, 0.04% or less, 0.02% or less, 0.01% or less, and especially less than 0.01%. On the other hand, ZrO ２ ZrO is a component that can be mixed in from the refractory material provided in the glass melting furnace, and as mentioned above, it is also a component that suppresses crystal precipitation in glass even in small amounts. Therefore, ZrO is present in amounts that do not affect the properties of the glass. ２ It may contain the following. For example, the ZrO2 content may be 0.0001% or more.

[0049] (MoO ３ , Cr ２ O ３ (Pt, Rh, etc.) Note that the glass fiber composition of this embodiment contains components that leach from melting equipment, etc., such as MoO ３ , Cr ２ O ３ It may contain Pt, Rh, etc. From the viewpoint of not adversely affecting the properties of the glass, the upper limits of the content of each are preferably 0.1% or less, 0.08% or less, 0.06% or less, 0.04% or less, 0.02% or less, 0.01% or less, and especially preferably less than 0.01%.

[0050] (Cl ２ Sb ２ O ３ As２ O ３ , CEO ２ (etc.) Also, for the purpose of improving the clarity or reducing the viscosity of the glass melt, Cl ２ Sb ２ O ３ As ２ O ３ , CEO ２ The following components may be included. From the viewpoint of preventing the generation of reboil foam, reducing environmental impact, and suppressing corrosion of equipment, the upper limits of the respective content are preferably 0.5% or less, 0.3% or less, 0.2% or less, 0.1% or less, 0.05% or less, 0.03% or less, and especially preferably 0.01% or less.

[0051] (F ２ ) Here, with the aim of improving the clarity or reducing the viscosity of the glass melt, F ２ While it is possible to use F, from the perspective of reducing the chemical resistance of glass, erosion of melting equipment, and environmental impact, ２ It is preferable to avoid containing as much as possible. Therefore, F ２ The upper limit of the content is less than 0.5%, 0.4% or less, 0.3% or less, 0.2% or less, 0.1% or less, 0.08% or less, 0.06% or less, 0.04% or less, 0.02% or less, 0.01% or less, and preferably less than 0.01%.

[0052] The glass composition described above can be measured, for example, by known X-ray fluorescence analysis (XRF).

[0053] As described above, the glass composition of the glass fiber composition of this embodiment has been explained, but the following [Composition 1] to [Composition 3] are examples of preferred glass compositions of the glass fiber composition of this embodiment.

[0054] [Composition 1] The glass composition is SiO2 by mass%. ２ 50-70% Al ２ O ３ 0-25% B ２ O ３ 10-35% MgO 0-6% CaO 0-8% SnO ２ 0-2%

[0055] [Composition 2] The glass composition is SiO2 by mass%.２ 50-70% Al ２ O ３ 0-25% B ２ O ３ 10-35% MgO 0-6% CaO 0-8% SnO ２ 0% to 2% Li ２ O 0-0.05% P ２ O ５ 0-3% F ２ 0-0.4%

[0056] [Composition 3] SiO ２ 50-70% Al ２ O ３ 0-25% B ２ O ３ MgO: Over 25% to less than 30%; CaO: 0-6%; SnO: 4-8% ２ 0% to 2% Li ２ O 0-0.05% P ２ O ５ 0-3% TiO ２ 0-0.5% F ２ 0-0.1%

[0057] The properties of the glass fiber composition and glass fibers of this embodiment, as well as the method for manufacturing glass fibers, will be described below.

[0058] The glass fiber composition of this embodiment preferably has a dielectric constant ε of 6 or less, 5.5 or less, 5 or less, 4.7 or less, 4.6 or less, and particularly 4.5 or less at 25°C and 10GHz. If the dielectric constant ε is too high, the dielectric loss will be large, and it will not be able to meet the low dielectric properties required for resin reinforcing materials such as printed circuit boards and communication equipment components. The lower limit of the dielectric constant ε at 25°C and 10GHz is not particularly limited, but in reality it is 3.7 or higher.

[0059] The glass fiber composition of this embodiment preferably has a dielectric constant ε of 6 or less, 5.5 or less, 5 or less, 4.7 or less, 4.6 or less, and particularly 4.5 or less at 25°C and 40GHz. If the dielectric constant ε is too high, the dielectric loss will be large, and it will not be able to meet the low dielectric properties required for resin reinforcing materials such as printed circuit boards and communication equipment components. The lower limit of the dielectric constant ε at 25°C and 40GHz is not particularly limited, but in reality it is 3.7 or higher.

