Glass composition for glass fiber, glass fiber, glass fiber fabric and glass fiber reinforced resin composition

Abstract

The present invention provides a glass composition for glass fibers. The glass composition for glass fibers is biosoluble and can be formed into long fibers. The glass composition for glass fibers of the present invention contains SiO2 in a range of 35.0 to 55.0 mass%, B2O3 in a range of 10.0 to 30.0 mass%, Al2O3 in a range of 14.5 to 30.0 mass%, and CaO and MgO in a range of 8.7 to 25.0 mass% in total, wherein the SiO2 content S, the B2O3 content B, the Al2O3 content A, the CaO content C, and the MgO content M satisfy the following formula (1): 11.3 ≤ S × (C + M) / (A + B) ≤ 20.7…(1).

Description

Technical Field

[0001] The present invention relates to a glass composition for glass fibers, glass fibers composed of the glass composition for glass fibers, glass fiber fabrics composed of the glass fibers, and a glass fiber-reinforced resin composition containing the glass fibers. Background Art

[0002] Conventionally, short glass fibers have been required to have biosolubility, which means they can be dissolved in physiological fluids such as lung fluid (for example, see Patent Document 1).

[0003] Short glass fibers are formed into a cotton-like shape by blowing molten glass through high-pressure air or centrifugal force. These fibers are then enclosed in bags or coated with external materials for use in building materials such as thermal insulation and sound absorption. During the manufacturing and use of short glass fibers, extremely fine fibers are occasionally generated. To reduce the health risks associated with inhalation and accumulation of these fine fibers in the human body, biosolubility is crucial for short glass fibers.

[0004] On the other hand, long glass fibers are used in glass fiber-reinforced resin compositions or glass fiber-reinforced resin molded articles, which are composite materials of glass fiber and resin. These long glass fibers are produced by flowing molten glass of controlled viscosity from a nozzle, winding them up with a winder, and then cutting them into filaments or braiding them. Long glass fibers are often larger in diameter than short glass fibers, and the likelihood of producing extremely fine fibers during the manufacturing process or use is extremely low. Therefore, their biosolubility has not been a priority.

[0005] However, in recent years, demands for lighter, thinner, and smaller printed wiring boards, including glass fiber-reinforced resin molded products, particularly glass fiber fabrics, have been increasing. Consequently, long glass fibers are being required to be extremely fine. Therefore, biosolubility is expected to become an important property in the future.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application No. 2007-507413 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] However, when using a glass composition recognized as biosoluble in short glass fibers, there is a problem in that it is difficult to produce long glass fibers.

[0011] Therefore, an object of the present invention is to solve the above-mentioned problems and provide a glass composition for glass fibers that is biosoluble and can be formed into long fibers.

[0012] Means for solving problems

[0013] In order to achieve the above-mentioned object, the glass composition for glass fiber of the present invention is characterized in that it contains SiO2 in a range of 35.0 to 55.0 mass%, B2O3 in a range of 10.0 to 30.0 mass%, Al2O3 in a range of 14.5 to 30.0 mass%, and CaO and MgO in a range of 8.7 to 25.0 mass% in total, and the content S of the SiO2, the content B of the B2O3, the content A of the Al2O3, the content C of the CaO and the content M of the MgO satisfy the following formula (1).

[0014] 11.3≤S×(C+M) / (A+B)≤20.7…(1)

[0015] In the glass composition for glass fibers of the present invention, when the content of the above-mentioned SiO2 relative to the total amount is set to S, the content of the above-mentioned B2O3 relative to the total amount is set to B, the content of the above-mentioned Al2O3 relative to the total amount is set to A, the content of the above-mentioned CaO relative to the total amount is set to C, and the content of the above-mentioned MgO relative to the total amount is set to M, by making the above-mentioned S, the above-mentioned B, the above-mentioned A, the above-mentioned C and the above-mentioned M satisfy the above-mentioned formula (1), when the glass composition for glass fibers is made into glass fibers, biosolubility can be obtained and long fibers can be achieved.

[0016] In addition, it is preferable that the above-mentioned S, the above-mentioned B, the above-mentioned A, the above-mentioned C, and the above-mentioned M in the glass composition for glass fibers of the present invention satisfy the following formula (2).

[0017] 12.5≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤70.2…(2)

[0018] In addition, it is preferable that the above-mentioned S, the above-mentioned B, the above-mentioned A, the above-mentioned C, and the above-mentioned M in the glass composition for glass fibers of the present invention satisfy the following formula (3).

[0019] 11.3≤S×(C+M) / (A+B)≤19.3…(3)

[0020] When the glass composition for glass fibers of the present invention satisfies the above formula (3), the glass composition for glass fibers can be made into glass fibers with excellent biosolubility and can be formed into long fibers.

[0021] From the perspective of reducing the melt viscosity of molten glass and facilitating the formation of long fibers, the glass composition for glass fibers of the present invention, which contains SiO2 in a range of 37.0 to 49.5 mass%, B2O3 in a range of 16.5 to 29.0 mass%, Al2O3 in a range of 15.0 to 28.0 mass%, CaO in a range of 10.5 to 21.0 mass%, and MgO in a range of 0 to 6.5 mass%, may contain TiO2 in a range of 0 to 0.4 mass% relative to the total amount. On the other hand, if the TiO2 content exceeds 0.4 mass% relative to the total amount in the above composition, the biosolubility of the glass fiber produced from the glass composition for glass fibers may be reduced.

[0022] In addition, the above-mentioned S, B, A, C and M in any of the above-mentioned glass compositions for glass fibers of the present invention more preferably satisfy the following formula (4), further preferably satisfy the following formula (5), and particularly preferably satisfy the following formula (6).

[0023] 13.6≤S×(C+M) / (A+B)≤17.5…(4)

[0024] 16.2≤S×(C+M) / (A+B)≤17.2…(5)

[0025] 16.6≤S×(C+M) / (A+B)≤16.9…(6)

[0026] By making the above-mentioned S, B, A, C and M of any one of the glass compositions for glass fibers of the present invention satisfy the above-mentioned formula (4), when the glass composition for glass fibers is made into glass fibers, it has excellent biosolubility, and the balance of biosolubility is good, and it is easy to achieve long fiberization. In addition, by making the above-mentioned S, B, A, C and M of any one of the glass compositions for glass fibers of the present invention satisfy the above-mentioned formula (5), when the glass composition for glass fibers is made into glass fibers, it has more excellent biosolubility, and the balance of biosolubility is good, and it is easy to achieve long fiberization. Moreover, by making the above-mentioned S, B, A, C and M of any one of the glass compositions for glass fibers of the present invention satisfy the above-mentioned formula (6), it is possible to more reliably have more excellent biosolubility, and the balance of biosolubility is good, and it is easy to achieve long fiberization.

[0027] The glass fiber of the present invention is characterized in that it comprises glass filaments formed from any of the above-mentioned glass compositions for glass fibers. In the glass fiber of the present invention, the glass filaments preferably have a filament diameter of less than 3.0 μm.

