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

Abstract

This invention provides a glass composition for glass fibers, which is biosoluble and can achieve long fiber formation. Even when exposed to water, high temperature, and high humidity environments, it can produce sufficiently high-strength glass filaments. The glass composition for glass fibers of this invention contains, relative to the total mass, 35.00–50.00% SiO2, 12.00–28.00% Al2O3, 10.00–25.00% B2O3, 2.00–18.00% MgO, and 5.00–25.00% CaO. The total content of MgO and CaO is 17.09–30.00% by mass, and the MgO / CaO ratio is 0.29–1.92.

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] In recent years, there has been a continuous push towards thinner and shorter designs in glass fiber reinforced resin compositions, especially in the field of printed wiring boards containing glass fiber fabrics. Consequently, there is a growing demand for extremely fine glass fibers. Therefore, it can be assumed that biocompatibility will also become an important property in the field of glass fibers in the future.

[0003] Therefore, the inventors have proposed a solution for a glass composition for glass fibers that is biosoluble and capable of long fiberization (see Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 7107468 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The aforementioned long glass fibers may be exposed to water during processes such as coating the surface of the glass fibers with a surface treatment agent during spinning, and during the fiber-opening process of processing the glass fibers into glass yarn bundles, glass yarns, glass fiber fabrics, etc. Furthermore, when these long glass fibers are processed into final products such as glass fiber reinforced resin compositions, and when used as final products, if they are stored for extended periods in warehouses with inadequate air conditioning management, they may be exposed to high temperature and humidity environments depending on weather conditions.

[0009] However, glass fibers that are biosoluble are hydrophilic and therefore have low water resistance. If exposed to water, high temperature and high humidity, the strength of the glass filaments will decrease, the product will deteriorate more rapidly, or the glass filaments will break due to tension during handling, which is the main cause of the formation of microfibers.

[0010] Therefore, the object of the present invention is to eliminate the above-mentioned problems and provide a glass composition for glass fiber: the glass composition for glass fiber is biosoluble, can achieve long fiber formation, and can obtain glass filaments with sufficiently high strength even when exposed to water, high temperature and high humidity.

[0011] Methods for solving problems

[0012] To achieve the above objectives, the glass composition for glass fibers of the present invention is characterized in that, relative to the total amount comprising SiO2 ranging from 35.00 to 50.00% by mass, Al2O3 ranging from 12.00 to 28.00% by mass, B2O3 ranging from 10.00 to 25.00% by mass, MgO ranging from 2.00 to 18.00% by mass, and CaO ranging from 5.00 to 25.00% by mass, the total content of MgO and CaO is in the range of 17.09 to 30.00% by mass, and the ratio of the content of MgO to the content of CaO (MgO / CaO) is in the range of 0.29 to 1.92.

[0013] With the above-described configuration, the glass composition for glass fibers of the present invention can produce glass filaments that are biosoluble, capable of long fiberization, and possess sufficiently high strength even when exposed to water, high temperature, and high humidity.

[0014] Among them, having biosolubility means that the biosolubility is 100 μg / h or higher; being able to achieve long fiber formation means that the operating temperature range, which is the difference between the 1000 poise temperature and the liquid phase temperature, is 0°C or higher; and having sufficiently high strength even when exposed to water, high temperature and high humidity environments means that the water absorption strength is 2.1 GPa or higher (i.e., having water absorption strength equal to or higher than that of glass fibers composed of E glass).

[0015] In the glass composition for glass fibers of the present invention, the ratio of MgO content to CaO content (MgO / CaO) is preferably in the range of 0.49 to 1.68, which can produce glass filaments that are biosoluble, easy to achieve long fiberization, and have excellent strength even when exposed to water, high temperature and high humidity environments.

[0016] The ability to easily achieve long fiber formation refers to a working temperature range of over 100°C, where the temperature difference between the 1000 poise temperature and the liquid phase temperature is greater than 100°C. Excellent strength even when exposed to water, high temperature and high humidity environments refers to a water absorption strength of over 2.3 GPa, as described later.

[0017] Furthermore, the glass fiber of the present invention is characterized in that it comprises glass filaments formed from the glass composition of the glass fiber of the present invention. Preferably, in the glass fiber of the present invention, the diameter of the glass filaments is less than 3.0 μm.

[0018] Furthermore, the glass fiber fabric and glass fiber reinforced resin composition of the present invention are characterized in that they contain the glass fiber described in the present invention. Detailed Implementation

[0019] Next, the embodiments of the present invention will be described in further detail.

[0020] The glass composition for glass fiber in this embodiment contains, relative to the total amount, 35.00 to 50.00% by mass of SiO2, 12.00 to 28.00% by mass of Al2O3, 10.00 to 25.00% by mass of B2O3, 2.00 to 18.00% by mass of MgO and 5.00 to 25.00% by mass of CaO, with a total content of MgO and CaO ranging from 17.09 to 30.00% by mass, and a ratio of MgO content to CaO content (MgO / CaO) ranging from 0.29 to 1.92.

[0021] In the glass composition for glass fibers of this embodiment, if the SiO2 content is less than 35.00% by mass relative to the total amount, the strength and elastic modulus of the long glass fibers decrease, and the effect of reinforcing the resin becomes insufficient when the long glass fibers are used in their composites with resins. On the other hand, if the SiO2 content exceeds 50.00% by mass relative to the total amount, it may lead to a decrease in biosolubility.

[0022] 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 35.50 to 49.40% by mass, more preferably in the range of 37.00 to 48.90% by mass, further preferably in the range of 38.00 to 47.90% by mass, particularly preferably in the range of 39.00 to 47.00% by mass, especially preferably in the range of 40.00 to 46.00% by mass, extremely preferably in the range of 41.00 to 45.00% by mass, and most preferably in the range of 41.60 to 44.40% by mass.

[0023] Furthermore, in the glass composition for glass fibers of this embodiment, if Al2O3 is less than 12.00% by mass relative to the total amount, the strength and elastic modulus of the long glass fibers decrease, and the effect of reinforcing the resin becomes insufficient when used to manufacture composite materials with resin. On the other hand, when Al2O3 exceeds 28.00% by mass relative to the total amount, the devitrification temperature of the molten glass becomes higher, which may make it difficult to carry out long fiber formation.

[0024] 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 15.10 to 27.00% by mass, more preferably in the range of 16.10 to 26.00% by mass, further preferably in the range of 17.00 to 25.00% by mass, particularly preferably in the range of 18.00 to 24.00% by mass, extremely preferably in the range of 18.50 to 23.00% by mass, and most preferably in the range of 19.00 to 22.00% by mass.