[0060] The glass fiber composition of this embodiment preferably has a dielectric loss tangent tanδ of 0.0080 or less, 0.0070 or less, 0.0060 or less, 0.0050 or less, 0.0040 or less, 0.0035 or less, 0.0030 or less, 0.0028 or less, 0.0026 or less, 0.0024 or less, and particularly preferably 0.0022 or less at 25°C and 10GHz. If the dielectric loss tangent tanδ is too high, the dielectric loss will increase, and the low dielectric properties required for resin reinforcing materials such as printed circuit boards and communication equipment components will not be met. The lower limit of the dielectric loss tangent tanδ at 25°C and 10GHz is not particularly limited, but in reality it is 0.0001 or more.

[0061] The glass fiber composition of this embodiment preferably has a dielectric loss tangent tanδ of 0.0100 or less, 0.0090 or less, 0.0080 or less, 0.0070 or less, 0.0060 or less, 0.0050 or less, 0.0040 or less, 0.0035 or less, and particularly preferably 0.0030 or less at 25°C and 40GHz. If the dielectric loss tangent tanδ is too high, the dielectric loss will increase, and the low dielectric properties required for resin reinforcing materials such as printed circuit boards and communication equipment components will not be met. The lower limit of the dielectric loss tangent tanδ at 25°C and 40GHz is not particularly limited, but in reality it is 0.0001 or more.

[0062] The glass fiber composition of this embodiment has a thermal expansion coefficient α of 3 × 10 at 50 to 200°C. －７ / ℃ or higher, 5 x 10 －７ / ℃ or higher, 8 x 10 －７ / ℃ or higher, 10 x 10 －７ / ℃ or higher, 15 x 10 －７ / ℃ or higher, 17 x 10 －７ / ℃ or higher, 19 x 10 －７ / ℃ or higher, especially 20 x 10 －７ A temperature of 1 / °C or higher is preferable. If the coefficient of thermal expansion α is too low, the difference in thermal expansion between the glass fibers and the resin in the glass fiber reinforced resin will be large, which may cause damage to the glass fiber reinforced resin. On the other hand, the glass fiber composition of this embodiment has a coefficient of thermal expansion α of 40 × 10 at 50 to 200°C. －７ / ℃ or below, 39 x 10 －７ / ℃ or below, 38 x 10 －７ / ℃ or below, 37 × 10 －７ / ℃ or lower, especially 36 × 10 －７ A temperature of / °C or lower is preferable. If the coefficient of thermal expansion α is too high, for example, when heat treatment is performed on a laminate of a printed circuit board, the upper and lower boards may shift due to thermal expansion and contraction, which may cause interference with signal transmission.

[0063] The glass fiber composition of this embodiment has a product of the thermal expansion coefficient α at 50 to 200°C and the dielectric loss tangent tanδ at 10 GHz (hereinafter sometimes referred to as α × tanδ) of 0.0009 × 10 －７ / ℃ or higher, 0.0010 × 10 －７ / ℃ or higher, 0.0015 × 10 －７ / ℃ or higher, 0.0020 × 10 －７ / ℃ or higher, 0.0050 × 10 －７ / ℃ or higher, 0.0080 × 10 －７ / ℃ or higher, 0.0100 × 10 －７ / ℃ or higher, 0.0150 × 10 －７ / ℃ or higher, 0.0200 × 10 －７ / ℃ or higher, 0.0250 × 10 －７ / ℃ or higher, 0.0300 × 10 －７ / ℃ or higher, 0.0350 × 10 －７ / ℃ or higher, 0.0400 × 10 －７ / ℃ or higher, especially 0.0450 × 10 －７ A temperature of 0.1000 × 10°C or higher is preferable. If α × tanδ is too low, when the glass fiber reinforced resin laminate is heat-treated, there is a risk of damage to the resin composite due to heat. On the other hand, the glass fiber composition of this embodiment has an α × tanδ of 0.1000 × 10°C. －７ / ℃ or lower, 0.0950 × 10 －７ / ℃ or lower, 0.0900 × 10 －７ / ℃ or lower, 0.0850 × 10 －７ / ℃ or less, 0.0800 × 10 －７ / ℃ or lower, 0.0750 × 10 －７ / ℃ or less, 0.0700 × 10 －７ / ℃ or lower, especially 0.0650 × 10 －７ A temperature of / °C or lower is preferable. If α × tanδ is too high, the values ​​of either the thermal expansion coefficient α or the dielectric loss tangent tanδ, or both, become large, and the low dielectric properties required for resin reinforcing materials such as printed circuit boards and communication equipment components will not be met.