[0028] Furthermore, the glass fiber fabric of the present invention is characterized in that it is composed of the above-mentioned glass fibers.

[0029] Furthermore, the glass fiber-reinforced resin composition of the present invention is characterized by containing the above-mentioned glass fiber. DETAILED DESCRIPTION

[0030] Next, embodiments of the present invention will be described in more detail.

[0031] The glass composition for glass fiber of this embodiment contains SiO2 in the range of 35.0 to 55.0 mass%, B2O3 in the range of 10.0 to 30.0 mass%, Al2O3 in the range of 14.5 to 30.0 mass%, and CaO and MgO in the range of 8.7 to 25.0 mass% in total, and the content S of SiO2, the content B of B2O3, the content A of Al2O3, the content C of CaO and the content M of MgO satisfy the following formula (1).

[0032] 11.3≤S×(C+M) / (A+B)≤20.7…(1)

[0033] In the glass composition for glass fibers of this embodiment, if the SiO2 content relative to the total amount is less than 35.0% by mass, the strength and elastic modulus of the long glass fibers decrease, and when used in a composite material with a resin, the resin reinforcement effect becomes insufficient. On the other hand, if the SiO2 content relative to the total amount exceeds 55.0% by mass, biosolubility may decrease.

[0034] In the glass composition for glass fiber of this embodiment, the content of SiO2 relative to the total amount is preferably in the range of 37.0 to 49.5 mass%, more preferably in the range of 37.5 to 48.5 mass%, further preferably in the range of 38.0 to 47.5 mass%, particularly preferably in the range of 38.5 to 46.5 mass%, and most preferably in the range of 39.0 to 45.0 mass%.

[0035] In addition, in the glass composition for glass fibers of this embodiment, when the content of B2O3 relative to the total amount is less than 10.0% by mass, the devitrification temperature of the molten glass becomes high, which may make it difficult to form long fibers and may also lead to a decrease in biosolubility. On the other hand, when the content of B2O3 relative to the total amount is greater than 30.0% by mass, phase separation occurs in the molten glass, making it difficult to form long fibers.

[0036] In the glass composition for glass fiber of the present embodiment, the content of B2O3 relative to the total amount is preferably in the range of 14.5 to 30.0 mass%, more preferably in the range of 15.5 to 29.5 mass%, further preferably in the range of 16.5 to 29.0 mass%, particularly preferably in the range of 16.7 to 25.5 mass%, particularly preferably in the range of 17.0 to 24.4 mass%, extremely preferably in the range of 17.2 to 22.0 mass%, and most preferably in the range of 17.5 to 20.5 mass%.

[0037] Furthermore, in the glass composition for glass fibers of this embodiment, when the Al2O3 content relative to the total amount is less than 14.5% by mass, the strength and elastic modulus of the long glass fibers decrease, and when the glass composition for glass fibers is used in a composite material with a resin, the resin reinforcement effect becomes insufficient. On the other hand, when the Al2O3 content relative to the total amount exceeds 30.0% by mass, the devitrification temperature of the molten glass becomes high, making it difficult to form long fibers.

[0038] In the glass composition for glass fiber of this embodiment, the content of Al2O3 relative to the total amount is preferably in the range of 15.0 to 28.0 mass%, more preferably in the range of 17.0 to 27.0 mass%, further preferably in the range of 19.0 to 26.0 mass%, particularly preferably in the range of 21.0 to 25.5 mass%, and most preferably in the range of 23.0 to 25.0 mass%.

[0039] In the glass composition for glass fibers of the present invention, if the combined content of CaO and MgO relative to the total amount is less than 8.7% by mass, the biosolubility of the long glass fibers may be reduced. On the other hand, if the combined content of CaO and MgO relative to the total amount exceeds 25.0% by mass, the devitrification temperature of the molten glass becomes high, making it difficult to form long fibers.

[0040] In the glass composition for glass fibers of the present embodiment, the combined content of CaO and MgO relative to the total amount is preferably in the range of 9.0 to 23.0 mass %, more preferably in the range of 14.0 to 22.0 mass %, further preferably in the range of 15.0 to 21.0 mass %, particularly preferably in the range of 16.0 to 20.0 mass %, and most preferably in the range of 17.0 to 19.5 mass %.

[0041] Here, the content of CaO relative to the total amount of the glass composition for glass fibers of the present embodiment is, for example, in the range of 8.0 to 25.0 mass %, preferably in the range of 10.5 to 21.0 mass %, more preferably in the range of 13.0 to 20.5 mass %, further preferably in the range of 14.5 to 20.0 mass %, particularly preferably in the range of 16.0 to 19.5 mass %, and most preferably in the range of 17.0 to 19.5 mass %.

[0042] On the other hand, the content of MgO relative to the total amount of the glass composition for glass fiber of this embodiment is, for example, in the range of 0 to 10.0 mass%, preferably in the range of 0 to 6.5 mass%, more preferably in the range of 0 to 6.0 mass%, further preferably in the range of 0 to 3.0 mass%, particularly preferably in the range of 0 to 1.0 mass%, and most preferably in the range of 0 to 0.9 mass%.

[0043] In the glass composition for glass fiber of the present embodiment, when the content of the above-mentioned SiO2 relative to the total amount is set to S, the content of the above-mentioned B2O3 relative to the total amount is set to B, the content of the above-mentioned Al2O3 relative to the total amount is set to A, the content of the above-mentioned CaO relative to the total amount is set to C, and the content of the above-mentioned MgO relative to the total amount is set to M, by making the above-mentioned S, the above-mentioned B, the above-mentioned A, the above-mentioned C and the above-mentioned M satisfy the above-mentioned formula (1), biosolubility can be obtained when the glass fiber is made, and long fiberization can be achieved.

[0044] Here, "biosoluble" means that the total amount of SiO2 and Al2O3 dissolved in artificial lung fluid, as measured by the method described below, is 100.0 μg / h or greater. Furthermore, "capable of lengthening the glass fiber" means that, when the operating temperature range ΔT (ΔT = 1000 poise temperature - liquidus temperature) is set using the 1000 poise temperature and the liquidus temperature, as measured by the method described below, ΔT is -10°C or greater.

[0045] In addition, the above-mentioned S, the above-mentioned B, the above-mentioned A, the above-mentioned C and the above-mentioned M of the glass composition for glass fiber of this embodiment satisfy the following formula (2), preferably satisfy the following formula (2-1), more preferably satisfy the following formula (2-2), further preferably satisfy the following formula (2-3), especially preferably satisfy the following formula (2-4), particularly preferably satisfy the following formula (2-5), extremely preferably satisfy the following formula (2-6) and most preferably satisfy the following formula (2-7).

