Glass compositions for glass fibers, glass fibers, glass fiber fabrics, and glass fiber reinforced resin compositions

Abstract

To provide a glass composition that can obtain glass fibers having excellent water resistance and dielectric properties and has a sufficient working temperature range. [Solution] Contains 59.00 to 65.00 mass% SiO2, 16.00 to 26.00 mass% B2O3, 7.00 to 14.00 mass% Al2O3, 0 to 5.00 mass% CaO, 0 to 4.00 mass% MgO, 0 to 6.00 mass% SrO, 0.10 to 5.00 mass% TiO2, 0 to 2.00 mass% F2 and Cl2 in total, less than 0.20 mass% P2O5, and less than 1.00 mass% Na2O, K2O, and Li2O in total.

Description

[Technical Field]

[0001] This invention relates to glass compositions for glass fibers, glass fibers, glass fiber fabrics, and glass fiber reinforced resin compositions. [Background technology]

[0002] Glass fibers are manufactured by melting glass raw materials, which have been prepared to form a glass fiber composition having a desired composition, in a glass melting furnace to form molten glass (molten glass composition for glass fibers), extruding the molten glass from a container (bushing) having a nozzle plate with several to several thousand nozzle tips, and cooling and solidifying it into fibers while being stretched by winding it at high speed (hereinafter, this operation may be referred to as "spinning"). The bushing is made of a precious metal such as platinum, for example.

[0003] Conventionally, glass fibers have been widely used in various applications to improve the strength of resin molded products, which are used in the casings or components of electronic devices such as servers, smartphones, and laptop computers.

[0004] Generally, glass absorbs energy as heat in response to alternating current, so when the aforementioned resin molded product is used as a housing or component of the electronic device, there is a problem that the resin molded product generates heat.

[0005] Here, the dielectric loss energy absorbed by the glass is proportional to the dielectric constant and dielectric loss tangent, which are determined by the composition and structure of the glass, and is expressed by the following equation (A). W=kfv 2 ×ε 1 / 2 ×tanδ ···(A)

[0006] Here, W is the dielectric loss energy, k is a constant, f is the frequency, and v 2ε represents the potential gradient, ε represents the dielectric constant, and tanδ represents the dielectric loss tangent. From equation (A) above, it can be seen that the larger the dielectric constant and dielectric loss tangent, and the higher the frequency, the greater the dielectric loss and the greater the heat generated by the resin molded product.

[0007] In recent years, due to the increasing frequency of the alternating current used in the aforementioned electronic devices (f in equation (A) above), there is a need for glass fibers used in the housing or components of such electronic devices to have lower dielectric constants and lower dielectric loss tangents in order to reduce dielectric loss energy. In particular, a low dielectric loss tangent is required because it has a greater impact on equation (A) than the dielectric constant which is raised to the power of 1 / 2.

[0008] In view of these circumstances, the applicant has proposed a glass composition for glass fibers that has a low dielectric constant and low dielectric loss tangent, suppresses the generation of phase separation, and further reduces viscosity at high temperatures, comprising, in a total amount of glass fiber composition, 52.0 to 59.5 mass% of SiO2, 17.5 to 25.5 mass% of B2O3, 9.0 to 14.0 mass% of Al2O3, 0.5 to 6.0 mass% of SrO, 1.0 to 5.0 mass% of MgO, 1.0 to 5.0 mass% of CaO, and a total of 0.1 to 2.5 mass% of F2 and Cl2 (see Patent Document 1). [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Patent No. 6468409 [Overview of the project] [Problems that the invention aims to solve]

[0010] On the other hand, there is a need for glass compositions for glass fibers that can produce glass fibers with lower dielectric constants and lower dielectric loss tangents, especially in the high-frequency range of around 10 GHz. To achieve this goal, it is conceivable to reduce the content of Al2O3 and alkaline earth metal oxides (CaO, MgO, and SrO) relative to the total amount of the glass composition for glass fibers, and increase the content of SiO2 and B2O3 accordingly.

[0011] However, if the content of SiO2 and B2O3 relative to the total amount of the glass fiber composition is increased in the glass fiber composition in exchange for the content of Al2O3 and alkaline earth metal oxides, the working temperature range, expressed as the difference between the 1000 poise temperature and the liquidus temperature, narrows, which can lead to a decrease in the manufacturability of the glass fiber, or the water resistance of the glass fiber may deteriorate, and the dielectric properties may worsen due to foreign matter precipitated on the surface of the glass fiber due to hydrolysis of the glass, or the strength of the glass fiber may decrease significantly.

[0012] The present invention aims to provide a glass composition for glass fibers that overcomes these disadvantages and allows for the acquisition of glass fibers having excellent water resistance and excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the high-frequency range, and that itself has a sufficient working temperature range. [Means for solving the problem]

[0013] To achieve this objective, the glass fiber composition of the present invention contains, in addition to the total amount of the glass fiber composition, 59.60 SiO2 in the range of ~65.00 mass%, 18.00 B2O3 in the range of ~26.00 mass% and 7.00~ 11.80 Al2O3 in the mass % range, and 0~ 4.80 CaO in the mass% range, MgO in the 0-4.00 mass% range, SrO in the 0-6.00 mass% range, TiO2 in the 0.10-5.00 mass% range, in total 0.80It contains F2 and Cl2 in the range of 0 to 2.00% by mass, the content rate of P2O5 is less than 0.20% by mass, and the total content rate of Na2O, K2O and Li2O is less than 1.00% by mass.

[0014] The glass composition for glass fiber of the present invention contains SiO2, B2O3, Al2O3, CaO, MgO, SrO, TiO2, F2 and Cl2, P2O5, Na2O, K2O and Li2O within the above ranges, thereby obtaining glass fiber having excellent water resistance and excellent dielectric properties (low dielectric constant and low dielectric tangent) in the high-frequency region, and having a sufficient working temperature range by itself.

[0015] Here, that the glass fiber obtained from the glass composition for glass fiber of the present invention has a low dielectric constant means that the dielectric constant is 4.2 or less at a measurement frequency of 10 GHz, and that it has a low dielectric tangent means that the dielectric tangent is 0.0011 or less at a measurement frequency of 10 GHz.

[0016] Also, that the glass fiber obtained from the glass composition for glass fiber of the present invention exhibits excellent water resistance means that when evaluated by the following water resistance evaluation method, the mass reduction rate is 2.0% or less and the components of the glass fiber hardly elute even in water.