[0064] The glass fiber composition of this embodiment has a density ρ of 2.5 g / cm³. ３ Below, 2.4g / cm ３ The following is particularly true for 2.36 g / cm³. ３ The following is preferable. If the density ρ is too high, the glass fiber reinforced resin becomes heavy, making weight reduction difficult, for example, when the number of layers of printed circuit boards increases. Although there is no particular lower limit to the density ρ, in practice, it is 2 g / cm³. ３ That's all.

[0065] The glass fiber composition of this embodiment preferably has a spinning temperature Tx of 1500°C or less, 1490°C or less, 1480°C or less, 1470°C or less, 1460°C or less, 1450°C or less, and particularly 1440°C or less. If the spinning temperature Tx is too high, the fiberization equipment such as bushings will be severely damaged, increasing the frequency of replacement and raising manufacturing costs. In addition, precious metal elements will leach from the fiberization equipment into the glass, causing phase separation and a decrease in chemical resistance of the glass. The lower limit of the spinning temperature Tx is not particularly limited, but in reality it is 1000°C or higher. As previously described, the spinning temperature Tx is the temperature at which the viscosity of the glass is 10 ３．０ This refers to temperature in dPa·s.

[0066] The glass fiber composition of this embodiment preferably has a liquidus temperature Ty of 1450°C or less, 1440°C or less, 1430°C or less, 1420°C or less, 1410°C or less, 1400°C or less, 1390°C or less, 1380°C or less, 1370°C or less, 1360°C or less, 1350°C or less, 1340°C or less, 1330°C or less, and particularly preferably 1320°C or less. If the liquidus temperature Ty is too high, the temperature difference ΔTxy between the spinning temperature Tx and the liquidus temperature Ty tends to become small, which tends to worsen productivity. The lower limit of the liquidus temperature Ty is not particularly limited, but in reality it is 900°C or higher.

[0067] In this embodiment, the glass fiber composition preferably has a temperature difference ΔTxy between the spinning temperature Tx and the liquidus temperature Ty of 20°C or more, 25°C or more, 30°C or more, 35°C or more, 40°C or more, 45°C or more, 50°C or more, 60°C or more, 70°C or more, 80°C or more, 90°C or more, 100°C or more, 110°C or more, 120°C or more, 150°C or more, 200°C or more, 250°C or more, and particularly preferably 300°C or more. If the temperature difference ΔTxy is too small, devitrified substances that cause nozzle clogging of the bushing are more likely to occur during glass fiber molding, which tends to worsen productivity. There is no particular upper limit to the temperature difference ΔTxy, but in reality it is 600°C or less.

[0068] The glass fiber composition of this embodiment preferably has a Young's modulus E of 30 GPa or more, 35 GPa or more, 40 GPa or more, 45 GPa or more, and particularly 50 GPa or more. If the Young's modulus E is too low, for example, it becomes difficult to obtain the effect of using it as a reinforcing material in printed circuit boards and the like, as well as the effect of suppressing thermal shrinkage and warping. On the other hand, the glass fiber composition of this embodiment preferably has a Young's modulus E of 90 GPa or less, and particularly 85 GPa or less. If the Young's modulus E is too high, for example, the drill bit used to drill holes in printed circuit boards and the like may be easily damaged, which may worsen productivity.

[0069] The glass fiber composition of this embodiment preferably has a weight loss rate of 60% or less, 59% or less, 58% or less, 57% or less, and particularly 56% or less after immersion in a 10% hydrochloric acid solution at 80°C for 90 hours. If the weight loss rate is too high, there is a risk that the glass fibers may be eroded, for example, during the etching process for glass fiber reinforced resin such as printed circuit boards. The lower limit of the weight loss rate is not particularly limited, but in reality it is 0.1% or more.