[0046] 12.5≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤70.2…(2)

[0047] 15.0≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤65.0…(2-1)

[0048] 17.5≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤62.5…(2-2)

[0049] 20.0≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤62.0…(2-3)

[0050] 25.0≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤61.5…(2-4)

[0051] 30.0≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤61.0…(2-5)

[0052] 40.0≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤60.5…(2-6)

[0053] 50.0≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤60.0…(2-7)

[0054] In addition, it is preferable that the above-mentioned S, the above-mentioned B, the above-mentioned A, the above-mentioned C, and the above-mentioned M in the glass composition for glass fibers of the present embodiment satisfy the following formula (3).

[0055] 11.3≤S×(C+M) / (A+B)≤19.3…(3)

[0056] By making the above-mentioned S, B, A, C and M of the glass composition for glass fibers of this embodiment satisfy the above-mentioned formula (3), when the glass composition for glass fibers is made into glass fibers, excellent biosolubility can be obtained and long fibers can be achieved.

[0057] Here, the glass fiber having excellent biosolubility means that the total amount of SiO 2 eluted into the artificial lung fluid and the amount of Al 2 O 3 eluted into the artificial lung fluid, as measured by the method described below, is 105.0 μg / h or more.

[0058] From the perspective of reducing the melt viscosity of the molten glass and thus facilitating the formation of long fibers, the glass composition for glass fibers of the present embodiment, which contains SiO2 in a range of 37.0 to 49.5 mass%, B2O3 in a range of 16.5 to 29.0 mass%, Al2O3 in a range of 15.0 to 28.0 mass%, CaO in a range of 10.5 to 21.0 mass%, and MgO in a range of 0 to 6.5 mass%, may contain TiO2 in a range of 0 to 0.4 mass% relative to the total amount. On the other hand, in the above composition, if the TiO2 content exceeds 0.4 mass% relative to the total amount, the biosolubility of the resulting glass fibers may be reduced.

[0059] When the glass composition for glass fibers of the present embodiment contains TiO2, the content of TiO2 relative to the total amount of the glass composition for glass fibers of the present embodiment is preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0060] In addition, it is more preferred that the above-mentioned S, the above-mentioned B, the above-mentioned A, the above-mentioned C and the above-mentioned M of any of the above-mentioned glass compositions for glass fibers of this embodiment satisfy the following formula (4), further preferably satisfy the following formula (5), and particularly preferably satisfy the following formula (6).

[0061] 13.6≤S×(C+M) / (A+B)≤17.5…(4)

[0062] 16.2≤S×(C+M) / (A+B)≤17.2…(5)

[0063] 16.6≤S×(C+M) / (A+B)≤16.9…(6)

[0064] By making the above-mentioned S, B, A, C and M of any of the glass compositions for glass fibers of this embodiment satisfy the above-mentioned formula (4), when glass fibers are made, they have excellent biosolubility, a good balance of biosolubility, and are easily transformed into long fibers. In addition, by making the above-mentioned S, B, A, C and M of any of the glass compositions for glass fibers of this embodiment satisfy the above-mentioned formula (5), when glass fibers are made, they have even better biosolubility, a good balance of biosolubility, and are easily transformed into long fibers. Moreover, by making the above-mentioned S, B, A, C and M of any of the glass compositions for glass fibers of this embodiment satisfy the above-mentioned formula (6), even better biosolubility can be more reliably obtained, and a good balance of biosolubility can be easily transformed into long fibers.

[0065] Here, a well-balanced biosolubility of the glass fiber means that the ratio of the amount of Al2O3 dissolved in the artificial lung fluid to the amount of SiO2 dissolved in the artificial lung fluid (Al2O3 dissolved / SiO2 dissolved) is within the range of 0.7 to 1.3; and even better biosolubility means that the total amount of SiO2 dissolved in the artificial lung fluid and the amount of Al2O3 dissolved in the artificial lung fluid is 120.0 μg / h or greater. Furthermore, easy fiberization of the glass fiber means that the operating temperature range ΔT is 99°C or greater.

[0066] Furthermore, the total content of SiO2, B2O3, Al2O3, CaO and MgO relative to the total amount in the glass composition for glass fiber of the present embodiment is, for example, 91.0 mass% or more, preferably 95.0 mass% or more, more preferably 98.0 mass% or more, further preferably 99.0 mass% or more, particularly preferably 99.3 mass% or more, particularly preferably 99.5 mass% or more, extremely preferably 99.7 mass% or more and most preferably 99.9 mass% or more.

[0067] Furthermore, from the perspective of improving the degassing properties of the molten glass and improving the stability of fiber formation, the glass composition for glass fibers of this embodiment may contain Fe2O3. The content of Fe2O3 relative to the total amount of the glass composition for glass fibers of this embodiment is, for example, in the range of 0 to 0.4 mass%, preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0068] Furthermore, from the perspective of reducing the melt viscosity of the molten glass and thereby facilitating the formation of long fibers, the glass composition for glass fibers of this embodiment may also contain ZrO2. The content of ZrO2 relative to the total amount of the glass composition for glass fibers of this embodiment is, for example, in the range of 0 to 0.4 mass%, preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0069] Furthermore, from the perspective of reducing the melt viscosity of the molten glass and thereby facilitating the formation of long fibers, the glass composition for glass fibers of this embodiment may also contain Li2O, K2O, and Na2O. The total content of Li2O, K2O, and Na2O relative to the total amount of the glass composition for glass fibers of this embodiment is, for example, in the range of 0 to 0.4 mass%, preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0070] Furthermore, from the perspective of improving the degassing properties of the molten glass and improving the stability of fiber formation, the glass composition for glass fibers of this embodiment may contain F2 and Cl2. The total content of F2 and Cl2 relative to the total amount of the glass composition for glass fibers of this embodiment is, for example, in the range of 0 to 0.4 mass%, preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0071] Furthermore, from the perspective of reducing the melt viscosity of the molten glass and facilitating the formation of long fibers, the glass composition for glass fibers of this embodiment may also contain SrO. The content of SrO relative to the total amount of the glass composition for glass fibers of this embodiment is, for example, in the range of 0 to 0.4 mass%, preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0072] Furthermore, from the perspective of suppressing the increase in the devitrification temperature of the molten glass and thus facilitating the formation of long fibers, the glass composition for glass fibers of this embodiment may also contain ZnO. The content of ZnO relative to the total amount of the glass composition for glass fibers of this embodiment is, for example, in the range of 0 to 0.4 mass%, preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0073] Furthermore, from the perspective of suppressing the increase in the devitrification temperature of the molten glass and thus facilitating the formation of long fibers, the glass composition for glass fibers of this embodiment may also contain SnO2. The content of SnO2 relative to the total amount of the glass composition for glass fibers of this embodiment is, for example, in the range of 0 to 0.4 mass%, preferably in the range of 0 to 0.3 mass%, more preferably in the range of 0 to 0.2 mass%, further preferably in the range of 0 to 0.1 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%.