[0017] In the water resistance evaluation method, first, a glass batch obtained by mixing glass raw materials so that the glass composition after melting and solidification becomes a predetermined glass composition for glass fibers is placed in a platinum crucible with a diameter of 80 mm, melted at 1550 °C for 4 hours and at 1650 °C for 2 hours, taken out from the crucible, and a homogeneous glass cullet obtained is placed in a small cylindrical platinum bushing having one circular nozzle tip at the bottom of the container. After heating and melting at a predetermined temperature, the molten glass discharged from the nozzle tip is wound around a stainless steel collet at a predetermined speed and cooled and solidified while being stretched to obtain glass fibers with a fiber diameter of 13 μm and a circular cross-section with a perfect circle. Next, about 1 g (test glass fibers) of the obtained glass fibers is collected from the collet, dried at 120 °C for 1 hour, and the mass (mass before operation) is measured. Then, the test glass fibers are left standing in 100 ml of distilled water at 80 °C for 24 hours, then the test glass fibers are taken on a wire mesh with an opening of approximately 150 μm, washed with distilled water, dried at 120 °C for 1 hour, and the mass (mass after operation) is measured. And from the mass before operation and the mass after operation, the mass reduction rate (100×(1 - (mass after operation / mass before operation))) is calculated.

[0018] In addition, that the glass composition for glass fibers of the present invention has a sufficient working temperature range means that the working temperature range is 20 °C or more. The upper limit of the working temperature range is not particularly limited, but for example, it is 500 °C or less, preferably 450 °C or less, more preferably 400 °C or less.

[0019] The present invention also relates to glass fibers characterized by being made of any of the above glass compositions for glass fibers, glass fiber fabrics characterized by containing the glass fibers, or glass fiber reinforced resin compositions characterized by containing the glass fibers.

[0020] The glass fibers of the present invention can be obtained, for example, by melting the glass composition for glass fibers of the present invention described above, extruding the resulting molten material from a bushing having 1 to 8,000 nozzle tips or a nozzle plate with holes, and cooling and solidifying it while being stretched by winding it at high speed to form fibers. Therefore, the glass fibers of the present invention have the same glass composition as the glass composition for glass fibers of the present invention described above. [Modes for carrying out the invention]

[0021] Next, embodiments of the present invention will be described in more detail.

[0022] The glass fiber composition of this embodiment is, in proportion to the total amount of the glass fiber composition, 59.60 SiO2 in the range of ~65.00 mass%, 18.00 B2O3 in the range of ~26.00 mass% and 7.00~ 11.80 Al2O3 in the mass % range, and 0~ 4.80 CaO in the mass% range, MgO in the 0-4.00 mass% range, SrO in the 0-6.00 mass% range, TiO2 in the 0.10-5.00 mass% range, in total 0.80 It contains F2 and Cl2 in the range of ~2.00 mass%, has a P2O5 content of less than 0.20 mass%, and the total content of Na2O, K2O, and Li2O is less than 1.00 mass. ru.

[0023] The glass fiber composition of this embodiment contains SiO2, B2O3, Al2O3, CaO, MgO, SrO, TiO2, F2 and Cl2, P2O5, Na2O, K2O and Li2O in the above-mentioned ranges. son-in-law This makes it possible to obtain glass fibers that possess excellent water resistance and excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the high-frequency range, and that themselves have a sufficient operating temperature range.

[0024] The glass fiber composition of this embodiment has an SiO2 content relative to the total amount of the glass fiber composition. 59.60If the SiO2 content is less than 65.00% by mass, the mechanical strength of the glass fibers obtained from the glass fiber composition will decrease significantly, impairing the function of the glass fibers as a reinforcing material in the glass fiber reinforced resin composition. Furthermore, the glass fibers will be more susceptible to degradation when exposed to acidic environments. On the other hand, if the SiO2 content exceeds 65.00% by mass relative to the total amount of the glass fiber composition, the viscosity at high temperatures will increase, requiring a higher melting temperature for the glass raw materials, making it unsuitable for industrial glass fiber production from a manufacturing cost standpoint.

[0025] The glass fiber composition of this embodiment preferably has an SiO2 content relative to the total amount of the glass fiber composition. 、5 The range is 9.60 to 62.80% by mass, most preferably 60.10 to 62.60% by mass.

[0026] The glass fiber composition of this embodiment has a B2O3 content relative to the total amount of the glass fiber composition. 18.00 If the B2O3 content is less than 26.00% by mass relative to the total amount of the glass fiber composition, phase separation may occur in the glass fibers obtained from the glass fiber composition, potentially reducing the chemical durability of the glass fibers.

[0027] The glass fiber composition of this embodiment has a B2O3 content of preferably 18.00 to 24.90% by mass, more preferably 19.00 to 24.50% by mass, even more preferably 19.60 to 24.00% by mass, particularly preferably 20.10 to 23.50% by mass, and most preferably 20.50 to 23.00% by mass, relative to the total amount of the glass fiber composition.

[0028] In this embodiment, if the Al2O3 content of the glass fiber composition is less than 7.00% by mass relative to the total amount of the glass fiber composition, phase separation may occur in the glass fibers obtained from the glass fiber composition, potentially reducing the chemical durability of the glass fibers. On the other hand, if the Al2O3 content relative to the total amount of the glass fiber composition is 11.80 If the amount exceeds mass%, the dielectric loss tangent of the glass fibers obtained from the glass composition for glass fibers cannot be sufficiently reduced.

[0029] The glass fiber composition of this embodiment preferably has an Al2O3 content relative to the total amount of the glass fiber composition. 、8 The range is 0.00 to 11.80 mass%, most preferably in the range of 8.20 to 9.90 mass%.

[0030] The glass fiber composition of this embodiment has a CaO content relative to the total amount of the glass fiber composition. 4.80 If the amount exceeds mass%, the dielectric loss tangent of the glass fibers obtained from the glass composition for glass fibers cannot be sufficiently reduced.

[0031] The glass fiber composition of this embodiment has a CaO content of preferably 0.60 to 4.80% by mass, more preferably 1.10 to 4.60% by mass, even more preferably 1.60 to 4.40% by mass, particularly preferably 1.80 to 4.20% by mass, especially preferably 2.00 to 4.00% by mass, and most preferably 2.10 to 3.60% by mass, based on the total amount of the glass fiber composition.

[0032] In this embodiment, if the MgO content of the glass fiber composition exceeds 4.00% by mass relative to the total amount of the glass fiber composition, striations may occur in the molten glass fiber composition, making it easier for glass fibers to break during spinning, and the water resistance of the glass fibers obtained from the glass fiber composition may deteriorate.

[0033] The glass fiber composition of this embodiment has an MgO content of less than 3.00% by mass, more preferably less than 2.00% by mass, even more preferably less than 1.50% by mass, particularly preferably less than 1.00% by mass, especially preferably less than 0.95% by mass, and most preferably less than 0.50% by mass, based on the total amount of the glass fiber composition.

[0034] In this embodiment, if the SrO content of the glass fiber composition exceeds 6.00% by mass relative to the total amount of the glass fiber composition, the dielectric properties of the glass fibers obtained from the glass fiber composition deteriorate, and the target dielectric properties cannot be met.

[0035] The glass fiber composition of this embodiment has a SrO content of less than 4.00% by mass, more preferably less than 3.00% by mass, even more preferably less than 2.00% by mass, particularly preferably less than 1.00% by mass, especially preferably less than 0.50% by mass, and most preferably less than 0.45% by mass, relative to the total amount of the glass fiber composition.