[0070] The glass fiber composition of this embodiment preferably has a weight loss rate of 60% or less, 59% or less, 58% or less, 57% or less, and particularly 56% or less after immersion in a 10% by mass sodium hydroxide solution at 80°C for 16 hours. If the weight loss rate is too high, there is a risk that the glass fibers may be eroded, for example, during the etching process for glass fiber reinforced resin such as printed circuit boards. The lower limit of the weight loss rate is not particularly limited, but in reality it is 0.1% or more.

[0071] The glass fiber composition of this embodiment preferably has a β-OH value of 0.3 / mm or more, 0.33 / mm or more, and particularly 0.35 / mm or more. If the β-OH value is too low, it becomes necessary to precisely control the molten atmosphere of the glass in order to reduce the moisture content in the glass, which may increase manufacturing costs. On the other hand, the glass fiber composition of this embodiment preferably has a β-OH value of 0.8 / mm or less, 0.75 / mm or less, and particularly 0.7 / mm or less. If the β-OH value is too high, the network in the glass structure is broken, causing local polarization, and the dielectric constant ε and dielectric loss tangent tanδ of the glass tend to increase.

[0072] Here, the β-OH value is an indicator of the amount of water contained in the glass and is calculated by the following [Equation 1]. [Equation 1] β-OH = (1 / t) × log10(T1 / T2) β-OH: Water content ( / mm) t: Glass thickness (mm) T1: Reference wavelength 3846 cm －１ Transmittance (%) at 2600 nm T2: Hydroxyl absorption wavelength 3600 cm －１ Transmittance (%) at 2800 nm

[0073] The glass fibers of this embodiment include glass made from the glass fiber composition described above.

[0074] The glass fibers of this embodiment preferably contain 95% or more of glass made from the glass fiber composition described above. If the glass fibers of this embodiment consist of 95% or more glass made from the glass fiber composition described above, and the remainder is organic matter such as a coating material, then scratches are less likely to occur on the glass fiber surface during various processing steps such as the glass fiber weaving process, and stable strength performance can be maintained. In addition, the glass fibers will be able to fully exhibit various physicochemical properties. The content of glass made from the glass fiber composition in the glass fibers of this embodiment is preferably 95% or more, 95.5% or more, 96% or more, 96.5% or more, 97% or more, particularly 97.5% or more, and 100% or less, less than 100%, particularly 99.9% or less, on a solid content basis. Here, the solid content basis is calculated by measuring the mass in a dry state where the moisture content of the glass surface is less than 0.1%, then heat-treating it at a high temperature to remove the organic matter coated on the glass fiber surface by heating, measuring the mass, and calculating from the ratio of the two obtained masses.

[0075] Furthermore, in this embodiment, if the glass fiber composition contains less than 95% solids, the protective performance of the organic material applied to the surface of the glass fiber will not be significantly improved, and the amount of organic material required for application will increase, thus raising manufacturing costs. Also, if the glass fiber composition contains more than 99.9% solids, the protective function of the glass fiber surface may not be fully realized.

[0076] In this embodiment, it is preferable that the coating on the surface of the glass fibers is 0.1% or more of the total amount of glass fibers. If the amount of coating is too small, the protective function of the glass fibers may not be fully exhibited. On the other hand, in this embodiment, it is preferable that the coating on the surface of the glass fibers is less than 2.5% of the total amount of glass fibers. If the amount of coating is too large, the amount of organic matter used in the coating increases, which raises the manufacturing cost. Examples of components that can be used in the coating include starch, polyurethane resin, epoxy resin, vinyl acetate resin, acid copolymer, acrylic resin, modified polypropylene resin, carboxylic acid, polycarboxylic acid, polyester resin, antistatic agent, surfactant, antioxidant, antifungal agent, silane coupling agent, or lubricant.

[0077] Examples of the silane coupling agents mentioned above include γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, epoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and vinyltriethoxysilane. Depending on the type of resin to be compounded, these may be used individually or in combination of two or more types.