[0025] Furthermore, in the glass composition for glass fibers of this embodiment, if the amount of B2O3 relative to the total amount is less than 10.00% by mass, the devitrification temperature of the molten glass becomes higher, making long fiber formation potentially difficult, and the biocompatibility may decrease. On the other hand, if the amount of B2O3 relative to the total amount exceeds 25.00% by mass, phase separation occurs in the molten glass, making long fiber formation difficult.

[0026] In the glass composition for glass fiber of this embodiment, the content of B2O3 relative to the total amount is preferably in the range of 11.10 to 24.00% by mass, more preferably in the range of 12.00 to 21.30% by mass, even more preferably in the range of 12.30 to 18.00% by mass, particularly preferably in the range of 12.50 to 17.50% by mass, especially preferably in the range of 12.70 to 17.00% by mass, extremely preferably in the range of 12.80 to 16.50% by mass, and most preferably in the range of 13.50 to 16.20% by mass.

[0027] Furthermore, in the glass composition for glass fibers of this embodiment, if the MgO content is less than 2.00% by mass relative to the total amount, the elastic modulus of the long glass fibers decreases, and when these long glass fibers are used to make composite materials with resins, the effect of reinforcing the resin becomes insufficient. On the other hand, if the MgO content exceeds 18.00% by mass relative to the total amount, the strength of the long glass fibers decreases, and when these long glass fibers are used to make composite materials with resins, the effect of reinforcing the resin becomes insufficient.

[0028] In the glass composition for glass fiber of this embodiment, the content of MgO relative to the total amount is preferably in the range of 3.10 to 17.00% by mass, more preferably in the range of 5.10 to 16.00% by mass, even more preferably in the range of 6.10 to 15.40% by mass, particularly preferably in the range of 8.10 to 15.00% by mass, especially preferably in the range of 8.40 to 14.00% by mass, extremely preferably in the range of 8.60 to 13.00% by mass, even more extremely preferably in the range of 8.70 to 12.00% by mass, and most preferably in the range of 9.10 to 11.95% by mass.

[0029] Furthermore, in the glass composition for glass fibers of this embodiment, if the amount of CaO relative to the total amount is less than 5.00% by mass, the elastic modulus of the long glass fibers decreases, and when these long glass fibers are used to make a composite material with resin, the effect of reinforcing the resin becomes insufficient. On the other hand, if the amount of CaO relative to the total amount exceeds 25.00% by mass, the strength of the long glass fibers decreases, and when these long glass fibers are used to make a composite material with resin, the effect of reinforcing the resin becomes insufficient.

[0030] In the glass composition for glass fiber of this embodiment, the content of CaO relative to the total amount is preferably in the range of 5.60 to 24.00% by mass, more preferably in the range of 6.60 to 23.00% by mass, further preferably in the range of 10.10 to 22.50% by mass, particularly preferably in the range of 13.40 to 22.00% by mass, especially preferably in the range of 13.80 to 21.90% by mass, and most preferably in the range of 14.00 to 17.90% by mass.

[0031] Furthermore, in the glass composition for glass fibers of this embodiment, if the total content of MgO and CaO relative to the total amount is less than 17.09% by mass, the strength of the glass filaments decreases when the glass fibers absorb water. On the other hand, if the total content of MgO and CaO relative to the total amount exceeds 30.00% by mass, the strength of the glass fibers decreases, and when these glass fibers are used to make composite materials with resins, the effect of reinforcing the resin becomes insufficient.

[0032] In the glass composition for glass fiber of this embodiment, the total content of MgO and CaO relative to the total amount is preferably in the range of 18.00 to 29.00% by mass, more preferably in the range of 19.00 to 28.00% by mass, further preferably in the range of 20.00 to 27.00% by mass, particularly preferably in the range of 20.50 to 26.00% by mass, especially preferably in the range of 21.00 to 25.00% by mass, and most preferably in the range of 22.00 to 24.50% by mass.

[0033] Furthermore, in the glass composition for glass fibers of this embodiment, if the ratio of MgO content to CaO content (MgO / CaO) is less than 0.29, the strength of the glass filaments decreases when the glass fibers absorb water. On the other hand, if the ratio of MgO content to CaO content (MgO / CaO) exceeds 1.92, the devitrification temperature of the molten glass becomes higher, and the formation of long fibers becomes more difficult.

[0034] In the glass composition for glass fiber of this embodiment, the ratio of MgO content to CaO content (MgO / CaO) is preferably in the range of 0.34 to 1.75, more preferably in the range of 0.49 to 1.68, even more preferably in the range of 0.51 to 1.30, particularly preferably in the range of 0.52 to 0.99, and most preferably in the range of 0.61 to 0.92.

[0035] In the glass composition for glass fiber of this embodiment, the total content of SiO2, B2O3, Al2O3, CaO and MgO relative to the total amount is, for example, 91.00% by mass or more, preferably 95.00% by mass or more, more preferably 98.00% by mass or more, further preferably 99.00% by mass or more, particularly preferably 99.30% by mass or more, especially preferably 99.50% by mass or more, extremely preferably 99.70% by mass or more, and most preferably 99.90% by mass or more.

[0036] From the viewpoint of improving the defoaming properties of molten glass and enhancing the stability of long fiber formation, the glass composition for glass fibers in this embodiment may contain Fe2O3. The content of Fe2O3 is, for example, in the range of 0 to 0.40% by mass relative to the total amount of the glass composition for glass fibers in this embodiment, preferably in the range of 0 to 0.30% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass.

[0037] Furthermore, from the viewpoint of facilitating the formation of long fibers by reducing the melt viscosity of the molten glass, the glass composition for glass fibers in this embodiment may contain ZrO2. The content of ZrO2 is, for example, in the range of 0 to 0.60% by mass relative to the total amount of the glass composition for glass fibers in this embodiment, preferably in the range of 0 to 0.30% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass.

[0038] From the viewpoint of improving the defoaming properties of molten glass and enhancing the stability of long fiber formation, the glass composition for glass fibers in 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 in this embodiment is, for example, in the range of 0 to 0.40% by mass, preferably in the range of 0 to 0.30% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass.

[0039] From the viewpoint of reducing the melt viscosity of molten glass and facilitating the formation of long fibers, the glass composition for glass fibers in this embodiment may contain SrO. The content of SrO is, for example, in the range of 0 to 0.40% by mass relative to the total amount of the glass composition for glass fibers in this embodiment, preferably in the range of 0 to 0.30% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass.

[0040] From the viewpoint of facilitating long fiber formation by suppressing the rise in devitrification temperature of molten glass, the glass composition for glass fibers in this embodiment may contain ZnO. The content of ZnO is, for example, in the range of 0 to 0.40% by mass relative to the total amount of the glass composition for glass fibers in this embodiment, preferably in the range of 0 to 0.30% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass.