[0036] In this embodiment, if the TiO2 content of the glass fiber composition is less than 0.10% by mass relative to the total amount of the glass fiber composition, the viscosity at high temperatures increases, which raises the melting temperature of the glass raw materials, making it unsuitable for industrial glass fiber production from the viewpoint of manufacturing costs. On the other hand, if the TiO2 content is greater than 5.00% by mass relative to the total amount of the glass fiber composition, the dielectric loss tangent of the glass fibers obtained from the glass fiber composition cannot be sufficiently reduced, and the liquidus temperature of the glass fiber composition increases significantly, making it impossible to produce stable glass fibers.

[0037] The glass fiber composition of this embodiment has a TiO2 content of preferably 0.60 to 4.90% by mass, more preferably 1.60 to 4.70% by mass, even more preferably 2.10 to 4.60% by mass, particularly preferably 2.50 to 4.50% by mass, and most preferably 2.80 to 4.40% by mass, based on the total amount of the glass fiber composition.

[0038] In this embodiment, if the combined content of F2 and Cl2 in the glass fiber composition exceeds 2.00% by mass relative to the total amount of the glass fiber composition, the chemical durability of the glass fibers obtained from the glass fiber composition decreases.

[0040] In this embodiment, if the glass composition for glass fibers contains more than 0.20% by mass of P2O5 relative to the total amount of the glass composition for glass fibers, and the SiO2 content is within the aforementioned range, the presence of P2O5 does not contribute to improving the dielectric properties of the glass fibers obtained from the glass composition for glass fibers. On the other hand, the generation of phase separation in the glass fibers cannot be suppressed, and the chemical durability of the glass fibers deteriorates.

[0041] The glass fiber composition of this embodiment preferably has a P2O5 content of less than 0.10% by mass, and more preferably less than 0.05% by mass, relative to the total amount of the glass fiber composition.

[0042] Furthermore, in the glass fiber composition of this embodiment, if the total content of Na2O, K2O, and Li2O exceeds 1.00% by mass relative to the total amount of the glass fiber composition, the dielectric properties of the glass fibers obtained from the glass fiber composition deteriorate significantly, and the target dielectric properties cannot be met.

[0043] The glass composition for glass fibers of the present embodiment has a total content of Na2O, K2O, and Li2O preferably in a range of less than 0.80% by mass, more preferably in a range of less than 0.50% by mass, still more preferably in a range of less than 0.20% by mass, particularly preferably in a range of less than 0.10% by mass, and most preferably in a range of less than 0.05% by mass, based on the total amount of the glass composition for glass fibers.

[0050] Further, in the glass composition for glass fibers of the present embodiment, the content rate (mass %) SI of SiO2, the content rate (mass %) B of B2O3, the content rate (mass %) A of Al2O3, the content rate (mass %) C of CaO, the content rate (mass %) M of MgO, the content rate (mass %) SR of SrO, the content rate (mass %) T of TiO2, and the total content rate (mass %) F of F2 and Cl2 preferably satisfy the following formula (1) and more preferably satisfy the following formula (2) and still more preferably satisfy the following formula (3) and particularly preferably satisfy the following formula (4) . 204.00 ≦ SI × B 2 × T 2 / [{C + (40.1 / 87.6) × SR - (40.1 / 24.3) × M - F} 1 / 2 × A 3 ≦ 422.40 ··· (1) 244.00 ≦ SI × B 2 × T 2 / [{C + (40.1 / 87.6) × SR - (40.1 / 24.3) × M - F} 1 / 2 × A 3 ≦ 410.00 ··· (2) 308.50 ≦ SI × B 2 × T 2 / [{C + (40.1 / 87.6) × SR - (40.1 / 24.3) × M - F} 1 / 2 × A 3 ≦ 400.50 ··· (3) 339.60 ≦ SI × B 2 × T 2 / [{C+(40.1 / 87.6)×SR-(40.1 / 24.3)×MF} 1 / 2 ×A 3 ] ≤ 377.80 ··· (4)

[0051] The glass fiber composition of this embodiment is a glass composition in which the SI, B, A, C, M, SR, T, and F are of the formula (1) By satisfying these conditions, it is possible to obtain glass fibers that possess excellent water resistance and excellent dielectric properties in the high-frequency range, and that themselves have a sufficient operating temperature range.

[0052] Furthermore, the glass fiber composition of this embodiment is a glass composition in which the SI, B, A, C, M, SR, T, and F are of the formula (2) By satisfying these conditions, it is possible to obtain glass fibers that have excellent water resistance and superior dielectric properties in the high-frequency range, and that themselves have a sufficient operating temperature range. Here, the glass fibers having superior dielectric properties means that the dielectric constant at a measurement frequency of 10 GHz is 4.1 or less and the dielectric loss tangent is 0.0010 or less.

[0053] Furthermore, the glass fiber composition of this embodiment is a glass composition in which the SI, B, A, C, M, SR, T, and F are of the formula (3) By satisfying these conditions, it is possible to obtain glass fibers that possess excellent water resistance and superior dielectric properties in the high-frequency range, and that themselves have an excellent working temperature range of 120°C or higher.

[0054] Furthermore, the glass fiber composition of this embodiment is a glass composition in which the SI, B, A, C, M, SR, T, and F are of the formula (4) By satisfying these conditions, it is possible to obtain glass fibers that possess excellent water resistance and extremely excellent dielectric properties in the high-frequency range, and that themselves have a superior working temperature range of 200°C or higher. Here, the glass fibers possessing extremely excellent dielectric properties means that the dielectric constant at a measurement frequency of 10 GHz is 4.0 or less and the dielectric loss tangent is less than 0.0010.

[0055] Furthermore, the glass fiber composition of this embodiment has a ratio of MgO content (mass%) to the total content (mass%) of CaO and SrO (MgO / (CaO+SrO)) that is, for example, less than 0.60. This suppresses the generation of phase separation in the glass fibers obtained from the glass fiber composition, which is promoted by MgO, while also reducing the viscosity of the glass fiber composition at high temperatures and lowering the liquidus temperature of the glass fiber composition, thereby contributing to an overall improvement in the manufacturability of the glass fiber composition. The glass fiber composition of this embodiment has a ratio of MgO content (mass%) to the total content (mass%) of CaO and SrO (MgO / (CaO+SrO)) that is preferably less than 0.40, more preferably less than 0.30, even more preferably less than 0.20, particularly preferably less than 0.10, and most preferably less than 0.05.