[0074] Furthermore, from the perspective of suppressing the increase in the devitrification temperature of the molten glass and thus facilitating the formation of long fibers, the glass composition for glass fibers of this embodiment may contain P2O5. From the perspective of suppressing the generation of bubbles in the molten glass, the content of P2O5 relative to the total amount of the glass composition for glass fibers of this embodiment is preferably, for example, less than 2.5% by mass. The content of P2O5 relative to the total amount of the glass composition for glass fibers of this embodiment is preferably, for example, less than 2.5% by mass, more preferably less than 2.0% by mass, further preferably less than 1.5% by mass, particularly preferably less than 1.0% by mass, particularly preferably less than 0.8% by mass, extremely preferably less than 0.6% by mass, and most preferably less than 0.5% by mass.

[0075] The glass composition for glass fibers of the present embodiment may contain oxides of Ba, Mn, Co, Ni, Cu, Cr, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb as impurities derived from the raw materials, with the total content being less than 1.00% by mass relative to the total amount of the glass composition for glass fibers. In particular, when the glass composition for glass fibers of the present embodiment contains BaO, CeO2, Y2O3, La2O3, Bi2O3, Gd2O3, Pr2O3, Sc2O3, or Yb2O3 as impurities, the content of each impurity 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.

[0076] In the glass composition for glass fibers of the present embodiment, the content of each component can be measured by using an ICP emission spectrometer to measure Li as a light element and a wavelength dispersive X-ray fluorescence analyzer to measure other elements.

[0077] The measurement method involves first placing a glass batch or glass fiber mixed with glass raw materials into a platinum crucible and stirring it in an electric furnace for 6 hours at 1500°C for glass batch or 1450°C for glass fiber, melting it while stirring to produce a homogeneous molten glass. If organic matter adheres to the surface of the glass fiber, or if the glass fiber is primarily contained in an organic material such as a resin as a reinforcing material, the glass fiber is heated in a muffle furnace for approximately 0.5 to 24 hours, for example, at 300 to 650°C, to remove the organic matter before use. The resulting molten glass is then poured onto a carbon plate to produce glass chips, which are then crushed and powdered to produce glass powder. The glass powder is then decomposed by heating with acid, and then quantitatively analyzed for Li, a light element, using an ICP emission spectrometer. After the glass powder is formed into a disc using a press, quantitative analysis of other elements is performed using a wavelength-dispersive X-ray fluorescence analyzer. These quantitative analysis results are converted into oxides to calculate the content and total amount of each component, and the content rate (mass %) of each component can be determined based on these values.

[0078] Next, the glass fiber of the present embodiment includes glass filaments composed of the glass composition for glass fibers of the present embodiment described above.

[0079] The glass fibers of this embodiment are produced as follows. First, glass raw materials (batch glass) are prepared to form the glass composition for the glass fibers of this embodiment based on the components contained in the ore serving as the glass raw material, the content ratios of the components, and the volatilization of the components during melting. This glass raw material is then supplied to a melting furnace and melted at a temperature ranging from, for example, 1450°C to 1550°C. The molten glass batch (molten glass) is then drawn from 1 to 20,000 nozzle heads of a sheath controlled at a predetermined temperature and rapidly cooled to form glass filaments.

[0080] In order to produce the above-mentioned glass fiber, when the glass composition for glass fiber of this embodiment is melted at a temperature within the above-mentioned range, 1000 poise temperature and liquidus temperature are used. When the operating temperature range ΔT is set to 1000 poise temperature - liquidus temperature, by making ΔT above -10°C, long fiberization can be achieved, and by making ΔT above 99°C, long fiberization can be easily achieved.

[0081] Here, the glass single fiber (glass filament) ejected from a nozzle head or hole and cooled and solidified usually has a perfect circular cross-sectional shape, preferably having a diameter (filament diameter) of less than 3.0 μm. On the other hand, when the above-mentioned nozzle head has a non-circular shape and has a protrusion or cutout portion that can quench the molten glass, by controlling the temperature conditions, it is possible to produce glass filaments with non-circular cross-sectional shapes such as elliptical and oblong. When the glass filament has an elliptical or oblong cross-sectional shape, it is preferred that the fiber diameter when the cross-sectional area is converted into a perfect circle, that is, the converted fiber diameter is less than 3.0 μm. It should be noted that the lower limit of the above-mentioned filament diameter is, for example, 0.5 μm, preferably 1.0 μm, and more preferably 2.0 μm.

[0082] The filament diameter of above-mentioned glass filament can be calculated by the following method for example.First, glass fiber is embedded in resin such as epoxy resin, this resin is solidified, and the resin after solidification is cut off, and its cross section is ground.Then, use electron microscope to observe the cross section of the resin after solidification, when the cross-sectional shape of this glass filament is a perfect circle or roughly perfect circle, measure the diameter of more than 50 glass filaments 50 exposed in the above-mentioned cross section.In addition, when the cross-sectional shape of this glass filament is beyond a perfect circle or roughly perfect circle, after calculating its cross-sectional area, calculate the conversion fiber diameter based on this cross-sectional area.Then, utilize the diameter measured or calculated or calculate by the mean value of obtaining the conversion fiber diameter to calculate filament diameter.In addition, also can measure the filament diameter of above-mentioned glass filament by utilizing automatic analysis device that the image obtained by electron microscope is carried out image processing.

[0083] On the other hand, when the glass fiber of this embodiment is a glass fiber-reinforced resin molded article, the filament diameter of the glass filaments can be measured, for example, as follows. First, the glass fiber-reinforced resin molded article is heated at 625°C for 30 minutes to burn off the thermoplastic resin, and the glass fibers are removed. Next, the filament diameter of the glass filaments is measured in the same manner as the method for measuring the filament diameter of the glass filaments in the glass fiber.

[0084] Next, a sizing agent or a binder is applied to the formed glass filaments using a coater as a coating device. 1 to 20,000 glass filaments are bundled using a gathering shoe and wound onto a bobbin at high speed using a winder to produce glass fibers.

[0085] To improve the bundling properties of the glass filaments, enhance the adhesion between the glass fibers and the resin, and enhance the uniform dispersion of the glass fibers in a mixture of the glass fibers and the resin or inorganic material, the glass fibers of this embodiment may also be coated with an organic material. Examples of such organic materials include starch, polyurethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene, particularly carboxylic acid-modified polypropylene, (poly)carboxylic acid, particularly copolymers of maleic acid and unsaturated monomers, and the like. Furthermore, in addition to being coated with these resins, the glass fibers of this embodiment may also be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, and the like. Alternatively, the glass fibers of this embodiment may not contain the aforementioned resins, but instead be coated with a treatment composition containing a silane coupling agent, a surfactant, and the like. Based on the mass of the glass fibers of this embodiment uncoated with the resin composition or treatment composition, the glass fibers are coated with such a resin composition or treatment composition at a ratio of 0.03 to 2.0 mass %. It should be noted that the coating of the glass fiber with the organic substance can be carried out, for example, by the following method: in the manufacturing process of the glass fiber, a resin solution or a resin composition solution is imparted to the glass fiber using a known method such as a roller coater, and then the glass fiber imparted with the resin solution or the resin composition solution is dried. Alternatively, the glass fiber of the present embodiment formed into a fabric form can be immersed in a treatment agent composition solution, and then the glass fiber imparted with the treatment agent composition is dried.