[0041] From the viewpoint of facilitating long fiber formation by suppressing the rise in devitrification temperature of molten glass, the glass composition for glass fibers in this embodiment may contain SnO2. The SnO2 content is, for example, in the range of 0 to 0.40% by mass relative to the total amount of the glass composition for glass fibers in this embodiment, preferably in the range of 0 to 0.30% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass.

[0042] From the viewpoint of facilitating long fiber formation by suppressing the rise in devitrification temperature of molten glass, the glass composition for glass fibers in this embodiment may contain P2O5. From the viewpoint of suppressing the generation of bubbles in molten glass, the content of P2O5 is, for example, less than 2.50% by mass relative to the total amount of the glass composition for glass fibers in this embodiment, preferably less than 1.50% by mass, more preferably less than 1.00% by mass, further preferably less than 0.80% by mass, extremely preferably less than 0.60% by mass, and most preferably less than 0.50% by mass.

[0043] When the glass composition for glass fibers in this embodiment contains TiO2, the content of TiO2 relative to the total amount of the glass composition for glass fibers in this embodiment is, for example, in the range of 1.90% by mass or less, preferably in the range of 0 to 0.40% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to less than 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass. If TiO2 exceeds 1.90% by mass, the biocompatibility may decrease when the glass composition for glass fibers is made into glass fibers.

[0044] From the viewpoint of facilitating the formation of long fibers by reducing the melt viscosity of molten glass, the glass composition for glass fibers in this embodiment may contain Li₂O, K₂O, and Na₂O. The total content of Li₂O, K₂O, and Na₂O is, for example, in the range of 0 to 0.90% by mass relative to the total amount of the glass composition for glass fibers in this embodiment, preferably in the range of 0 to 0.40% by mass, more preferably in the range of 0 to 0.20% by mass, further preferably in the range of 0 to 0.10% by mass, particularly preferably in the range of 0 to 0.05% by mass, and most preferably in the range of 0 to 0.01% by mass.

[0045] In the glass composition for glass fibers of this embodiment, impurities such as oxides of Ba, Mn, Co, Ni, Cu, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb may be included in an amount less than 1.00% by mass relative to the total amount of the glass composition for glass fibers, wherein the impurities originate from raw materials. Particularly when the glass composition for glass fibers of this embodiment contains BaO, CeO, Y₂O₃, La₂O₃, Bi₂O₃, Gd₂O₃, Pr₂O₃, Sc₂O₃, or Yb₂O₃ as impurities, the content of each oxide is preferably less than 0.40% by mass, more preferably less than 0.20% by mass, further preferably less than 0.10% by mass, particularly preferably less than 0.05% by mass, extremely preferably less than 0.01% by mass, and most preferably less than 0.004% by mass.

[0046] Furthermore, when the glass fiber of this embodiment is made into glass fiber using the glass composition, from the viewpoint of having a more superior elastic modulus, the ratio of MgO content to Al2O3 content (MgO / Al2O3) is preferably 0.28 or more, and from the viewpoint of having excellent water resistance when made into glass fiber, it is preferably 0.63 or less. The ratio of MgO content to Al2O3 content (MgO / Al2O3) is preferably in the range of 0.28 to 0.77, and more preferably in the range of 0.41 to 0.63.

[0047] Furthermore, when the glass fiber of this embodiment is made into glass fiber using a glass composition, from the viewpoint of having better biosolubility and being easier to achieve long fiber formation, the content of SiO2 S, the content of Al2O3 A, the content of B2O3 B, the content of MgO M, and the content of CaO C preferably satisfy the following formula (1), and more preferably satisfy the following formula (2).

[0048] 20.8≤S×(C+M) / (A+B)≤34.0…(1)

[0049] 27.0≤S×(C+M) / (A+B)≤33.0…(2)

[0050] In equation (1) or equation (2) above, as mentioned above, if C+M is too small, there is a tendency for the strength of the glass filaments to decrease when the glass fibers absorb water. On the other hand, if C+M is too large, the viscosity of the glass decreases and the operating temperature range narrows, thus making it difficult to achieve long fiber formation. In addition, S / (A+B) represents the ratio of the content of SiO2 in the components forming the glass skeleton to the total content of Al2O3 and B2O3. If this ratio is too small, there is a tendency for the mechanical properties of the glass fibers to deteriorate. On the other hand, if this ratio is too large, there is a tendency for the meltability to deteriorate and the solubility in organisms to decrease.

[0051] By setting the lower limit in formula (1) or formula (2) above to 20.8 or more, and preferably above 27.0, there is a tendency to maintain the biosolubility of the glass fibers while preventing the glass filaments from deteriorating during water absorption. In addition, by setting the upper limit in formula (1) or formula (2) below 34.0, and preferably below 33.0, the biosolubility is improved, and the stability of the long fiber is improved by increasing the operating temperature range.

[0052] To determine the content of each of the above-mentioned components in the glass composition for glass fiber according to this embodiment, the oil content of Li, as a light element, can be determined using an ICP emission spectrophotometer, and the content of other elements can be determined using a wavelength dispersive fluorescence X-ray analyzer. Specifically, the content of each of the aforementioned components can be determined in the following manner.

[0053] First, a glass batch or glass fiber, prepared by mixing glass raw materials, is placed in a platinum crucible. In an electric furnace, when using the glass batch, the mixture is held at 1350–1550°C for 6 hours; when using glass fiber, it is held at 1300–1450°C for 6 hours, while stirring to melt the mixture, thereby obtaining a homogeneous molten glass. If organic matter adheres to the surface of the glass fiber, or if the glass fiber contains organic materials such as resin as the main reinforcing material, the organic matter is removed, for example, by heating in a muffle furnace at 300–650°C for approximately 0.5–24 hours, before using the glass fiber.

[0054] Next, the molten glass is poured onto a carbon plate to create glass shavings, which are then pulverized to form glass powder. This glass powder is then heated and decomposed with acid, and Li, as a light element, is quantitatively analyzed using an ICP-based fluorescence spectrophotometer. Alternatively, the glass powder can be shaped into a disc using a press, and other elements can be quantitatively analyzed using a wavelength dispersive X-ray fluorescence spectrophotometer. Specifically, the quantitative analysis using a wavelength dispersive X-ray fluorescence spectrophotometer can be performed as follows: a standard curve sample is prepared based on the results determined by the basic parameter method, and analysis is conducted using the standard curve method. It should be noted that the content of each component in the calibration curve sample can be quantitatively analyzed using an ICP-based fluorescence spectrophotometer.

[0055] These quantitative analysis results are converted to oxides to calculate the content and total amount of each component. Based on these values, the content rate (mass%) of each component can be determined.

[0056] Next, the glass fiber of this embodiment comprises a glass filament formed from the glass composition for glass fibers described above. The glass fiber of this embodiment can be manufactured in the following manner.