[0078] Examples of the above-mentioned surfactants include ethylene oxide propylene oxide alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene-block copolymer, alkyl polyoxyethylene-polyoxypropylene-block copolymer ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid monoester, polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester ethylene oxide adduct, polyoxyethylene castor oil ether, hydrogenated castor oil ethylene oxide adduct, alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, and sucrose fat. Nonionic surfactants such as acid esters, polyhydric alcohol alkyl ethers, fatty acid alkanolamides, acetylene glycol, acetylene alcohol, ethylene oxide adducts of acetylene glycol, and ethylene oxide adducts of acetylene alcohol; cationic surfactants; anionic surfactants such as higher alcohol sulfate salts, higher alkyl ether sulfate salts, α-olefin sulfate salts, alkylbenzene sulfonates, α-olefin sulfonates, reaction products of fatty acid halides and N-methyl taurine, dialkyl sulfosuccinate salts, higher alcohol phosphate salts, and phosphate salts of higher alcohol ethylene oxide adducts; and amphoteric surfactants such as amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants can be used, and these may be used alone or in combination of two or more types.

[0079] Examples of the above-mentioned lubricants include modified silicone oil, animal oil and its hydrogenated counterparts, vegetable oils such as soybean oil, rapeseed oil, coconut oil, palm oil, and peanut oil and their hydrogenated counterparts, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, triacylglycerols, paraffins, polyethyleneimines, polyalkylpolyamine alkylamide derivatives, fatty acid amides such as dehydrated condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid, and quaternary ammonium salts such as alkyltrimethylammonium salts such as lauryltrimethylammonium chloride. These may be used individually or in combination of two or more types.

[0080] The glass fibers of the present invention can be used in mixture with fibers other than those in this embodiment, as long as it does not hinder the objectives of the present invention. Examples of fibers other than those in this embodiment include glass fibers such as E glass fibers and S glass fibers, and fibers other than glass fibers such as carbon fibers and metal fibers.

[0081] The glass fibers in this embodiment preferably have a diameter of 3 to 20 μm, and more preferably 3 to 10 μm. Within this range, the effect as a resin reinforcing material can be suitably exhibited.

[0082] In this embodiment, the glass fiber is preferably in the form of glass yarn, glass cloth for resin reinforcement, glass chopped strand, or glass chopped strand mat.

[0083] The glass yarn of this embodiment is obtained by bundling and twisting multiple glass fibers of this embodiment. The glass yarn preferably contains 30 to 400 glass fibers and preferably has a twist of 0 to 1 turn / 25 mm. It is also preferably a yarn count of 0.9 to 69 tex.

[0084] The glass cloth of this embodiment is a woven fabric containing the glass fibers of this embodiment. Preferably, the warp thread density of the glass cloth is 40 to 120 threads / 25 mm, and the weft thread density is 40 to 120 threads / 25 mm.

[0085] The glass chopped strand of this embodiment is obtained by bundling multiple glass fibers of this embodiment together and cutting them to a predetermined length. The glass chopped strand preferably contains 30 to 400 glass fibers and has a length of 1 to 150 mm.

[0086] The glass chopped strand mat of this embodiment is made by depositing multiple glass chopped strands of this embodiment in an unoriented manner and bonding them together with resin. The glass chopped strand mat has a basis weight of 40 g / m². ２ ~200g / m ２ It is preferable that this be the case.

[0087] Furthermore, the glass fiber reinforced product of this embodiment preferably contains the glass fibers of this embodiment. Examples of glass fiber reinforced products include electronic components such as printed circuit boards, electrical equipment housings, vehicle exterior components, vehicle engine components, muffler-related components, high-pressure tanks, and communication signal transmission media.

[0088] The printed circuit board of this embodiment is an electronic circuit board comprising the glass cloth of this embodiment and a thermoplastic resin. Preferably, the mass of the glass cloth in the printed circuit board is 10 to 90% of the total mass of the printed circuit board.

[0089] The thermoplastic resins mentioned above include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycarbonate, polyarylene sulfide, and polysulfone. Examples include polyethersulfone (PES), polyphenylsulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryl ether ketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), polyetherether ketone, polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate (PEN), ethylene / vinyl acetate (EVA) resin, ionomer (IO) resin, polybutadiene, styrene / butadiene resin, polybutylene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, etc., and these may be used individually or in combination of two or more types.