[0086] Here, examples of the silane coupling agent include aminosilane, urea silane, chlorosilane, epoxy silane, mercaptosilane, vinyl silane, (meth)acrylic silane, phenyl silane, styryl silane, and isocyanate silane. In this embodiment, one of the above silane coupling agents may be used alone, or two or more of the above silane coupling agents may be used in combination.

[0087] Examples of the aminosilane include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N′-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0088] Examples of ureidosilane include γ-ureidopropyltriethoxysilane and the like.

[0089] Examples of the chlorosilane include γ-chloropropyltrimethoxysilane and the like.

[0090] Examples of epoxysilane include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0091] Examples of the mercaptosilane include γ-mercaptotrimethoxysilane and γ-mercaptopropyltrimethoxysilane.

[0092] Examples of the vinylsilane include vinyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, and N-benzyl-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0093] As the (meth)acrylic silane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc. can be mentioned.

[0094] Examples of phenylsilane include phenyltrimethoxysilane and the like.

[0095] Examples of the styrylsilane include p-styryltrimethoxysilane.

[0096] Examples of the isocyanate silane include γ-isocyanate propyltriethoxysilane and the like.

[0097] Examples of lubricants include modified silicone oils, animal oils and their hydrides, vegetable oils and their hydrides, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimine, polyalkylpolyamine alkyl linolenic acid derivatives, fatty acid amides, and quaternary ammonium salts. In this embodiment, one of these lubricants may be used alone, or two or more may be used in combination.

[0098] Examples of animal oils include beef tallow and the like.

[0099] Examples of the vegetable oil include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.

[0100] Examples of animal wax include beeswax and wool.

[0101] Examples of the vegetable wax include candelilla wax and carnauba wax.

[0102] Examples of the mineral wax include paraffin wax and montan wax.

[0103] Examples of the condensation product of a higher saturated fatty acid and a higher saturated alcohol include stearic acid esters such as lauryl stearate.

[0104] Examples of the fatty acid amide include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid.

[0105] Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0106] Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, one of these surfactants may be used alone, or two or more of these surfactants may be used in combination.

[0107] Examples of the nonionic surfactant include ethylene oxide propylene oxide alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene-block copolymers, alkyl polyoxyethylene-polyoxypropylene-block copolymer ethers, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid monoesters, polyoxyethylene fatty acid diesters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid ester ethylene oxide adducts, polyoxyethylene stearyl ethers, hydrogenated castor oil ethylene oxide adducts, alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, glycerol fatty acid esters, polyglycerol fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyol alkyl ethers, fatty acid alkanolamides, acetylene glycols, ethylene oxide adducts of acetylene glycols, and ethylene oxide adducts of acetylene alcohols.

[0108] Examples of the cationic surfactant include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethylsulfate, higher alkylamine salts (acetates or hydrochlorides, etc.), ethylene oxide adducts of higher alkylamines, condensates of higher fatty acids and polyalkylenepolyamines, ester salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridinium salts.

[0109] Examples of the anionic surfactant include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzenesulfonates, α-olefinsulfonates, reaction products of fatty acid halides and N-methyltaurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphates of higher alcohol ethylene oxide adducts.

[0110] Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as alkylaminopropionic acid alkali metal salts, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.

[0111] Examples of the form of glass fiber include woven fabric (glass cloth), braid, yarn, chopped strand, roving, chopped strand mat, paper, web, combined cloth, and milled fiber. Woven fabric (glass cloth) is preferably used.

[0112] Next, the glass fiber fabric of this embodiment is composed of the glass fibers of this embodiment. The glass fabric of this embodiment can be obtained by weaving the glass fibers of this embodiment as warp and weft yarns using a known loom. Examples of such looms include jet looms such as air jet looms and water jet looms, shuttle looms, and rapier looms. Furthermore, examples of weaving methods used on such looms include plain weave, satin weave, basket weave, and twill weave. From the perspective of manufacturing efficiency, plain weave is preferably used.

[0113] The above-mentioned glass fibers of this embodiment contained in the glass fiber fabric of this embodiment are preferably composed of glass filaments having a filament diameter of greater than 2.0 μm and less than 9.0 μm, and have a mass of 0.5 to 70.0 tex (g / 1000 m). More preferably, the above-mentioned glass fibers are composed of glass filaments having a filament diameter of greater than 2.0 μm and less than 3.0 μm, and have a mass of 0.5 to 1.5 tex.

[0114] Here, the filament diameter of the above-mentioned glass fiber of this embodiment contained in the glass fiber fabric of this embodiment is the average value of the following measured values: the measured values ​​when the diameter of the glass filaments constituting the above-mentioned glass fiber is measured with a scanning electron microscope (manufactured by Hitachi High-Technologies Co., Ltd., trade name: S-3400N, magnification: 3000 times) for at least 50 cross sections of the above-mentioned glass fiber.

[0115] Furthermore, the glass fiber fabric of the present embodiment is preferably composed of warp yarns having a weave density of 40 to 150 yarns / 25 mm and weft yarns having a weave density of 40 to 150 yarns / 25 mm.

[0116] The warp yarn density can be determined by counting the number of warp yarns within a 25 mm range in the warp direction using a fabric analyzer in accordance with JIS R 3420. The weft yarn density can be determined by counting the number of weft yarns within a 25 mm range in the weft direction using a fabric analyzer in accordance with JIS R 3420.

[0117] The glass fiber fabric of this embodiment may be subjected to deoiling, surface treatment, and fiber opening treatment after weaving.

[0118] As the deoiling treatment, there can be mentioned a treatment in which the glass fiber fabric is placed in a heating furnace at an atmospheric temperature of 350° C. to 400° C. for 40 to 80 hours to thermally decompose organic matter adhering to the glass fiber.

[0119] Examples of the surface treatment include immersing the glass fiber fabric in a solution containing the aforementioned silane coupling agent or in a solution containing the aforementioned silane coupling agent and the aforementioned surfactant, removing excess water, and then heating and drying the woven fabric at a temperature in the range of 80 to 180° C. for 1 to 30 minutes.

[0120] Examples of fiber-opening treatments include applying a tension of 20 to 200 N to the warp yarns of the glass fiber fabric and then performing fiber-opening using water pressure, fiber-opening using high-frequency vibration using a liquid as a medium, fiber-opening using fluid pressure having surface pressure, fiber-opening using roller pressure, etc., thereby widening the linear width of the warp and weft yarns.

[0121] In addition, the glass fiber fabric of this embodiment preferably has a weight of 5.0 to 220 g / m 2 The quality is in the range of and has a thickness in the range of 4.0 to 200.0 μm.

[0122] The glass fiber fabric of this embodiment may also include a surface-treated layer containing the aforementioned silane coupling agent or containing the aforementioned silane coupling agent and the aforementioned surfactant. When the glass fiber fabric of this embodiment includes such a surface-treated layer, the surface-treated layer may, for example, have a mass in the range of 0.03 to 1.50 mass % relative to the total mass of the glass fiber fabric including the surface-treated layer.