[0057] First, a glass raw material (glass batch) prepared according to the composition of the ore used as the glass raw material, the content of each component, and the amount of volatilization of each component during the melting process, is supplied to a melting furnace in a manner that will form the composition of the glass composition for glass fibers in this embodiment. For example, melting is carried out at a temperature in the range of 1350 to 1550°C. Next, the molten glass batch (molten glass) is drawn out from 1 to 20,000 nozzles of a sleeve controlled at a specified temperature and quenched, thereby forming glass filaments.

[0058] Next, a bundler or adhesive is applied to the formed glass filaments using a coater, which is a coating device. Then, while bundling 1 to 20,000 glass filaments using a bundler, they are wound onto a tube at high speed using a winding machine, thereby obtaining glass fiber.

[0059] In order to manufacture the glass fiber using the glass composition of this embodiment into the aforementioned glass fiber, when melting the glass composition using the glass fiber at a temperature within the aforementioned range, long fiber formation can be achieved by making the operating temperature range ΔT (operating temperature range ΔT = 1000 poise temperature - liquid phase temperature) calculated using the 1000 poise temperature and the liquid phase temperature above 0°C, and long fiber formation can be easily achieved by making the operating temperature range ΔT above 100°C.

[0060] The glass filaments ejected from a nozzle or orifice and cooled and solidified typically have a circular cross-sectional shape, and preferably a diameter (filament diameter) of less than 3.0 μm. On the other hand, when the nozzle has a non-circular shape and has protrusions or cuts for quenching the molten glass, glass filaments with non-circular cross-sectional shapes such as elliptical or oblong can be obtained by controlling the temperature conditions. When the glass filament has an elliptical or oblong cross-sectional shape, the fiber diameter converted to a circle (i.e., the converted fiber diameter) is preferably less than 3.0 μm. It should be noted that the lower limit of the filament diameter is, for example, 0.5 μm, and preferably 1.0 μm, more preferably 2.0 μm.

[0061] The diameter of the aforementioned glass filament can be calculated, for example, as follows: First, glass fibers are embedded in a resin such as epoxy resin and the resin is cured. The cured resin is then cut and its cross-section is ground. Next, the cross-section of the cured resin is observed using an electron microscope. For 50 or more glass filaments exposed from the cross-section, if the cross-sectional shape of the glass filament is circular or approximately circular, the diameter of the glass filament is measured. If the cross-sectional shape of the glass filament is not circular or approximately circular, its cross-sectional area is calculated, and then the equivalent fiber diameter is calculated based on this cross-sectional area. Then, the average value of the measured or calculated diameter or equivalent fiber diameter is obtained, thereby calculating the diameter of the glass filament. Alternatively, the diameter of the aforementioned glass filament can also be determined by image processing of the image obtained from the electron microscope using an automatic analysis device.

[0062] On the other hand, when the glass fiber of this embodiment is included in the glass fiber reinforced resin molded article, the filament diameter of the glass filament can be measured, for example, by the following method. First, the glass fiber reinforced resin molded article is heated at 625°C for 30 minutes, and the glass fiber is removed after the thermoplastic resin is burned. Then, the filament diameter of the glass filament is measured in the same manner as the method described above for measuring the filament diameter of the glass filament in the glass fiber.

[0063] To improve the bundle properties of glass filaments, enhance the adhesion between glass fibers and resins, and improve the uniform dispersion of glass fibers in mixtures of glass fibers with resins or inorganic materials, the glass fibers of this embodiment can 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, and copolymers of maleic acid and unsaturated monomers.

[0064] In addition to the resin coating described above, the glass fibers of this embodiment can also be coated with a resin composition containing a silane coupling agent, lubricant, surfactant, etc. Alternatively, the glass fibers of this embodiment can also be coated with a treatment agent composition containing a silane coupling agent, surfactant, etc., but not the resin described above. Based on the mass of the glass fibers of this embodiment not coated with the resin composition or treatment agent composition, the resin composition or treatment agent composition coats the glass fibers at a ratio of 0.03 to 2.0% by mass.

[0065] It should be noted that the coating of glass fibers with organic materials can be carried out, for example, by the following method: in the glass fiber manufacturing process, a resin solution or resin composition solution is applied to the glass fibers using a known method such as a roller coater, and then the glass fibers coated with the resin solution or resin composition solution are dried. Alternatively, the coating of glass fibers with the above-mentioned organic materials can also be carried out by immersing the glass fibers of this embodiment, which are in the form of a fabric, in a treatment agent composition solution, and then drying the glass fibers coated with the treatment agent composition.

[0066] Examples of silane coupling agents include: aminosilanes, ureosilanes, chlorosilanes, epoxysilanes, mercaptosilanes, vinylsilanes, (meth)acrylate silanes, phenylsilanes, styrylsilanes, and isocyanate silanes. In this embodiment, each of the above-mentioned silane coupling agents can be used alone, or two or more can be used in combination.

[0067] Examples of aminosilanes include: γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinepropyltrimethoxysilane.

[0068] Examples of ureosilanes include γ-ureopropyltriethoxysilane.

[0069] Examples of chlorosilanes include γ-chloropropyltrimethoxysilane.

[0070] Examples of epoxy silanes include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-epoxypropoxypropyltrimethoxysilane.

[0071] Examples of mercaptosilanes include γ-mercaptotrimethoxysilane and γ-mercaptopropyltrimethoxysilane.

[0072] Examples of vinyl silanes include: vinyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, and N-benzyl-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0073] Examples of (meth)acrylic silanes include γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane.

[0074] Examples of phenylsilanes include phenyltrimethoxysilane.

[0075] Examples of styrylsilanes include p-styryltrimethoxysilane.

[0076] Examples of isocyanate silanes include γ-isocyanate propyltriethoxysilane.

[0077] Examples of lubricants include: modified silicone oils, animal oils and their hydrogenated additives, vegetable oils and their hydrogenated additives, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimine, polyalkyl polyamine alkyl linolenic acid derivatives, fatty acid amides, and quaternary ammonium salts. In this embodiment, each of the above-mentioned lubricants may be used alone, or two or more may be used in combination.

[0078] Examples of animal fats include beef tallow.

[0079] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.

[0080] Examples of animal-derived waxes include beeswax and lanolin.

[0081] Examples of plant-based waxes include candelilla wax and carnauba wax.

[0082] Examples of mineral waxes include paraffin wax and lignite wax.

[0083] Examples of condensates of higher saturated fatty acids and higher saturated alcohols include stearates such as lauryl stearate.

[0084] 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.

[0085] Examples of quaternary ammonium salts include alkyl trimethylammonium salts such as lauryltrimethylammonium chloride.

[0086] Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, each of the above surfactants may be used alone, or two or more may be used in combination.