[0056] Furthermore, in the glass fiber composition of this embodiment, the ratio of TiO2 content (mass%) to Al2O3 content (mass%) (TiO2 / Al2O3) is, for example, in the range of 0.24 to 0.72, thereby suppressing the rise in liquidus temperature of the glass fiber composition due to crystal formation promoted by TiO2, while simultaneously achieving the effect of reducing dielectric loss tangent by containing TiO2 and the effect of improving water resistance by containing Al2O3. In the glass fiber composition of this embodiment, the ratio of TiO2 content (mass%) to Al2O3 content (mass%) (TiO2 / Al2O3) is preferably in the range of 0.28 to 0.56, more preferably in the range of 0.29 to 0.50, even more preferably in the range of 0.30 to 0.45, and most preferably in the range of 0.35 to 0.44.

[0057] Furthermore, the glass fiber composition of this embodiment has the following formula for the content (mass) of B, A, C, M, SR, T, F and P2O5: (5)By satisfying these conditions, it is possible to obtain glass fibers that possess excellent water resistance and excellent dielectric properties in the high-frequency range, and that themselves have a sufficient operating temperature range. 1.08 ≦ {2×(0.72×C+M+0.39×SR)-1.06×F}×(B / 1.2+A / 1.7+P / 1.3+T / 4.7) / (1.37×B / 1.2+1.77×A / 1.7+1.63×P / 1.3+1.96×T / 4.7) ≦ 2.34... (5)

[0058] The glass fiber composition of this embodiment preferably contains B, A, C, M, SR, T, F, and P in the following formula (6) Satisfying the following conditions, and more preferably the following formula (7) Satisfying the following equation, and especially preferably the following equation (8) It satisfies the condition. 1.47 ≦ {2×(0.72×C+M+0.39×SR)-1.06×F}×(B / 1.2+A / 1.7+P / 1.3+T / 4.7) / (1.37×B / 1.2+1.77×A / 1.7+1.63×P / 1.3+1.96×T / 4.7) ≦ 2.33... (6) 1.47 ≦ {2×(0.72×C+M+0.39×SR)-1.06×F}×(B / 1.2+A / 1.7+P / 1.3+T / 4.7) / (1.37×B / 1.2+1.77×A / 1.7+1.63×P / 1.3+1.96×T / 4.7) ≦ 2.32... (7) 2.14 ≦ {2×(0.72×C+M+0.39×SR)-1.06×F}×(B / 1.2+A / 1.7+P / 1.3+T / 4.7) / (1.37×B / 1.2+1.77×A / 1.7+1.63×P / 1.3+1.96×T / 4.7) ≦ 2.32... (8)

[0059] The glass fiber composition of this embodiment is such that B, A, C, M, SR, T, F and P are of the formula (6) By satisfying these conditions, it is possible to obtain glass fibers that possess excellent water resistance and superior dielectric properties in the high-frequency range, and that themselves have a sufficient operating temperature range.

[0060] Furthermore, the glass fiber composition of this embodiment is such that B, A, C, M, SR, T, F, and P are of the formula (7) By satisfying these conditions, it is possible to obtain glass fibers that possess excellent water resistance and superior dielectric properties in the high-frequency range, and that themselves have an excellent working temperature range of 120°C or higher.

[0061] Furthermore, the glass fiber composition of this embodiment is such that B, A, C, M, SR, T, F, and P are of the formula (8) By satisfying these conditions, it is possible to obtain glass fibers that possess excellent water resistance and extremely excellent dielectric properties in the high-frequency range, and which themselves can have a superior working temperature range of 200°C or higher.

[0062] Furthermore, the glass fiber composition of this embodiment may contain ZnO in an amount of 0 to 3.00% by mass relative to the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains ZnO, and the ZnO content exceeds 3.00% by mass, devitrified materials are more likely to occur, making it impossible to manufacture glass fibers stably.

[0063] When the glass fiber composition of this embodiment contains ZnO, the ZnO content relative to the total amount of the glass fiber composition is preferably 2.50% by mass or less, more preferably 1.50% by mass or less, and even more preferably 0.50% by mass or less.

[0064] Furthermore, the glass fiber composition of this embodiment may contain MnO2 in an amount of 0 to 3.00% by mass relative to the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains MnO2, and the MnO2 content exceeds 3.00% by mass, the dielectric properties will deteriorate, and the desired dielectric properties cannot be obtained.

[0065] When the glass fiber composition of this embodiment contains MnO2, the MnO2 content relative to the total amount of the glass fiber composition is preferably 2.50% by mass or less, more preferably 1.50% by mass or less, and even more preferably 0.50% by mass or less.

[0066] Furthermore, the glass fiber composition of this embodiment may contain Fe2O3 in an amount of 0% to 1.00% by mass relative to the total amount of the glass fiber composition. When the glass fiber composition of this embodiment contains Fe2O3, it is effective to set the Fe2O3 content in the range of 0.10% to 0.60% by mass from the viewpoint of suppressing air bubbles contained in the glass fibers.

[0067] Furthermore, the glass fiber composition of this embodiment may contain SnO2 in an amount of 0% to 1.00% by mass relative to the total amount of the glass fiber composition. When the glass fiber composition of this embodiment contains SnO2, it is effective to set the SnO2 content in the range of 0.10% to 0.60% by mass from the viewpoint of suppressing air bubbles contained in the glass fibers.

[0068] Furthermore, in the glass fiber composition of this embodiment, ZrO2 may be included if its ZrO2 content is less than 0.50% by mass of the total amount of the glass fiber composition. If the ZrO2 content is 0.50% by mass or more of the total amount of the glass fiber composition, devitrified substances are more likely to occur, making it impossible to manufacture glass fibers stably.

[0069] When the glass fiber composition of this embodiment contains ZrO2, the ZrO2 content relative to the total amount of the glass fiber composition is preferably in the range of less than 0.45% by mass, more preferably in the range of less than 0.40% by mass, even more preferably in the range of less than 0.20% by mass, particularly preferably in the range of less than 0.10% by mass, and most preferably in the range of less than 0.05% by mass.

[0070] Furthermore, in the glass fiber composition of this embodiment, Cr2O3 may be included if its content is less than 0.05% by mass relative to the total amount of the glass fiber composition. If the Cr2O3 content is 0.05% by mass or more relative to the total amount of the glass fiber composition, devitrified materials are more likely to occur, making it impossible to manufacture glass fibers stably.

[0071] Furthermore, the glass fiber composition of this embodiment may contain, in total, less than 1.00% by mass of oxides of Ba, Co, Ni, Cu, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb as impurities originating from the raw materials, relative to the total amount of the glass fiber composition. In particular, if the glass fiber composition of this embodiment contains BaO, CeO2, Y2O3, La2O3, Bi2O3, Gd2O3, Pr2O3, Sc2O3, or Yb2O3 as impurities, their respective content is preferably less than 0.40% by mass, more preferably less than 0.20% by mass, even more preferably less than 0.10% by mass, particularly preferably less than 0.05% by mass, and most preferably less than 0.01% by mass.

[0072] In the glass fiber composition of this embodiment, the content of each component can be measured using an ICP emission spectrometer for the light element Li, and using a wavelength-dispersive X-ray fluorescence spectrometer for the other elements.