[0123] The glass fiber-reinforced resin composition of this embodiment contains the glass fiber of this embodiment described above. Specifically, the glass fiber-reinforced resin composition of this embodiment comprises a resin (thermoplastic resin or thermosetting resin), glass fiber, and other additives, and contains 10 to 90% by mass of glass fiber relative to 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 the resin and 0 to 40% by mass of other additives relative to the total amount of the glass fiber-reinforced resin composition.

[0124] Here, examples of the thermoplastic resin 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), polypropylene terephthalate (PPT ... Poly(vinyl thiophene) (PTT), polycarbonate, polyarylene sulfide, polyethersulfone (PES), polyphenylene sulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryletherketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), 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, polybutene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, etc.

[0125] 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.

[0126] Examples of the polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0127] Examples of polystyrene include general-purpose polystyrene (GPPS) which is atactic polystyrene having an atactic structure, high-impact polystyrene (HIPS) obtained by adding a rubber component to GPPS, and syndiotactic polystyrene having a syndiotactic structure.

[0128] Examples of the methacrylic resin include polymers obtained by polymerizing one methacrylic acid resin selected from 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 the above methacrylic resins.

[0129] 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 with monomers copolymerizable with vinyl chloride monomers, and graft copolymers in which vinyl chloride monomers are graft-polymerized onto polymers.

[0130] Examples of polyamides include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanamide (nylon 612), polydecamethylene adipamide (nylon 106), polymethyl decanediol (nylon 106), polyhexamethylene adipamide (nylon 106), polyhexamethylene dodecan ... Polydecaneamide (nylon 1010), polydecaneamide (nylon 1012), polyundecanamide (nylon 11), polyhexamethylene adipamide (nylon 116), polydodecanamide (nylon 12), polyxylene adipamide (nylon D6), polyxylene sebacamide (nylon MXD10), polymethylene adipamide (nylon MXD6), polyparaxylene adipamide (nylon PXD6), polyterephthalamide (nylon 4T), polypentaethylene adipamide (nylon 116), polyhexamethylene adipamide (nylon 116), polydodecaneamide (nylon 112), polyxylene adipamide (nylon D6), polyxylene adipamide (nylon MXD10), polymethylene adipamide (nylon MXD6), polyparaxylene adipamide (nylon PXD6), polyterephthalamide (nylon 4T), polypentaethylene adipamide (nylon 116), polytetramethylene adipamide (nylon 116), polytetramethylene adipamide (nylon 116), polydodecaneamide (nylon 112), polyxylene adipamide (nylon D6), polyxylene adipamide (nylon MXD10), polymethylene adipamide (nylon MXD6), polytetramethylene adipamide (nylon 116), polytetramethylene adipamide (nylon 116), polytetramethylene adipamide (nylon 116), polydodecane ... Methyl terephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene terephthalamide (nylon 9T), polymethyl terephthalamide (nylon 10T), polyhexamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), polytetramethylene polyphthalamide (nylon 4I), polybis(3-methyl-4-amino) One of the components such as poly(3-methyl-4-aminohexyl)methane terephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methane isophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methane dodecylamide (nylon PACM12), polybis(3-methyl-4-aminohexyl)methane tetradecylamide (nylon PACM14), or a copolymer of two or more of the above components, or a mixture of the above components and the above copolymers, etc.

[0131] Examples of the polyacetal include homopolymers having oxymethylene units as main repeating units and copolymers mainly composed of oxymethylene units and containing oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0132] Examples of polyethylene terephthalate include polymers obtained by polycondensing ethylene glycol and terephthalic acid or a derivative thereof.

[0133] Examples of the polybutylene terephthalate include polymers obtained by polycondensing 1,4-butanediol and terephthalic acid or a derivative thereof.

[0134] Examples of polytrimethylene terephthalate include polymers obtained by polycondensing 1,3-propylene glycol and terephthalic acid or a derivative thereof.

[0135] Examples of the polycarbonate include polymers obtainable by an ester exchange method in which a dihydroxydiaryl compound is reacted with a carbonate such as diphenyl carbonate in a molten state, and polymers obtainable by a phosgene method in which a dihydroxydiaryl compound is reacted with phosgene.

[0136] Examples of the polyarylene sulfide include linear polyphenylene sulfide, cross-linked polyphenylene sulfide whose molecular weight is increased by a curing reaction after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.

[0137] Examples of the polyphenylene ether 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), poly(2-phenyl-1 4-phenylene ether), 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), poly(2,6-dimethyl-1,4-phenylene ether), and the like.

[0138] Examples of the modified polyphenylene ether 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 copolymers, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / maleic anhydride copolymers, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polyamides, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene / acrylonitrile copolymers, modified polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxyl groups, and styryl groups are introduced into the polymer chain terminals of the above polyphenylene ethers, and modified polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxyl groups, styryl groups, and methacryloyl groups are introduced into the side chains of the polymer chains of the above polyphenylene ethers.

[0139] Examples of the polyaryletherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).

[0140] As liquid crystal polymers (LCP), there can be mentioned (co)polymers composed of structural units of one or more components selected from the following components, such as aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, etc., which are thermotropic liquid crystal polyesters.

[0141] Examples of the fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyethylene fluoroethylene (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0142] Examples of the ionomer (IO) resin include copolymers of olefins or styrene and unsaturated carboxylic acids, wherein a portion of the carboxyl groups are neutralized with metal ions.

[0143] Examples of the olefin / vinyl alcohol resin include ethylene / vinyl alcohol copolymers, propylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymer saponification products, and propylene / vinyl acetate copolymer saponification products.

[0144] Examples of the cyclic olefin resin include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclic cycloolefins, and polymers of cyclic olefin monomers.

[0145] Examples of the polylactic acid include poly-L-lactic acid which is an L-isomer homopolymer, poly-D-lactic acid which is a D-isomer homopolymer, and stereocomplex polylactic acid which is a mixture thereof.

[0146] Examples of the cellulose resin include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0147] In addition, examples of the above-mentioned thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic resins (PF), polyurethane resins (PU), polyisocyanates, polyisocyanurates, modified polyimide (PI) resins, urea (UF) resins, silicone (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismaleimide triazine (BT) resins, diallyl phthalate resins (PDAP), and the like.

[0148] Specifically, examples of the unsaturated polyester resin include resins obtained by esterification reaction of an aliphatic unsaturated dicarboxylic acid and an aliphatic diol.

[0149] Examples of the vinyl ester resin include divinyl ester resin and novolac-based vinyl ester resin.