[0087] Examples of nonionic surfactants include: ethylene oxide and 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, ethylene oxide and propylene oxide alkyl 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, sorbitol fatty acid esters, sucrose fatty acid esters, polyol alkyl ethers, fatty acid alkanolamides, acetylenol, ethylene oxide adducts of acetylenol, and ethylene oxide adducts of acetylenol.

[0088] Examples of cationic surfactants include: alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, alkyl dimethyl ethyl ammonium ethyl sulfate, higher alkylamine salts (acetates, hydrochlorides, etc.), ethylene oxide adducts of 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.

[0089] Examples of anionic surfactants include: higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfonates, α-olefin sulfonates, reaction products of fatty acid halides and N-methyl taurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphates of higher alcohol ethylene oxide adducts.

[0090] Examples of amphoteric surfactants include: amino acid-type amphoteric surfactants such as alkali metal salts of alkylaminopropionic acid, betaine-type amphoteric surfactants such as alkyl dimethyl betaine, and imidazoline-type amphoteric surfactants.

[0091] Examples of glass fiber forms include: fabrics (glass cloth), woven fabrics, yarns, chopped strands, rovings, chopped strand mats, fiber paper, fiber webs, woven fabrics, and ground fibers, with chopped strands, rovings, and fabrics (glass cloth) being preferred, and fabrics (glass cloth) being even more preferred.

[0092] For example, when the glass fiber in this embodiment is a chopped filament, the number of glass filaments constituting the glass fiber in this embodiment is, for example, 10 to 20,000, preferably 50 to 10,000, and more preferably 1,000 to 8,000. Furthermore, the length of the chopped filament of the glass fiber in this embodiment can be, for example, 1.0 to 100.0 mm, preferably 1.2 to 51.0 mm, more preferably 1.5 to 30.0 mm, further preferably 2.0 to 15.0 mm, and particularly preferably 2.3 to 7.8 mm. Here, the chopped filament can be obtained by cutting the glass fiber produced by the aforementioned method to the specified length using a known device such as a long fiber cutting device. The long fiber cutting device is a device that cuts the glass filament fed between a cutter roller and a rubber roller. Cutters (cutting blades) are mounted radially and at equal intervals on the cutter roller, and the rubber roller rotates in contact with the cutter roller and is equipped with rubber on its outer circumferential surface.

[0093] In this embodiment, when the glass fiber is roving, the number of glass filaments constituting the glass fiber of this embodiment is, for example, 200 to 30,000. Furthermore, the roving used as the glass fiber in this embodiment has a mass per unit length of 0.5 to 10,000 tex (g / 1000m).

[0094] The glass fiber fabric of this embodiment is composed of the glass fibers described in this embodiment. This glass fiber fabric can be obtained by weaving the glass fibers as warp and weft yarns using a well-known loom. Examples of such looms include jet looms (such as air-jet looms or water-jet looms), shuttle looms, and rapier looms. Furthermore, examples of weaving methods using such looms include plain weave, satin weave, square weave, and twill weave; from a manufacturing efficiency perspective, plain weave is preferred.

[0095] The glass fibers contained in the glass fiber fabric of this embodiment are composed of glass filaments having a filament diameter of 2.0 μm or more and 9.0 μm or less, and preferably have a mass of 0.35 to 70.0 tex (g / 1000m), more preferably have a mass of 0.5 to 70.0 tex (g / 1000m), even more preferably are composed of glass filaments having a filament diameter of 2.0 μm or more and less than 3.0 μm, even more preferably have a mass of 0.35 to 1.5 tex, and particularly preferably have a mass of 0.5 to 1.5 tex.

[0096] In this embodiment, the diameter of the glass fiber filaments contained in the glass fiber fabric is the average of the following measured values: the measured values ​​when the diameter of at least 50 glass filaments constituting the glass fiber in the cross section of the glass fiber is measured using a scanning electron microscope (manufactured by Nippon Electron Co., Ltd., trade name: JSM-IT800, magnification: 3000x).

[0097] In addition, the glass fiber fabric of this embodiment is preferably composed of warp yarns having a weave density of 40 to 150 threads / 25 mm and weft yarns having a weave density of 40 to 150 threads / 25 mm.

[0098] Furthermore, the weave density of the warp yarns can be determined as follows: according to JIS R 3420, count the number of warp yarns within a 25mm range in the warp direction using a fabric analysis microscope. Similarly, the weft yarn weave density can be determined as follows: according to JIS R 3420, count the number of weft yarns within a 25mm range in the weft direction using a fabric analysis microscope.

[0099] The glass fiber fabric of this embodiment can be subjected to degreasing treatment, surface treatment and fiber opening treatment after weaving.

[0100] As a degreasing treatment, the following process can be cited: placing glass fiber fabric in a heating furnace at an atmosphere temperature of 350℃~400℃ for 40~80 hours to decompose the organic matter attached to the glass fiber by heating.

[0101] As a surface treatment, the following treatment can be used: immersing the glass fiber fabric in a solution containing the above-mentioned silane coupling agent or the above-mentioned silane coupling agent and the above-mentioned surfactant, squeezing out the excess water, and then heating and drying it in a temperature range of 80°C to 180°C for 1 to 30 minutes.

[0102] As a fiber opening process, examples include the following: while applying a tension of 20 to 200 N to the warp yarns of the glass fiber fabric, fiber opening is performed using water flow pressure, high-frequency vibration using a liquid as a medium, pressure of a fluid with surface pressure, or pressure of a roller, etc., to increase the width of the warp and weft yarns.

[0103] Furthermore, the glass fiber fabric in this embodiment preferably has a strength of 2.5 to 220 g / m². 2 The mass range is more preferably 5.0 to 220 g / m³. 2 The mass range is specified. Additionally, a thickness range of 4.0 to 200.0 μm is preferred.

[0104] Furthermore, the glass fiber fabric of this embodiment may have a surface treatment layer comprising the aforementioned silane coupling agent or a surface treatment layer comprising the aforementioned silane coupling agent and the aforementioned surfactant. When the glass fiber fabric of this embodiment comprises the surface treatment layer, the total amount of the surface treatment layer relative to the total amount of the glass fiber fabric comprising the surface treatment layer may, for example, be in the range of 0.03 to 1.50% by mass.

[0105] The glass fiber reinforced resin composition of this embodiment contains the glass fibers described in this embodiment. Specifically, the glass fiber reinforced resin composition of this embodiment is a glass fiber reinforced resin composition containing resin (thermoplastic resin or thermosetting resin), glass fibers, and other additives, wherein the glass fiber reinforced resin composition contains glass fibers in an amount of 10 to 90% by mass relative to the total amount of the glass fiber reinforced resin composition. Furthermore, the glass fiber reinforced resin composition of this embodiment contains resin in an amount of 90 to 10% by mass relative to the total amount of the glass fiber reinforced resin composition, and contains other additives in the range of 0 to 40% by mass.