[0090] Furthermore, the glass fibers of this embodiment can also be used in forms other than those described above, such as glass chopped strands, glass fillers, continuous strand mats, knitted fabrics, glass rovings, and milled fibers, by being mixed with thermoplastic resins or thermosetting resins.

[0091] Examples of the thermosetting resins mentioned above include unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic (PF) resins, urethane (PU) resins, polyisocyanates, polyisocyanurates, polyimide (PI), urea (UF) resins, silicone (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismalade triazine (BT) resins, diallyl phthalate (PDAP) resins, and others. These may be used individually or in combination of two or more types.

[0092] The glass fiber reinforced resin, which is a combination of the above-mentioned thermoplastic resin or thermosetting resin and glass fibers, can be molded using known molding methods such as injection molding, injection compression molding, two-color molding, hollow molding, foam molding (including supercritical fluid), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, stamping molding, infusion, hand lay-up, spray-up, resin transfer molding, sheet molding compound, bulk molding compound, pultrusion, and filament winding.

[0093] Next, the method for manufacturing glass fibers according to this embodiment will be described. In the following description, the direct melt method (DM method) and the marble melt method (MM method) will be described as examples, but the invention is not limited to these.

[0094] The method for producing glass fibers according to this embodiment comprises the steps of: preparing a batch of glass raw materials so as to yield the above-mentioned glass fiber composition; melting the batch of glass raw materials to obtain molten glass; and forming the molten glass into fibers.

[0095] In the process of preparing a batch of glass raw materials to obtain the above-mentioned glass fiber composition, various glass raw materials are weighed and blended to achieve the above-mentioned composition and properties. The composition and properties are as described and will not be explained here. In addition, cullet may be used in part or all of the glass raw materials.

[0096] In the process of melting a batch of glass raw materials to obtain molten glass, the mixed batch of glass raw materials is placed in a glass melting furnace, and the batch of glass raw materials is melted, and the molten glass is homogenized and clarified in an appropriate temperature and atmosphere.

[0097] In the process of forming molten glass into fibers, glass fibers are obtained by continuously drawing the molten glass from a bushing and forming it into fibers (DM method). Alternatively, glass fibers are obtained by first forming the molten glass into a marbled shape, and then remelting the molten glass and drawing it from a bushing and forming it into fibers (MM method).

[0098] The glass fibers formed in this manner according to this embodiment can be processed into, for example, glass chopped strands, glass chopped strand mats, glass yarn, glass cloth, or composite materials combined with resin, etc., and used for various applications.

[0099] The present invention will be described in detail below based on the following examples. Note that the following examples are merely illustrative, and the present invention is not limited in any way to these embodiments.

[0100] Tables 1 to 11 show examples of the present invention (samples No. 1 to 50) and comparative examples (samples No. 51 and 52).

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] Each sample was prepared as follows:

[0113] First, various glass raw materials were weighed and mixed in predetermined amounts using arbitrary natural and / or chemical raw materials to achieve the glass composition shown in the table, thereby preparing glass raw material batches. Next, these glass raw material batches were placed in a 300cc platinum-rhodium crucible and left to stand in an indirectly heated electric furnace. Heating and melting was carried out at 1550°C in an atmospheric environment for 20 hours. In order to ensure that the molten glass was homogeneous, the molten glass was stirred twice during the heating and melting process using a heat-resistant stirring rod. After the second stirring, the temperature was raised to 1650°C and held for 4 hours.

[0114] The obtained molten glass was poured into a carbon mold to form an ingot measuring 60 mm (width) x 170 mm (length) x 15 mm (wall thickness). The formed ingot was held at a constant temperature of 650°C to 750°C for 30 minutes, then cooled to approximately 450°C to 550°C at a rate of 3°C / min, and then cooled to room temperature at a rate of 10°C / min.

[0115] The properties of the obtained glass were measured as follows.

[0116] The transparency of the glass sample was evaluated by observing an arbitrary character through the free surface of a 15 mm thick glass ingot and determining whether the character was visible or not. Here, ○ was used if the character was clearly visible, △ if the character was visible but not, and × if the character was not visible.

[0117] The dielectric constant ε and dielectric loss tangent tanδ of glass at frequencies of 10 GHz and 40 GHz were measured by cutting a 50 mm (width) x 50 mm (length) x 0.15 mm (thickness) glass sample from a molded glass ingot, polishing both sides to a mirror finish, and then measuring at 25°C using the split cylinder method with a 10 GHz or 40 GHz resonator and vector analyzer.