[0150] Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, bisphenol M epoxy resin (4,4'-(1,3-phenylenediisopropylidene) bisphenol type epoxy resin), bisphenol P epoxy resin (4,4'-(1,4-phenylenediisopropylidene) bisphenol type epoxy resin), bisphenol Z epoxy resin (4,4'-cyclohexene bisphenol type epoxy resin), phenol novolac epoxy resin, cresol novolac epoxy resin, and tetraphenylethane novolac epoxy resin. Varnish-type epoxy resins, novolac-type epoxy resins having a condensed-ring aromatic hydrocarbon structure, biphenyl-type epoxy resins, xylylene-type epoxy resins, phenyl aralkyl-type epoxy resins and other aralkyl-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalene diol-type epoxy resins, bifunctional or tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalene aralkyl-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, fluorene-type epoxy resins, etc.

[0151] Examples of the melamine resin include polymers formed by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0152] Examples of the phenolic resin include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol A novolac resin, resol-type phenolic resins such as methylol resol resin and dimethylene ether resol resin, and aryl alkylene resol resins, or a combination of two or more thereof.

[0153] Examples of the urea-formaldehyde resin include resins obtained by condensation of urea and formaldehyde.

[0154] The above-mentioned thermoplastic resin or thermosetting resin may be used alone or in combination of two or more resins.

[0155] Examples of the above-mentioned other additives include reinforcing fibers other than glass fibers such as carbon fibers and metal fibers, fillers other than glass fibers such as glass powder, talc, and mica, flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, flow improvers, anti-blocking agents, lubricants, nucleating agents, antibacterial agents, pigments, and the like.

[0156] The glass fiber reinforced resin composition of the present embodiment may be a prepreg obtained by impregnating the glass fiber fabric of the present embodiment with the resin by a known method and semi-curing the impregnated resin.

[0157] The glass fiber reinforced resin composition of the present embodiment can be molded by known molding methods to obtain various glass fiber reinforced resin molded products. As known molding methods, injection molding, injection compression molding, two-color molding, hollow molding, foaming molding including supercritical fluid, insert molding, in-mold coating molding, autoclave molding, extrusion molding, sheet molding, thermoforming, rotational molding, stacking molding, compression molding, blow molding, stamping molding, melting, hand lay-up molding, spraying, low-pressure RIM molding, resin transfer molding, sheet molding compound molding, bulk molding compound molding, pultrusion, filament winding, etc. can be used. In addition, by curing the above-mentioned prepreg, glass fiber reinforced resin molded products can also be obtained.

[0158] Examples of uses of such molded articles include printed wiring boards, electronic components such as connectors, housings of electronic devices such as antennas and radars, and separators for fuel cells.

[0159] Next, examples of the present invention and comparative examples are shown.

[0160] Example

[0161] (Examples 1 to 7, Comparative Examples 1 to 3)

[0162] First, glass raw materials were mixed so that the compositions of the glasses after melting and solidification would correspond to the compositions of Examples 1 to 7 and Comparative Examples 1 to 3 shown in Tables 2 to 4, thereby obtaining glass batch materials. The resulting glass batch materials were then placed in a platinum crucible and held in an electric furnace for 4 hours at a temperature suitable for melting the glass batch materials of each Example and Comparative Example, ranging from 1400°C to 1550°C. The glass batch materials were stirred and melted, thereby obtaining homogeneous molten glass. The resulting molten glass was then poured onto a carbon plate and cooled to obtain bulk glass chips.

[0163] Next, the obtained glass chips were used to evaluate biosolubility and the possibility of forming long fibers by the following methods.

[0164] [Biosoluble]

[0165] First, according to K. Sebastian et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2020), reagents No. 1 to 12 shown in Table 1 were added sequentially to approximately 800 mL of distilled water. The pH was adjusted to 4.5 using hydrochloric acid No. 13, resulting in a final volume of 1 L of artificial lung fluid with the composition shown in Table 1 and a pH of 4.5 that simulated the intrapulmonary environment. The prepared artificial lung fluid was then allowed to stand for 24 hours. Since the pH of the artificial lung fluid after standing increased with the desorption of carbon dioxide, the pH was adjusted back to 4.5 using hydrochloric acid.

[0166] It is known that when fibers are inhaled into the lungs, they are taken up by macrophages. Since the pH around macrophages is 4.5, fibers that are highly soluble in the artificial lung fluid at pH 4.5 can be expected to dissolve in the lungs.

[0167] (Table 1)

[0168] No. Components of artificial lung fluid Content (g / L) 1 Sodium chloride 7.12 2 Sodium bicarbonate 1.95 3 calcium chloride 0.022 4 Disodium hydrogen phosphate 0.148 5 sodium sulfate 0.079 6 Magnesium chloride hexahydrate 0.212 7 Glycine 0.118 8 Trisodium citrate dihydrate 0.152 9 Sodium tartrate dihydrate 0.18 10 Sodium pyruvate 0.172 11 90% lactic acid 0.156 12 formaldehyde 3mL 13 Hydrochloric acid (1:1) 4-5mL

[0169] Next, the glass chips were coarsely pulverized to obtain glass particles with a particle size of 0.5 to 1.5 mm. The obtained glass particles were then finely pulverized using an automatic mill and a ball mill. Particles that passed through a sieve with a nominal mesh size of 38 μm in accordance with JIS Z 8801-1 were used as test glass powder samples.

[0170] Next, according to K. Sebastian. et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2020), the test glass powder sample was loaded into a silicone tube with syringe filters at the top and bottom, and the artificial lung fluid heated to 37°C was infused at a flow rate of 140 to 170 mL / day using a pump and sent into the silicone tube. The filtrate passing through the test glass powder sample and the filter was accumulated in a container, thereby implementing a dissolution test. At this time, the mass of the test glass powder sample filled in the silicone tube was adjusted so that the flow rate of the artificial lung fluid (unit: μm 3 / s) and sample surface area (unit: μm 2 ) ratio (artificial lung fluid flow rate / sample surface area) becomes 0.030±0.005μm / s. After 24 hours, the filtrate is recovered from the container, and the analysis target ions are set to Si and Al. The eluted ion components in the filtrate are quantified using inductively coupled plasma mass spectrometry (ICP-MS). The quantitative results (μg) of ICP-MS for Si or Al are divided by 24 hours to calculate the dissolution rate (μg / h) of each component. The results of Examples 1 to 4 are shown in Table 2, the results of Examples 5 to 7 are shown in Table 3, and the results of Comparative Examples 1 to 3 are shown in Table 4.

[0171] (Possibility of long fiber formation)

[0172] The glass chips were melted in a platinum crucible using a high-temperature electric furnace equipped with a rotational viscometer (manufactured by Shibaura Systems Co., Ltd.). The viscosity of the molten glass was continuously measured using a rotational Brookfield viscometer. The viscosity of the molten glass was continuously measured while varying the melting temperature. The 1000 poise temperature was determined by measuring the temperature corresponding to a rotational viscosity of 1000 poise.

[0173] Next, 40 g of glass particles with a particle size of 0.5 to 1.5 mm, obtained by crushing the glass chips, were placed in a 180 × 20 × 15 mm platinum crucible and heated for at least 8 hours in a tubular electric furnace set at a temperature gradient of 900 to 1300°C. The glass particles were then removed from the tubular furnace and observed using a polarizing microscope to determine the location where crystals of the devitrified glass began to precipitate. The temperature within the tubular furnace was measured using a B thermocouple, and the temperature at the location where precipitation began was determined and used as the liquidus temperature.