[0106] Examples of 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 acid resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polycarbonate, polyaryl sulfide, polyethersulfone (PES), and polyphenylene sulfone (PPS). Poly(phenylene oxide), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyarylether ketone, liquid crystal polymer (LCP), fluoropolymers, polyetherimide (PEI), polyarylether (PAR), polysulfone (PSF), polyamide-imide (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, polyvinyl alcohol (PVA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene adipate succinate (PBSA), polybutylene terephthalate (PBAT), etc.

[0107] 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.

[0108] Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures of the above polypropylenes.

[0109] Examples of polystyrene include general-purpose polystyrene (GPPS), which is a random stereostructured polystyrene; impact-resistant polystyrene (HIPS), which incorporates rubber components into GPPS; and syndiotactic polystyrene, which has a homo-stereostructure.

[0110] Examples of methacrylic resins include polymers formed by polymerizing one of the following methacrylic resins: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and vinyl fatty acid esters; and polymers formed by copolymerizing two or more of the above-mentioned methacrylic resins.

[0111] Examples of polyvinyl chloride include: homopolymers of vinyl chloride polymerized using existing known methods such as emulsion polymerization, suspension polymerization, micro-suspension polymerization, and bulk polymerization; copolymers of vinyl chloride monomers that can copolymerize with vinyl chloride monomers; and graft copolymers of polymers to which vinyl chloride monomers have been grafted.

[0112] Examples of polyamides include: polycaprolactam (Nylon 6), polyhexamethylene adipamide (Nylon 66), polybutylene adipamide (Nylon 46), polybutylene decanedamide (Nylon 410), polypentylene adipamide (Nylon 56), polydecanoyl diamine (Nylon 510), polyhexamethylene decanedamide (Nylon 610), polyhexamethylene dodecanoyl diamine (Nylon 612), polydemoethylene adipamide (Nylon 106), and polydecanoyl decanedamide. (Nylon 1010), Polydodecanoic acid decylamine (Nylon 1012), Polyundecylamide (Nylon 11), Polyhexamethylene adipamide (Nylon 116), Polydodecanoic acid amide (Nylon 12), Polyxylene hexamethylenediamine (Nylon XD6), Polyxylene sebacate amide (Nylon XD10), Poly(m-phenylene adipate) (Nylon MXD6), Poly(m-phenylene adipate) (Nylon PXD6), Poly(terephthalamide) (Nylon 4T), Poly Poly(pentanediamine terephthalamide) (Nylon 5T), poly(hexamethylene terephthalamide) (Nylon 6T), poly(hexamethylene isophthalamide) (Nylon 6I), poly(nonanediamine terephthalamide) (Nylon 9T), poly(decyl terephthalamide) (Nylon 10T), poly(undecanthoxymethyl terephthalamide) (Nylon 11T), poly(dodecyl terephthalamide) (Nylon 12T), polytetramethylene polyphthalamide (Nylon 4I), poly(3-methyl-4-aminohexylene) The ingredients include one of the following: poly(3-methyl-4-aminohexyl)methane terephthalamide (Nylon PACMT), poly(3-methyl-4-aminohexyl)methane isophthalamide (Nylon PACMI), poly(3-methyl-4-aminohexyl)methane dodecylamide (Nylon PACM12), poly(3-methyl-4-aminohexyl)methane tetradecylamide (Nylon PACM14), or a copolymer of two or more of these ingredients, or a mixture of these ingredients.

[0113] Examples of polyacetals include homopolymers with oxymethylene units as the main repeating units and copolymers of oxyalkylene units that mainly contain oxymethylene units, such as copolymers of oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain of the oxyalkylene units.

[0114] Polyethylene terephthalate can be exemplified by polymers obtained by polycondensation of terephthalic acid or its derivatives with ethylene glycol.

[0115] Examples of polybutylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,4-butanediol.

[0116] Examples of polypropylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,3-propanediol.

[0117] Examples of polycarbonates include polymers obtained by transesterification, which involves reacting a dihydroxy aryl compound with a carbonate such as diphenyl carbonate in a molten state, and polymers obtained by phosgene reaction, which involves reacting a dihydroxy aryl compound with phosgene.

[0118] Examples of polyaryl sulfides include linear polyphenylene sulfides, cross-linked polyphenylene sulfides that are polymerized by curing after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.

[0119] 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), poly(2-phenyl-1... 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-dipropyl-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), etc.

[0120] 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; modified polyphenylene ethers with amino, epoxy, carboxyl, styrene, or other functional groups introduced into the polymer chain ends of the above-mentioned polyphenylene ethers; and modified polyphenylene ethers with amino, epoxy, carboxyl, styrene, methacrylic acid, or other functional groups introduced into the side chains of the polymer chains of the above-mentioned polyphenylene ethers.

[0121] Examples of polyaryletherketones include: polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).

[0122] Examples of liquid crystal polymers (LCPs) include (co)polymers composed of one or more structural units selected from the following components: aromatic hydroxy carbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, etc., which are thermotropic liquid crystal polyesters.

[0123] Examples of fluoropolymers include: polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyethylene fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0124] Examples of ionomer (IO) resins include copolymers of olefins or styrene with unsaturated carboxylic acids, where a portion of the carboxyl group is neutralized with metal ions.

[0125] Examples of olefin / vinyl alcohol resins include: ethylene / vinyl alcohol copolymers, propylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymer saponifications, and propylene / vinyl acetate copolymer saponifications.

[0126] Examples of cyclic olefin resins include: monocyclic resins such as cyclohexene, polycyclic resins such as tetracyclic cyclic olefins, and polymers of cyclic olefin monomers.

[0127] Examples of polylactic acid include: poly-L-lactic acid as an L-type homopolymer, poly-D-lactic acid as a D-type homopolymer, or stereocomposite polylactic acid as a mixture thereof.

[0128] Examples of cellulose resins include: methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0129] In addition, examples of the aforementioned 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-formaldehyde (UF) resins, silicone (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismaleimide triazine (BT) resins, diallyl phthalate resins (PDAP), etc.

[0130] Specifically, as an example of an unsaturated polyester resin, a resin obtained by esterification of an aliphatic unsaturated dicarboxylic acid with an aliphatic diol can be cited.

[0131] Examples of vinyl ester resins include: divinyl ester resins and phenolic varnish-based vinyl ester resins.

[0132] Examples of 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-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexylene diphenol type epoxy resin), phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, and tetraphenolic ethane type phenolic resin. Varnish-type epoxy resins, phenolic varnish-type epoxy resins with fused ring aromatic hydrocarbon structures, biphenyl-type epoxy resins, xylene-type epoxy resins or phenylarylene-type epoxy resins and other aralkyl-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalene glycol-type epoxy resins, difunctional or tetrafunctional naphthalene epoxy resins, binatyl-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.