[0118] The thermal expansion coefficient α between 50 and 200°C was measured by cutting a glass sample of appropriate dimensions from a molded glass ingot, processing it into a cylindrical shape of 5 mmφ (diameter) x 20 mm (length), and then heating the cylindrical glass sample from 30°C to the bending point Tf. During this measurement process, the glass transition temperature Tg and bending point Tf were also measured.

[0119] α × tanδ was calculated by multiplying the measured thermal expansion coefficient α at 50–200°C by the dielectric loss tangent tanδ at 25°C and 10 GHz.

[0120] The density ρ was measured by the Archimedes method after cutting approximately 10 g of glass sample from a molded glass ingot.

[0121] The viscosity of the glass is 10 ２．０ Temperature at dPa·s (hereinafter, T(10) ２．０ ) and 10 ２．５ Temperature at dPa·s (hereinafter, T(10) ２．５ ) and 10 ４．０ Temperature at dPa·s (hereinafter, T(10) ４．０ The spinning temperature Tx was measured by crushing a portion of the molded glass ingot, placing it in a platinum crucible and reheating it to a molten state, and then pulling out the platinum ball. As previously mentioned, the spinning temperature Tx was measured when the viscosity of the glass was 10 ３．０ This refers to temperature in dPa·s.

[0122] The liquidus temperature Ty was determined by the following procedure. After crushing a portion of the molded glass ingot, the glass powder was passed through a 500 μm sieve and deposited on a 300 μm sieve. This glass powder was then packed into a platinum container measuring 10 mm (width) x 120 mm (length) x 20 mm (depth). The container was then placed in an indirect heating temperature gradient furnace with a maximum temperature set to 1470 °C and subjected to a heat treatment for 16 hours under atmospheric conditions. After that, the glass sample was removed from the platinum container and slowly cooled to room temperature. The interfaces of the glass sample (glass-platinum interface, glass-air interface) and the bottom surface were then mirror-polished. The polished surface of the glass sample was observed using a polarizing microscope to identify the crystal deposition locations. The temperature corresponding to the crystal deposition locations was calculated from the temperature gradient of the temperature gradient furnace and defined as the liquidus temperature Ty.

[0123] The temperature difference ΔTxy between the spinning temperature Tx and the liquidus temperature Ty was calculated as spinning temperature Tx - liquidus temperature Ty.

[0124] The Young's modulus E was measured at 25°C using a free-resonance elastic modulus measuring device (JE-RT3, manufactured by Nippon Techno Plus Co., Ltd.) after cutting a glass sample measuring 20 mm (width) x 40 mm (length) x 2 mm (thickness) from a molded ingot, polishing both main surfaces with a polishing solution of 1200-grit alumina powder dispersed in water, and then cutting the sample.

[0125] Acid and alkali resistance tests were conducted according to the following procedure. A portion of the molded glass ingot was crushed, passed through a sieve with a mesh size of 500 μm, and the glass powder deposited on a sieve with a mesh size of 300 μm was washed with deionized water and dried. A certain weight (W1) of the obtained glass powder was taken out and transferred to a 100 mL chemical-resistant container. A 10% by mass hydrochloric acid solution or a 10% by mass sodium hydroxide solution was added to this chemical-resistant container, and the mixture was shaken in an 80°C high-temperature water bath at 50 rpm. The shaking of the glass powder was carried out for 90 hours in the acid resistance test and for 16 hours in the alkali resistance test. After drying the glass powder after shaking, its weight was measured (W2), and the weight loss rate was calculated using the following [Equation 2]. [Equation 2] Weight loss rate = ((W1 - W2) / W1) × 100 (%) W1: Weight of glass powder transferred to a chemical-resistant container (g) W2: Weight of glass powder dried after shaking (g)

[0126] The β-OH value was measured using the following procedure. A glass sample measuring 20 mm (width) x 30 mm (length) x 1 mm (thickness) was cut from a molded glass ingot, and both main surfaces were polished to a mirror finish. The transmittance of the glass sample was measured using FT-IR, and the β-OH value was calculated using the obtained measurement value and the above-mentioned [Equation 1].