[0174] Next, the operating temperature range ΔT (ΔT = 1000 poise temperature - liquidus temperature) was calculated based on the 1000 poise temperature and liquidus temperature measured by the above method. When ΔT was +99°C or higher, the likelihood of fiber formation was evaluated as "A," when ΔT was -10°C or higher and less than +99°C, the likelihood of fiber formation was evaluated as "B," and when ΔT was less than -10°C, the likelihood of fiber formation was evaluated as "C." The results of Examples 1 to 4 are shown in Table 2, the results of Examples 5 to 7 are shown in Table 3, and the results of Comparative Examples 1 to 3 are shown in Table 4.

[0175] (Example 8)

[0176] In this example, the glass chips obtained in Example 1 were first added to a platinum container equipped with a nozzle at the bottom. The container was then heated to 1150-1350°C, melting the glass chips to produce molten glass. The molten glass was then drawn from the nozzle and wound onto a take-up device. The heating temperature of the platinum container was then adjusted, and the take-up device was rotated. Glass fibers were then wound onto the take-up device at a spinning temperature of 1150-1350°C, suitable for the glass composition of each example, and a spinning speed of 800-1100 rpm, suitable for the glass composition of each example. This yielded glass fiber samples with a fiber diameter of 13.0 μm.

[0177] Next, according to K. Sebastian. et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2020), the glass fiber sample is cut into a length that can be contained in an in-line filter holder, that is, 1 to 3 mm, and used as a glass fiber sample for a dissolution test. The glass fiber sample for the dissolution test is placed on a membrane filter arranged in the in-line filter holder, and the artificial lung fluid heated to 37°C is pumped into the in-line filter holder at a flow rate of 140 to 170 mL / day, and the artificial lung fluid is sent into the in-line filter holder. The filtrate that has passed through the test glass fiber sample and the filter holder is accumulated in a container, thereby implementing a dissolution test. At this time, the flow rate of the artificial lung fluid (unit: μm 3 / s) and sample surface area (unit: μm 2The sample mass placed on the membrane filter was adjusted so that the ratio (artificial lung fluid flow rate / sample surface area) was 0.030 ± 0.005 μm / s. After 24 hours, the filtrate was recovered from the container. The ion components dissolved in the filtrate were quantified using inductively coupled plasma mass spectrometry (ICP-MS), with Si and Al as the target ions. The ICP-MS quantitative results (μg) for Si or Al were divided by 24 hours to calculate the dissolution rate (μg / h) of each component. The results are shown in Table 5.

[0178] (Example 9)

[0179] In this example, a glass fiber sample having a fiber diameter of 13.0 μm was prepared in the same manner as in Example 8 except that the glass chips obtained in Example 4 were used.

[0180] Next, a dissolution test was conducted in exactly the same manner as in Example 8, except that the glass fiber sample having a fiber diameter of 13.0 μm obtained in this example was used, and the dissolution rate (μg / h) of each component was calculated. The results are shown in Table 5.

[0181] (Table 2)

[0182]

[0183] (Table 3)

[0184]

[0185] (Table 4)

[0186]

[0187] (Table 5)

[0188]

[0189] As clearly shown in Tables 1 to 4, the glass powder samples obtained from the glass compositions for glass fibers of Examples 1 to 7 exhibited a combined SiO2 and Al2O3 dissolution rate of 103.5 μg / h or higher, indicating biosolubility and the ability to form long fibers. On the other hand, the glass powder obtained from the glass composition for glass fibers of Comparative Example 1 exhibited excellent biosolubility with a combined SiO2 and Al2O3 dissolution rate of 180.2 μg / h, but showed poor potential for forming long fibers. The glass powder obtained from the glass composition for glass fibers of Comparative Example 2 exhibited a relatively high combined SiO2 and Al2O3 dissolution rate of 96.6 μg / h, but showed poor potential for forming long fibers. The glass powder obtained from the glass composition for glass fibers of Comparative Example 3 exhibited biosolubility with a combined SiO2 and Al2O3 dissolution rate of 41.7 μg / h.

[0190] Furthermore, as is apparent from Table 5, the glass fiber samples of Examples 8 and 9 have biosolubility comparable to that of the glass powder samples of Examples 1 and 4 obtained from the same glass composition for glass fibers. Therefore, it is highly likely that the glass fiber samples obtained from the glass compositions for glass fibers of Examples 2, 3, and 5 to 7 also have biosolubility comparable to that of the glass powder samples of Examples 2, 3, and 5 to 7.

Claims

1. A glass composition for glass fiber, characterized in that: The total amount contains 35.0-55.0 mass % of SiO2, 10.0-30.0 mass % of B2O3, 14.5-30.0 mass % of Al2O3, and a total of 8.7-25.0 mass % of CaO and MgO. Contains Li2O, K2O and Na2O in a total amount ranging from 0 to 0.4 mass %, The SiO2 content S, the B2O3 content B, the Al2O3 content A, the CaO content C, and the MgO content M satisfy the following formula (1), and the S, B, A, C, and M satisfy the following formula (2): 11.3≤S×(C+M) / (A+B)≤20.7…(1) 12.5≤(A+0.9×B) 3 ×(3×C+2×M) / S 3 ≤70.2…(2)。 2. The glass composition for glass fiber according to claim 1, wherein The S, the B, the A, the C, and the M satisfy the following formula (3): 11.3≤S×(C+M) / (A+B)≤19.3…(3).

3. The glass composition for glass fiber according to claim 1, wherein Relative to the total amount, it contains SiO2 in the range of 37.0 to 49.5 mass%, B2O3 in the range of 16.5 to 29.0 mass%, Al2O3 in the range of 15.0 to 28.0 mass%, CaO in the range of 10.5 to 21.0 mass%, MgO in the range of 0 to 6.5 mass% and TiO2 in the range of 0 to 0.4 mass%.

4. The glass composition for glass fiber according to claim 1, wherein The S, the B, the A, the C, and the M satisfy the following formula (4): 13.6≤S×(C+M) / (A+B)≤17.5…(4).

5. The glass composition for glass fiber according to claim 1, wherein The S, the B, the A, the C, and the M satisfy the following formula (5): 16.2≤S×(C+M) / (A+B)≤17.2…(5).

6. The glass composition for glass fiber according to claim 1, wherein The S, the B, the A, the C, and the M satisfy the following formula (6): 16.6≤S×(C+M) / (A+B)≤16.9…(6).

7. A glass fiber, characterized in that: Contains glass filaments composed of the glass composition for glass fibers according to any one of claims 1 to 6.

8. The glass fiber according to claim 7, characterized in that The glass filaments have a filament diameter of less than 3.0 μm.

9. A glass fiber fabric, characterized in that: Composed of the glass fiber according to claim 7.

10. A glass fiber reinforced resin composition, characterized in that Containing the glass fiber according to claim 7.

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