[0133] Examples of melamine resins include polymers formed by the condensation polymerization of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0134] Examples of phenolic resins include: phenolic varnish resins, cresol varnish resins, bisphenol A varnish resins, methyl phenolic resins, dimethylene ether methyl phenolic resins, arylalkylene phenolic resins, and other phenolic varnish-type phenolic resins; methyl phenolic resins; and other methyl phenolic resins; or arylalkylene phenolic resins.

[0135] Examples of urea-formaldehyde resins include those obtained by the condensation of urea and formaldehyde.

[0136] The above-mentioned thermoplastic resin or thermosetting resin can be used alone or in combination of two or more.

[0137] Other additives mentioned above include: reinforcing fibers other than glass fibers such as carbon fiber and metal fiber; fillers other than glass fibers such as glass powder, talc, and mica; flame retardants; ultraviolet absorbers; heat stabilizers; antioxidants; antistatic agents; flow modifiers; anti-blocking agents; lubricants; nucleating agents; antibacterial agents; and pigments.

[0138] The glass fiber reinforced resin composition of this embodiment can also be a prepreg prepared by impregnating the above-mentioned resin into the glass fiber fabric of this embodiment and semi-curing it using a method known to the public.

[0139] The glass fiber reinforced resin composition of this embodiment can be molded using known molding methods to obtain various glass fiber reinforced resin molded articles. Known molding methods include: injection molding, injection compression molding, two-color molding, hollow molding, foaming molding including supercritical fluids, insert molding, in-mold coating molding, autoclave molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, compression molding, blow molding, stamping molding, injection molding, hand lay-up molding, spraying, RIM (reinforced in-mold molding), resin transfer molding, sheet molding compound molding, bulk molding compound molding, pultrusion molding, and filament winding. Furthermore, glass fiber reinforced resin molded articles can also be obtained by curing the aforementioned prepreg.

[0140] Examples of uses for such molded products include: printed wiring boards, connectors and other electronic components, housings of electronic devices, interior parts of vehicles, exterior parts of vehicles, housings of electronic devices such as antennas and radars, and separators for fuel cells.

[0141] The following are embodiments and comparative examples of the present invention.

[0142] Example

[0143] [Examples 1-4, Comparative Examples 1-4, Reference Examples]

[0144] First, glass raw materials are mixed to prepare glass batches, such that the composition of the glass after melting and solidification will be the composition of Examples 1-4, Comparative Examples 1-4 and Reference Examples as shown in Table 2.

[0145] Next, the prepared glass batch was placed in a platinum crucible and kept in an electric furnace for 4 hours at a melting temperature suitable for the glass batches of each embodiment, comparative example, and reference example, within the temperature range of 1350–1550°C, while stirring the glass batch to melt it, thereby obtaining homogeneous molten glass. Then, the obtained molten glass was poured onto a carbon plate and cooled to obtain blocky glass shavings.

[0146] Next, using the obtained glass shards, the biosolubility, the potential for long fibrous formation, and the strength during water absorption were evaluated using the methods shown below. The results are shown in Table 2.

[0147] It should be noted that the total dissolution rate of Si, B, Al and Ca of the glass fiber obtained by the glass composition for glass fiber in Example 1 is 106 μg / h, the operating temperature range is 159°C, and the coefficient of linear expansion is 5.5 ppm / K.

[0148] [Organic solubility]

[0149] First, the aforementioned glass shavings were placed into a platinum container with a nozzle at the bottom. The platinum container was heated to a temperature range of 1150–1350°C to melt the glass shavings and obtain molten glass. Next, the molten glass was pulled out from the nozzle and wound into a winding device. Then, the heating temperature of the platinum container and the winding speed of the winding device were adjusted to wind the glass fiber into the winding device at a heating temperature range of 1150–1350°C, suitable for the glass compositions of each embodiment, comparative example, and reference example, and a winding speed range of 600–1200 rpm, suitable for the glass compositions of each embodiment, comparative example, and reference example, to obtain a glass fiber sample with a filament diameter of 13.0 μm.

[0150] Next, according to K. Sebastian et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2002), the dissolution test of the aforementioned glass fiber samples was conducted. Specifically, firstly, reagents No. 1 to 12 as shown in Table 1 were added sequentially to approximately 800 mL of distilled water kept at 37°C. The pH was adjusted to 4.5 using hydrochloric acid (No. 13), and finally adjusted to 1 L, to prepare an artificial lung fluid with the composition shown in Table 1, simulating the intrapulmonary environment at pH 4.5. The prepared artificial lung fluid was then allowed to stand for 24 hours. Subsequently, the pH of the artificial lung fluid increased due to the removal of carbon dioxide after standing; therefore, hydrochloric acid was used to adjust the pH of the artificial lung fluid kept at 37°C to 4.5 again.

[0151] It should be noted that fibers are known to be absorbed by macrophages after being inhaled by the lungs. The pH around macrophages is 4.5. Therefore, it can be expected that fibers with high solubility in artificial lung fluid at pH 4.5 will be dissolved in the lungs.

[0152] [Table 1]

[0153] No. Composition 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

[0154] Next, the glass fiber sample was cut into lengths of 1–3 mm that could be housed within an in-line filter holder, thus preparing a glass fiber sample for the dissolution test. This glass fiber sample was placed on a 0.2 μm pore size membrane filter housed within the in-line filter holder. Artificial lung fluid heated to 37°C was pumped into the in-line filter holder at a flow rate of 140–170 mL / day using a pump. The filtrate that had passed through the test glass fiber sample and the filter holder was collected in a container, thereby conducting the dissolution test. The flow rate of the artificial lung fluid (unit: μm³) was then used to measure the dissolution. 3 / s) and sample surface area (unit: μm) 2 The mass of the sample placed on the membrane filter was adjusted so that the ratio of artificial lung fluid flow rate to sample surface area was 0.030±0.005μm / s.

[0155] After 24 hours, the filtrate was recovered from the container. Si, Al, B, and Ca were used as analyte ions, and inductively coupled plasma atomic emission spectrometry (IPC-AES) was used to quantitatively analyze the dissolved ion components in the filtrate. The ICP-AES quantitative results (μg) for Si, Al, B, and Ca were converted to oxide values ​​and divided by 24 hours to calculate the dissolution rate (μg / h) of each component. If the total dissolution rate (μg / h) of all components was above 100 μg / h, the biocompatibility was rated as "OK"; if the total dissolution rate (μg / h) of all components was less than 100 μg / h, the biocompatibility was rated as "NG". The results are shown in Table 2.