[0073] The measurement method involves first placing a glass batch (a mixture of glass raw materials) or glass fibers (if organic matter is attached to the surface of the glass fibers, or if the glass fibers are mainly included as a reinforcing material in the organic matter (resin), the organic matter is removed by heating in a muffle furnace at 300-650°C for 0.5-24 hours before use) into a platinum crucible. In an electric furnace, the glass batch is melted while stirring at 1550°C for 4 hours and 1650°C for 2 hours, while the glass fibers are melted while stirring at 1550°C for 6 hours, thereby obtaining homogeneous molten glass. Next, the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then crushed and powdered to obtain glass powder. For the light element Li, the obtained glass powder is heated and decomposed with acid, and then quantitatively analyzed using an ICP emission spectrometer. For other elements, the glass powder is formed into a disc shape using a press, and then quantitatively analyzed using a wavelength-dispersive X-ray fluorescence analyzer. Quantitative analysis using a wavelength-dispersive X-ray fluorescence spectrometer can be performed by preparing calibration curve samples based on results measured by the fundamental parameter method, and then analyzing them using the calibration curve method. The content of each component in the calibration curve sample can be quantitatively analyzed using an ICP emission spectrometer. These quantitative analysis results can then be converted to oxide values ​​to calculate the content and total amount of each component, and from these values, the aforementioned content rates of each component can be determined.

[0074] The glass fiber composition of this embodiment can be obtained by melting a glass raw material (glass batch) that has been prepared to have the aforementioned composition after melting and solidifying, and then cooling and solidifying it.

[0075] When forming glass fibers according to this embodiment from the glass composition for glass fibers according to this embodiment, first, the glass raw material prepared as described above is supplied to a glass melting furnace and melted at a temperature range of 1000 poise temperature or higher, specifically in the range of 1400°C to 1700°C. Then, the molten glass melted at the above temperature is extruded from 1 to 8000 nozzle tips or holes controlled to a predetermined temperature, and cooled and solidified while being stretched by winding at high speed to form glass fibers.

[0076] Here, a single glass fiber (glass filament) extruded from a nozzle tip or hole and cooled and solidified typically has a circular cross-sectional shape and a diameter of 3.0 to 35.0 μm. For applications requiring low dielectric properties, the glass filament preferably has a diameter of 3.0 to 6.0 μm, and more preferably a diameter in the range of 3.0 to 4.5 μm. On the other hand, if the nozzle tip has a non-circular shape and includes protrusions or notches for rapidly cooling the molten glass, a glass filament with a non-circular (e.g., elliptical, oblong) cross-sectional shape can be obtained by controlling the temperature conditions. When the glass filament has an elliptical or oblong cross-sectional shape, the ratio of the major axis to the minor axis of the cross-sectional shape (major axis / minor axis) is, for example, in the range of 2.0 to 10.0, and the fiber diameter when the cross-sectional area is converted to a circle (converted fiber diameter) is in the range of 3.0 to 35.0 μm.

[0077] In this embodiment, the glass fibers typically take the form of a glass fiber bundle (glass strand) consisting of 10 to 8,000 glass filaments, and have a weight in the range of 1 to 10,000 tex (g / km). Note that glass filaments extruded from multiple nozzle tips or holes may be bundled into a single glass fiber bundle or into multiple glass fiber bundles.

[0078] The glass fibers of this embodiment can take various forms, such as yarn, woven fabric, knitted fabric, nonwoven fabric (including chopped strand mats and multiaxial nonwoven fabrics), chopped strands, roving, and powder, obtained by further processing the glass strands.

[0079] The glass fibers of this embodiment may be coated on their surface with an organic substance for purposes such as improving the bundling ability of the glass filaments, improving the adhesion between the glass fibers and the resin, and improving the uniform dispersion of the glass fibers in a mixture of glass fibers and resin or inorganic material. Examples of such organic substances include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (especially carboxylic acid-modified polypropylene), and copolymers of (poly)carboxylic acid (especially maleic acid) and unsaturated monomers. In addition, the glass fibers of this embodiment may be coated with a resin composition containing a silane coupling agent, lubricant, surfactant, etc., in addition to these resins. Alternatively, the glass fibers of this embodiment may be coated with a treatment agent composition that does not contain the above resins but contains a silane coupling agent, surfactant, etc. The resin composition or treatment agent composition coats the glass fibers at a ratio of 0.03 to 2.0% by mass, based on the mass of the glass fibers of this embodiment in an uncoated state. Furthermore, the coating of glass fibers with organic matter can be carried out, for example, in the glass fiber manufacturing process by applying a resin solution or resin composition solution to the glass fibers using a known method such as a roller-type applicator, and then drying the glass fibers to which the resin solution or resin composition solution has been applied. Alternatively, the glass fibers of this embodiment, which are in the form of a woven fabric, can be immersed in a treatment agent composition solution, and then the glass fibers to which the treatment agent composition has been applied can be dried.

[0080] Examples of silane coupling agents include aminosilane, chlorsilane, epoxysilane, mercaptosilane, vinylsilane, and (meth)acrylsilane.

[0081] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0082] Examples of chlorsilanes include γ-chloropropyltrimethoxysilane.

[0083] Examples of epoxysilanes include (β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0084] Examples of mercaptosilanes include γ-mercaptotrimethoxysilane.

[0085] Examples of vinylsilanes include vinyltrimethoxysilane and N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane.

[0086] Examples of (meth)acryloxypropyltrimethoxysilanes include γ-methacryloxypropyltrimethoxysilane.

[0087] In this embodiment, the silane coupling agent may be used alone, or two or more may be used in combination.

[0088] Examples of lubricants include modified silicone oils, animal oils and their hydrogenated counterparts, vegetable oils and their hydrogenated counterparts, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimines, polyalkylpolyamine alkylamide derivatives, fatty acid amides, and quaternary ammonium salts.

[0089] Examples of animal fats include beef tallow.

[0090] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.

[0091] Examples of animal-derived waxes include beeswax and lanolin.

[0092] Examples of plant-based waxes include candelilla wax and carnauba wax.

[0093] Examples of mineral-based waxes include paraffin wax and montan wax.

[0094] Examples of condensates of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.

[0095] Examples of fatty acid amides include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid.

[0096] Examples of quaternary ammonium salts include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0097] In this embodiment, the lubricant may be used alone, or two or more may be used in combination.

[0098] Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, the surfactants may be used individually or in combination of two or more types.

[0099] Examples of nonionic 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, sucrose fatty acid ester, polyhydric alcohol alkyl ether, fatty acid alkanolamide, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, and ethylene oxide adduct of acetylene alcohol.

[0100] Examples of cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (such as acetates and hydrochlorides), ethylene oxide adducts to higher alkylamines, condensates of higher fatty acids and polyalkylene polyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridinium salts.

[0101] Examples of anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfons, α-olefin sulfons, reaction products of fatty acid halides and N-methyl taurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphate salts of higher alcohol ethylene oxide adducts.