[0127] As is clear from Tables 1 to 10, samples No. 1 to 50, which are examples that satisfy the glass composition of the present invention, all possessed the required transparency and exhibited low dielectric properties, with a dielectric constant ε of 4.6 or less and a dielectric loss tangent tanδ of 0.0037 or less at 25°C, 10 GHz, or 40 GHz. Furthermore, all samples had a thermal expansion coefficient α of 35.9 × 10⁻¹⁰ at 50 to 200°C.－７ It exhibited sufficient strength and suitable thermal properties as a reinforcing material for resins, with a Young's modulus E of 51.6 GPa or higher at temperatures below / °C. In addition, in chemical resistance tests using hydrochloric acid solution and sodium hydroxide solution, the weight loss rate was 48.1% or less in both cases, demonstrating chemical resistance that can withstand plating and etching processes.

[0128] Next, we will explain examples of glass fiber fabrication.

[0129] After melting glass fiber compositions having the glass composition of sample Nos. 1, 40, 45, and 50 in the example, multiple glass monofilaments with diameters of 3 μm, 4 μm, 4.5 μm, and 5 μm were continuously molded using a bushing device with a platinum nozzle. Regardless of the diameter of the glass monofilament, no thread breakage occurred during molding, and glass fibers with stable fiber diameters were obtained.

[0130] As described above, the glass fibers and glass fiber-reinforced resins using the glass fiber composition of the present invention exhibit excellent performance and can be applied to all fields of industry.

[0131] Glass fibers produced using the glass fiber composition of the present invention can be used as reinforcing fibers for printed circuit boards and glass fiber reinforced resins in the casings and components of portable electronic devices such as smartphones, tablets, laptops, portable music players, and portable games, as well as in communication components used in the millimeter-wave band, such as in-vehicle millimeter-wave radar, vehicle exterior components, vehicle interior components, vehicle engine components, electronic device casings, and electronic components. Furthermore, the glass composition of the glass fiber composition of the present invention can also be used as the composition of glass used in applications such as glass substrates, glass tubes, and glass containers.

Claims

1. As a glass composition, SiO is present in mass%. ２ 45-70%, Al ２ O ３ 0-40%, B ２ O ３ 5-40%, CaO 0-10%, MgO 0-10%, SnO ２ A composition for glass fibers characterized by containing 0-5%.

2. In terms of mass%, SiO ２ + B ２ O ３ The glass fiber composition according to claim 1, containing 50 to 90%.

3. TiO ２ A glass fiber composition according to claim 1 or 2, containing 0 to less than 2%.

4. Mass ratio SiO ２ / SnO ２ The glass fiber composition according to claim 1 or 2, wherein the value of is 10 to 10000.

5. Mass ratio Al ２ O ３ The glass fiber composition according to claim 1 or 2, wherein the value of / MgO is 10 to 500.

6. Li (in mass %) ２ O + Na ２ O+K ２ O+SrO+BaO+ZnO+P ２ O ５ A glass fiber composition according to claim 1 or 2, containing 0.002 to 3%.

7. The glass fiber composition according to claim 1 or 2, wherein the dielectric constant ε at 25°C and 10 GHz is 6 or less and the dielectric loss tangent tanδ is 0.0080 or less.

8. The glass fiber composition according to claim 1 or 2, wherein the dielectric constant ε at 25°C and 40 GHz is 6 or less, and the dielectric loss tangent tanδ is 0.0100 or less.

9. The glass fiber composition according to claim 1 or 2, wherein the spinning temperature Tx is 1500°C or less.

10. The glass fiber composition according to claim 1 or 2, wherein the Young's modulus E at 25°C is 30 GPa or more.

11. The coefficient of thermal expansion α at 50-200°C is 40 × 10⁻⁶. －７ The glass fiber composition according to claim 1 or 2, wherein the temperature is less than or equal to / ℃.

12. Glass fiber comprising glass made from the glass fiber composition according to claim 1 or 2.

13. A glass fiber reinforced product containing glass fibers as described in claim 12.

14. A method for producing glass fibers, comprising the steps of: preparing a batch of glass raw materials so as to obtain the glass fiber composition described in claim 1 or 2; melting the batch of glass raw materials to obtain molten glass; and forming the molten glass into fibers.

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