[0156] [Possibility of long fiber formation]

[0157] Using a high-temperature electric furnace equipped with a rotational viscometer (manufactured by MOTOYAMA Co., Ltd.), the aforementioned glass shavings were melted in a platinum crucible. The viscosity of the molten glass was continuously measured while the melting temperature was changed using the rotational viscometer. The temperature corresponding to a rotational viscosity of 1000 poise was measured, and the 1000 poise temperature was thus determined.

[0158] Next, 40g of glass particles with a diameter of 0.5–1.5 mm, obtained by crushing the aforementioned glass shards, were placed in a 180×20×15mm platinum dish. The dish was heated for at least 8 hours in a tubular electric furnace with a temperature gradient set to 900–1300°C. Afterward, the dish was removed from the furnace and observed using a polarizing microscope to determine the location where crystallization from the devitrified glass began to precipitate. The temperature inside the tubular furnace was measured using a thermocouple B, and the temperature at which precipitation began was determined as the liquidus temperature.

[0159] Next, the operating temperature range ΔT (ΔT = 1000 poise temperature - liquid phase temperature) was calculated based on the 1000 poise temperature and liquid phase temperature measured using the above method. When ΔT is above 100℃, the likelihood of long fiber formation is rated "A"; when ΔT is above 0℃ but below 100℃, the likelihood of long fiber formation is rated "B"; and when ΔT is below 0℃, the likelihood of long fiber formation is rated "C". The results are shown in Table 2.

[0160] [Strength during water absorption]

[0161] The aforementioned glass shavings were placed into a platinum container with a nozzle at the bottom. The platinum container was heated to a temperature range of 1150°C to 1350°C to melt the glass shavings and obtain molten glass. The molten glass was then pulled out from the nozzle and wound onto a winding device. Next, the heating temperature of the platinum container and the winding speed of the winding device were adjusted to wind the glass fibers onto the winding device at a heating temperature of 1150°C to 1350°C, suitable for the glass compositions of each embodiment, comparative example, and reference example, and a winding speed of 600 to 1200 rpm, suitable for the glass compositions of each embodiment, comparative example, and reference example, to obtain glass fibers with a filament diameter of 13.0 μm.

[0162] Next, a single fiber (monofilament) is extracted from between the nozzle head and the winding device, and the fiber that has not deteriorated due to contact or friction is taken as a sample.

[0163] Next, the monofilaments were bonded to a specified backing paper with a central hole of 25 mm diameter. The backing paper was then completely immersed in distilled water at 25°C. After immersion for 3 hours, the backing paper was removed from the distilled water and dried in a dryer set at 50°C for 1 hour to prepare a test piece. This test piece was placed on the fixture of a tensile testing machine (manufactured by ORIENTEC Co., Ltd.), and after cutting off the ends of the backing paper, a tensile test was performed at a crosshead speed of 5 mm / min. The water absorption strength was calculated based on the maximum load at break and the fiber cross-sectional area. The fiber cross-sectional area was calculated using the fiber diameter obtained by observing the monofilaments using a scanning electron microscope (manufactured by Nippon Electron Co., Ltd., trade name: JSM-IT800). Test pieces that experienced yarn shedding during the test were removed, and the average value of n=12 was taken as the measured value of the water absorption strength. The results are shown in Table 2.

[0164] [Coefficient of linear expansion]

[0165] To remove the strain from the glass fragments, the sample was heated at a slow cooling temperature (550–750°C) for 2 hours and then cooled to room temperature for 8 hours to obtain a test piece. Next, it was machined into a 4mm × 4mm × 20mm test piece for determining the coefficient of linear expansion using a cutting machine, such as a diamond cutter and grinder. Then, the obtained test piece for determining the coefficient of linear expansion was heated at a heating rate of 10°C / min, and the elongation was measured using a thermal expansion coefficient measuring device (NETZSCH, trade name: DIL402) within a temperature range of 50–200°C. The coefficient of linear expansion was calculated based on this elongation.

[0166] [Table 2]

[0167]

[0168] As can be clearly seen from Table 2, the glass compositions for glass fibers according to Examples 1-4 can produce glass filaments that are biosoluble, can be made into long fibers, and have sufficiently high strength when absorbing water.

[0169] On the other hand, it is evident that the glass filaments obtained from the glass compositions for glass fibers of Comparative Examples 1 and 2, where the ratio of MgO content to CaO content (MgO / CaO) is less than 0.29, while possessing biosolubility, cannot achieve sufficiently high strength when absorbing water. Furthermore, it is evident that the glass filaments obtained from the glass composition for glass fibers of Comparative Example 3, where the ratio of MgO content to CaO content (MgO / CaO) exceeds 1.92 and the total content of MgO and CaO is less than 17.09% by mass, while possessing biosolubility, cannot achieve sufficiently high strength when absorbing water, and have a low likelihood of becoming long fibers. Additionally, it is evident that the glass filaments obtained from the glass composition for glass fibers of Comparative Example 4, where the ratio of MgO content to CaO content (MgO / CaO) is within the scope of the present invention, but the total content of MgO and CaO is less than 17.09% by mass, while possessing biosolubility, cannot achieve sufficiently high strength when absorbing water.

[0170] Furthermore, the glass filaments made from the glass composition for glass fibers in the reference example, where the SiO2 content relative to the total amount exceeds 50.00% by mass and the MgO content is less than 2.00% by mass, clearly lack biosolubility. It should be noted that the glass composition of the glass composition for glass fibers in the reference example is the E glass composition, which is the most commonly used glass composition for glass fibers.

Claims

1. A glass composition for glass fiber, characterized in that, Relative to the total amount, it includes: SiO2 in the range of 35.00% to 50.00% by mass Al2O3 in the range of 12.00% to 28.00% by mass B2O3 in the range of 10.00% to 25.00% by mass MgO in the range of 2.00% to 18.00% by mass CaO ranging from 5.00% to 25.00% by mass, The combined content of MgO and CaO ranges from 17.09% to 30.00% by mass. The ratio of MgO content to CaO content, i.e., MgO / CaO, is in the range of 0.29 to 1.

92. The content of SiO2 S, the content of Al2O3 A, the content of B2O3 B, the content of MgO M, and the content of CaO C satisfy the following formula (1). 20.8≤S×(C+M) / (A+B)≤34.0…(1).

2. The glass composition for glass fiber according to claim 1, characterized in that, The ratio of MgO content to CaO content, i.e., MgO / CaO, is in the range of 0.49 to 1.

68.

3. A type of glass fiber, characterized in that, It comprises glass filaments formed from the glass composition for glass fibers as described in claim 1.

4. The glass fiber according to claim 3, characterized in that, The diameter of the glass filament is less than 3.0 μm.

5. A glass fiber fabric, characterized in that, It contains the glass fiber as described in claim 3 or 4.

6. A glass fiber reinforced resin composition, characterized in that, It contains the glass fiber as described in claim 3 or 4.

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