[0102] Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as alkali metal alkylaminopropionates, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.

[0103] The glass fiber fabric of this embodiment includes the glass fibers of this embodiment as described above. Specifically, the glass fiber fabric of this embodiment can be obtained by weaving the glass fibers of this embodiment as described above, at least as part of the warp or weft, using a loom that is known in itself. Examples of the loom include jet looms such as air jet or water jet looms, shuttle looms, rapier looms, etc. Examples of weaving methods using the loom include plain weave, satin weave, twill weave, etc., with plain weave being preferred from the viewpoint of manufacturing efficiency. It is preferable to use the glass fibers of this embodiment as warp and weft in the glass fiber fabric of this embodiment.

[0104] In the glass fiber fabric of this embodiment, the glass fibers of this embodiment preferably consist of 35 to 400 glass filaments with a filament diameter of 3.0 to 9.0 μm bundled together, with a twist of 0 to 1.0 turns / 25 mm and a mass of 0.9 to 69.0 tex (g / km).

[0105] In the glass fiber fabric of this embodiment, when the aforementioned glass fibers of this embodiment are used as warp or weft threads, the warp weave density is preferably 40 to 120 threads / 25 mm, and the weft weave density is preferably 40 to 120 threads / 25 mm.

[0106] The glass fiber fabric of this embodiment may undergo de-oiling treatment, surface treatment, and fiber opening treatment after weaving.

[0107] As a de-oiling treatment, one method involves placing the glass fiber fabric in a heating furnace at an ambient temperature of 350°C to 400°C for 40 to 80 hours to thermally decompose any organic matter adhering to the glass fibers.

[0108] As a surface treatment, one example is to immerse the glass fiber fabric in the silane coupling agent, or in a solution containing the silane coupling agent and the surfactant, squeeze out the excess water, and then heat-dry it at a temperature range of 80 to 180°C for 1 to 30 minutes.

[0109] Examples of fiber opening processes include applying a tension of 30 to 200 N to the warp threads of a glass fiber fabric while opening the fibers by water flow pressure, opening the fibers by high-frequency vibration using a liquid as a medium, opening the fibers by the pressure of a fluid with surface pressure, and opening the fibers by pressing with a roll, thereby widening the width of the warp and weft threads.

[0110] The glass fiber fabric of this embodiment has a density of 7.0 to 190.0 g / m². 2 It is preferable that the mass per unit area is in the range of , and the thickness is in the range of 8.0 to 200.0 μm.

[0111] In this embodiment, the warp thread width of the glass fiber fabric is preferably 110 to 600 μm, and the weft thread width is preferably 110 to 600 μm.

[0112] The glass fiber fabric of this embodiment may include a surface treatment layer containing the silane coupling agent, or the silane coupling agent and the surfactant. When the glass fiber fabric of this embodiment includes the surface treatment layer, the surface treatment layer may have a mass in the range of, for example, 0.03 to 1.50% by mass relative to the total amount of the glass fiber fabric including the surface treatment layer.

[0113] The glass fiber reinforced resin composition of this embodiment contains the glass fibers of this embodiment as described above. Specifically, the glass fiber reinforced resin composition of this embodiment is a glass fiber reinforced resin composition containing a resin (thermoplastic resin or thermosetting resin), glass fibers, and other additives, and contains 10 to 90% by mass of glass fibers based on the total amount of the glass fiber reinforced resin composition. Furthermore, the glass fiber reinforced resin composition of this embodiment contains 90 to 10% by mass of resin and 0 to 40% by mass of other additives based on the total amount of the glass fiber reinforced resin composition.

[0114] Here, the thermoplastic resins 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), and polycarbonate. Examples include polyphosphates, polyarylene sulfides, polyethersulfones (PES), polyphenylsulfones (PPSU), polyphenylene ethers (PPE), modified polyphenylene ethers (m-PPE), polyarylether ketones, liquid crystal polymers (LCP), fluororesins, polyetherimides (PEI), polyarylates (PAR), polysulfones (PSF), polyamideimides (PAI), polyaminobismaleimides (PABM), thermoplastic polyimides (TPI), polyethylene naphthalates (PEN), ethylene / vinyl acetate (EVA) resins, ionomer (IO) resins, polybutadiene, styrene / butadiene resins, polybutylene, polymethylpentene, olefin / vinyl alcohol resins, cyclic olefin resins, cellulose resins, and polylactic acid.

[0115] Specifically, examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.

[0116] Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0117] Examples of polystyrene include general-purpose polystyrene (GPPS), which is atactic polystyrene having an atactic structure; high-impact polystyrene (HIPS), which is GPPS with added rubber components; and syndiotactic polystyrene, which has a syndiotactic structure.

[0118] Examples of methacrylic resins include polymers obtained by homopolymerizing one of the following: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl esters, or polymers obtained by copolymerizing two or more of these.

[0119] Examples of polyvinyl chloride include vinyl chloride homopolymers polymerized by conventionally known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization, copolymers of vinyl chloride monomer and copolymerizable monomers, and graft copolymers obtained by graft polymerization of vinyl chloride monomer onto a polymer.

[0120] Examples of polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sevacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sevacamide (nylon 510), polyhexamethylene sevacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), and polydecamethylene. Polyethylene sevacamide (Nylon 1010), Polydecamethylene dodecamide (Nylon 1012), Polyundecaneamide (Nylon 11), Polyundecamethylene adipamide (Nylon 116), Polydodecaneamide (Nylon 12), Polyxylene adipamide (Nylon XD6), Polyxylene sevacamide (Nylon XD10), Polymetaxylylene adipamide (Nylon MXD6), Polyparaxylylene adipamide (Nylon PXD6), Polytetramethylene terephthalamide (Nylon 4T), polypentamethylene terephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), polytetramethylene isophthalamide (nylon 4I), polybis( Examples include copolymers or mixtures thereof, consisting of one or more of the following components: 3-methyl-4-aminohexyl)methaneterephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methaneisophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methanendodecamido (nylon PACM12), polybis(3-methyl-4-aminohexyl)methanetetradecamide (nylon PACM14).

[0121] Examples of polyacetals include homopolymers in which oxymethylene units are the main repeating units, and copolymers that mainly consist of oxymethylene units and contain oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0122] Examples of polyethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with ethylene glycol.

[0123] Examples of polybutylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,4-butanediol.

[0124] Examples of polytrimethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,3-propanediol.

[0125] Examples of polycarbonates include polymers obtained by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate in a molten state, or polymers obtained by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

[0126] Examples of polyarylene sulfides include linear polyphenylene sulfides, cross-linked polyphenylene sulfides with high molecular weight obtained by curing reactions after polymerization, polyphenylene sulfide sulfones, polyphenylene sulfide ethers, and polyphenylene sulfide ketones.

[0127] Examples of polyphenylene ethers include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2-phenyl-1,4-phenylene Examples include poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), and poly(2,6-dimethyl-1,4-phenylene ether).

[0128] Examples of modified polyphenylene ethers include polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / maleic anhydride copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polyamide, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene / acrylonitrile copolymer, polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxyl groups, and styryl groups are introduced at the polymer chain ends, and polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxyl groups, styryl groups, and methacrylic groups are introduced at the polymer chain side chains.

[0129] Examples of polyaryl ether ketones include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK).

[0130] Examples of liquid crystal polymers (LCPs) include (co)polymers consisting of one or more structural units selected from thermotropic liquid crystal polyesters such as aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, and aliphatic dicarbonyl units.

[0131] Examples of fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluoroethylene propylene resin (FEP), fluoroethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0132] Examples of ionomer (IO) resins include polymers obtained by copolymerizing olefins or styrene with unsaturated carboxylic acids, in which some of the carboxyl groups are neutralized with metal ions.

[0133] Examples of olefin / vinyl alcohol resins include ethylene / vinyl alcohol copolymers, propylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymer saponifies, and propylene / vinyl acetate copolymer saponifies.

[0134] Examples of cyclic olefin resins include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0135] Examples of polylactic acid include poly-L-lactic acid, which is a homopolymer of the L-isomer; poly-D-lactic acid, which is a homopolymer of the D-isomer; and stereocomplex-type polylactic acid, which is a mixture thereof.

[0136] Examples of cellulose resins include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0137] Furthermore, examples of thermosetting resins 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 the like.

[0138] Specifically, examples of unsaturated polyester resins include resins obtained by esterifying an aliphatic unsaturated dicarboxylic acid with an aliphatic diol.

[0139] Examples of vinyl ester resins include bis-based vinyl ester resins and novolac-based vinyl ester resins.

[0140] Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexydiene bisphenol type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, and tetraphenol group ethane type novolac type epoxy resin. Examples include epoxy resins, novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure, biphenyl-type epoxy resins, aralkyl-type epoxy resins such as xylylene-type epoxy resins and phenylaralkyl-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins, bifunctional or tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalenearalkyl-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, and fluorene-type epoxy resins.

[0141] Examples of melamine resins include polymers formed by the polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0142] Examples of phenolic resins include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol A type novolac resin; resol-type phenolic resins such as methylol-type resol resin and dimethylene ether-type resol resin; and arylalkylene-type phenolic resins. One of these, or a combination of two or more, may be used.

[0143] Examples of urea resins include those obtained by the condensation of urea and formaldehyde.

[0144] The thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more types.

[0145] Since the glass fiber reinforced resin composition of this embodiment is used in applications where low dielectric properties are required, the resin is preferably epoxy resin, modified polyphenylene ether, polybutylene terephthalate, polypropylene, fluororesin, or liquid crystal polymer (LCP).

[0146] Other additives include reinforcing fibers other than glass fibers (e.g., carbon fibers, metal fibers), fillers other than glass fibers (e.g., glass powder, talc, mica), flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments, and the like.

[0147] The glass fiber reinforced resin composition of this embodiment may be a prepreg obtained by impregnating the glass fiber fabric of this embodiment with the resin using a method known to that effect and then semi-curing it.

[0148] The glass fiber reinforced resin composition of this embodiment 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, infusion, hand lay-up, spray-up, resin transfer molding, sheet molding compound, bulk molding compound, pultrusion, and filament winding to obtain various glass fiber reinforced resin molded products. Furthermore, glass fiber reinforced resin molded products can also be obtained by curing the prepreg.

[0149] Applications for such molded products include, for example, electronic equipment housings, electronic components, vehicle exterior components, vehicle interior components, vehicle engine components, muffler-related components, and high-pressure tanks.

[0150] One example of an electronic component is a printed circuit board.

[0151] Examples of vehicle exterior components include bumpers, fenders, hoods, air dams, and wheel covers.

[0152] Examples of vehicle interior components include door trims and ceiling materials.

[0153] Examples of components around a vehicle engine include the oil pan, engine cover, intake manifold, and exhaust manifold.

[0154] Examples of muffler-related components include sound-absorbing components.

[0155] Furthermore, the glass fibers of this embodiment can be suitably used not only as a glass fiber reinforced resin composition of this embodiment, but also as a reinforcing material for inorganic materials such as gypsum and cement. For example, when used as a reinforcing material for gypsum (particularly gypsum board with a thickness of 4 to 60 mm), glass fibers having the glass composition within the above range can be included in an amount of 0.1 to 4.0% by mass relative to the total mass of the gypsum.

[0156] Examples and comparative examples of the present invention are shown below. [Examples]

[0157] First, the glass composition after melting and solidifying is as shown in Examples 1 to 4 in Table 1 and Comparative Examples 1 to 4 in Tables 2 and 3. 9 Glass raw materials were mixed to obtain glass batches with the respective compositions.

[0158] Next, Example 1~ 3 Or Comparative Example 1~ 9 Glass batches corresponding to the glass composition for glass fibers were placed in an 80 mm diameter platinum crucible and melted at 1550°C for 4 hours and 1650°C for 2 hours. The melted batches were then removed from the crucible to obtain homogeneous glass bulk and glass cullet. Next, the obtained glass bulk and glass cullet were annealed at 620°C for 8 hours to obtain test specimens. The dielectric constant and dielectric loss tangent of the obtained test specimens were evaluated using the method described below. Furthermore, the water resistance was evaluated using the glass cullet obtained during the test specimen preparation process using the method described below. Additionally, the working temperature range was calculated using the glass cullet obtained during the test specimen preparation process using the method described below. Examples 1- 3 The results for Comparative Examples 1-5 are shown in Table 1, the results for Comparative Examples 6- 9 The results are shown in Table 3.

[0159] [Method for evaluating water resistance] The glass cullet obtained as described above was placed in a small cylindrical platinum bushing having a circular nozzle tip at the bottom of the container, heated to a predetermined temperature to melt, and then the molten glass extruded from the nozzle tip was wound onto a stainless steel collet at a predetermined speed, stretched and cooled to solidify, thereby obtaining glass fibers with a perfectly circular cross-section and a fiber diameter of 13 μm. Approximately 1 g of the obtained glass fibers (test glass fibers) was taken from the collet, dried at 120°C for 1 hour, and its mass (mass before operation) was measured. Next, the test glass fibers were left to stand in 100 ml of distilled water at 80°C for 24 hours. After that, the test glass fibers were placed on a wire mesh with holes of approximately 150 μm, washed with distilled water, dried at 120°C for 1 hour, and its mass (mass after operation) was measured.

[0160] The mass reduction rate (100 × (1 - (mass after operation / mass before operation))) was calculated from the mass before and after operation. A mass reduction rate of 2.0% or less, where almost no glass fiber components leached out in water, was considered OK, while a mass reduction rate exceeding 2.0%, where a large amount of glass fiber components leached out in water, was considered NG.

[0161] [Method for measuring dielectric constant and dielectric loss tangent] The test specimens were polished to create polished specimens measuring 80 mm x 3 mm (1 mm thick). The resulting polished specimens were then completely dried and stored in a room at 23°C and 60% humidity for 24 hours. Subsequently, the dielectric constant (dielectric constant Dk) and dielectric loss tangent (dissipation rate Df) of the resulting polished specimens were measured at 10 GHz using an AET Corporation cavity resonator dielectric constant measuring device ADMS01Oc1 (product name), in accordance with JIS C 2565:1992.

[0162] [Method for calculating the working temperature range] First, using a high-temperature electric furnace with a rotational viscometer (manufactured by Shibaura Systems Co., Ltd.), glass cullet was melted in a platinum crucible. The viscosity of the molten glass was continuously measured using a rotational Brookfield viscometer while varying the melting temperature. The 1000 poise temperature was determined by measuring the temperature corresponding to when the rotational viscosity reached 1000 poise.

[0163] Next, the glass cullet was crushed, and 40 g of glass particles with a particle size of 0.5 to 1.5 mm was placed in a platinum boat measuring 180 × 20 × 15 mm. After heating in a tubular electric furnace with a temperature gradient of 1000 to 1400°C for more than 8 hours, the boat was removed from the tubular electric furnace and observed with a polarizing microscope to identify the position where glass-derived crystals (devitrification) began to precipitate. The temperature inside the tubular electric furnace was measured using a B thermocouple, and the temperature at the position where the crystals began to precipitate was determined and defined as the liquidus temperature.

[0164] Next, the operating temperature range was calculated based on the difference between the 1000 poise temperature and the liquid phase temperature.

[0165] [Table 1]

[0166] [Table 2]

[0167] [Table 3]

[0168] Table 1 shows that, relative to the total amount of glass composition for glass fibers, 59.60 SiO2 in the range of ~65.00 mass%, 18.00 B2O3 in the range of ~26.00 mass%, Al2O3 in the range of 7.00~11.80 mass%, CaO in the range of 0~4.80 mass%, MgO in the range of 0~4.00 mass%, SrO in the range of 0~6.00 mass%, and TiO2 in the range of 0.10~5.00 mass%, in total 0.80 It contains F2 and Cl2 in the range of ~2.00 mass%, has a P2O5 content of less than 0.20 mass%, and the total content of Na2O, K2O, and Li2O is less than 1.00 mass. ru, in fact Example 1~ 3According to the glass composition for glass fibers, it is possible to obtain glass fibers that have excellent water resistance and excellent dielectric properties, with a dielectric constant of 4.2 or less and a dielectric loss tangent of 0.0011 or less in the high-frequency range of 10 GHz, and that themselves have a sufficient working temperature range of 26°C or higher.

[0169] On the other hand, Table 2 shows that the SiO2 content relative to the total amount of glass composition for glass fibers is 59.60 It is clear that, according to the glass composition for glass fibers of Comparative Example 1, in which the B2O3 content is less than 26.00 mass%, the Al2O3 content is less than 7.00 mass%, and the TiO2 content is less than 0.10 mass%, it is not possible to obtain glass fibers with sufficient water resistance.

[0170] Furthermore, the SiO2 content relative to the total amount of glass composition for glass fibers 59.60 Mass% It is clear that even in the glass composition for glass fibers of Comparative Example 2, which has a B2O3 content of more than 26.00% by mass and an Al2O3 content of less than 7.00% by mass, it is not possible to obtain glass fibers with sufficient water resistance.

[0171] Furthermore, the SiO2 content relative to the total amount of glass composition for glass fibers 59.60 It is clear that even in the glass composition for glass fibers of Comparative Example 3, which has a B2O3 content of less than 26.00% by mass and an Al2O3 content of less than 7.00% by mass, it is not possible to obtain glass fibers with sufficient water resistance.

[0172] Furthermore, the SiO2 content relative to the total amount of glass composition for glass fibers 59.60 In Comparative Example 4, a glass composition for glass fibers in which the content of B2O3 is less than 26.00 mass%, the content of Al2O3 is less than 7.00 mass%, and the content of TiO2 is more than 5.00 mass%, it is clear that glass fibers with sufficient water resistance cannot be obtained, and crystallization occurs.

[0173] Furthermore, the SiO2 content relative to the total amount of glass composition for glass fibers 59.60 It is clear that even in the glass composition for glass fibers of Comparative Example 5, which has a B2O3 content of less than 26.00% by mass and a B2O3 content of more than 26.00% by mass, it is not possible to obtain glass fibers with sufficient water resistance.

[0174] Furthermore, Table 3 shows that the SiO2 content relative to the total amount of glass fiber composition is 59.60 less than mass%, Al2O3 content 11.80 mass% Super In one example, Comparative Example 6, a glass composition for glass fibers fails to produce glass fibers with sufficient water resistance, and it is clear that phase separation occurs.

[0175] Furthermore, the SiO2 content relative to the total amount of glass composition for glass fibers 59.60 It is clear that even in the glass composition for glass fibers of Comparative Example 7, which has a B2O3 content of less than 26.00% by mass and a B2O3 content of more than 26.00% by mass, it is not possible to obtain glass fibers with sufficient water resistance.

[0176] Furthermore, the Al2O3 content relative to the total amount of glass composition for glass fibers 11.80 Over a certain mass ru It is clear that the glass composition for glass fibers of Comparative Example 8 does not have a sufficient working temperature range, and therefore cannot produce glass fibers with a sufficiently low dielectric loss tangent in the high-frequency region of 10 GHz.

[0177] Furthermore, it is clear that, according to the glass fiber composition of Comparative Example 9, in which the P2O5 content exceeds 0.20% by mass relative to the total amount of the glass fiber composition, it is not possible to obtain glass fibers with sufficiently low dielectric constant and dielectric loss tangent in the high-frequency range of 10 GHz.

Claims

1. SiO in the range of 59.60 to 65.00% by mass based on the total amount of the glass composition for glass fibers ２ and B in the range of 18.00 to 26.00% by mass ２ O ３ and Al in the range of 7.00 to 11.80% by mass ２ O ３ and CaO in the range of 0 to 4.80% by mass, MgO in the range of 0 to 4.00% by mass, SrO in the range of 0 to 6.00% by mass, and TiO in the range of 0.10 to 5.00% by mass ２ and F and Cl in a total range of 0.80 to 2.00% by mass ２ and Cl ２ and containing ２ O ５ with a P content of less than 0.20% by mass and a total content of Na ２ O, K ２ O and Li ２ O of less than 1.00% by mass, a glass composition for glass fibers.

2. Glass fiber comprising the glass composition for glass fiber according to claim 1.

3. A glass fiber fabric characterized by containing the glass fibers described in claim 2.

4. A glass fiber reinforced resin composition characterized by containing the glass fibers described in claim 2.

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