Glass composition for glass fibers, glass fiber, glass fiber woven fabric, and glass fiber-reinforced resin composition

Abstract

Provided is a glass composition for glass fibers, which is biosoluble, which can be made into a long fiber, and from which it is possible to obtain a glass filament that has a sufficiently high strength even when exposed to water or to a high-temperature and high-humidity environment. A glass composition for glass fibers according to the present invention contains, with respect to the total amount, 35.00-50.00 mass% of SiO2, 12.00-28.00 mass% of Al2O3, 10.00-25.00 mass% of B2O3, 2.00-18.00 mass% of MgO, and 5.00-25.00 mass% of CaO. The total percentage content of MgO and CaO is 17.09-30.00 mass%, and MgO / CaO is 0.29-1.92.

Description

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

[0001] The present invention relates to a glass composition for glass fibers, a glass fiber, a glass fiber fabric, and a glass fiber reinforced resin composition.

[0002] In recent years, glass fiber reinforced resin compositions, particularly printed wiring boards containing glass fiber fabrics, have become lighter, thinner, shorter, and smaller, and accordingly, extremely fine long glass fibers are being required. Therefore, it is thought that biosolubility will become an important property of long glass fibers in the future.

[0003] Therefore, the present inventors have already proposed a glass composition for glass fiber that is biosoluble and can be made into long fibers (see Patent Document 1).

[0004] Patent No. 7107468

[0005] The long glass fibers may be exposed to water during the spinning process, in a step of applying a surface treatment agent to the surface of the glass fibers, or during the process of opening a glass fiber fabric in the process of processing the glass fibers into a form such as a glass roving, a glass yarn, or a glass fiber fabric. Furthermore, if the long glass fibers are stored for a long period of time in a warehouse with insufficient air conditioning during the process of processing them into a final product such as a glass fiber reinforced resin composition or when they are used as a final product, they may be exposed to a high-temperature and high-humidity environment depending on the weather conditions.

[0006] However, biosoluble long glass fibers are hydrophilic and therefore have low water resistance. When exposed to water or a high-temperature, high-humidity environment, the strength of the glass filaments decreases, which accelerates product deterioration. In addition, the tension applied when transporting the glass fibers can cause the glass filaments to break, resulting in the generation of minute fluff.

[0007] Therefore, an object of the present invention is to provide a glass composition for glass fiber that eliminates such inconveniences, has biosolubility, can be made into long fibers, and can provide glass filaments that have sufficiently high strength even when exposed to water or a high-temperature, high-humidity environment.

[0008] In order to achieve this object, the glass composition for glass fiber of the present invention contains SiO in the range of 35.00 to 50.00 mass % based on the total amount. ２ and Al in the range of 12.00 to 28.00 mass%. ２ O ３ and B in the range of 10.00 to 25.00 mass% ２ O ３ and 2.00 to 18.00 mass% of MgO and 5.00 to 25.00 mass% of CaO, wherein the total content of MgO and CaO is in the range of 17.09 to 30.00 mass%, and the ratio of the MgO content to the CaO content (MgO / CaO) is in the range of 0.29 to 1.92.

[0009] The glass composition for glass fiber of the present invention has the above-mentioned constitution, and therefore it is possible to obtain glass filaments that are biosoluble, can be made into long fibers, and have sufficiently high strength even when exposed to water or a high-temperature, high-humidity environment.

[0010] Here, "having biosolubility" means that the biosolubility described below is 100 μg / h or more, "being able to be made into long fibers" means that the working temperature range, which is the difference between the 1000 poise temperature and the liquidus temperature, is 0°C or higher, and "having sufficiently high strength even when exposed to water or a high-temperature, high-humidity environment" means that the strength when absorbing water, described below, is 2.1 GPa or more (i.e., having a strength when absorbing water that is equal to or greater than that of glass fiber made of E-glass composition).

[0011] In the glass composition for glass fiber of the present invention, the ratio of the MgO content to the CaO content (MgO / CaO) is preferably in the range of 0.49 to 1.68, and glass filaments can be obtained that are biosoluble, easy to be lengthened, and have excellent strength even when exposed to water or a high-temperature, high-humidity environment.

[0012] Here, "easily made into long fibers" means that the working temperature range, which is the difference between the 1000 poise temperature and the liquidus temperature, is 100°C or higher, and "having excellent strength even when exposed to water or a high-temperature and high-humidity environment" means that the strength when absorbing water, which will be described later, is 2.3 GPa or higher.

[0013] The glass fiber of the present invention is characterized by containing glass filaments made of the glass composition for glass fiber of the present invention. In the glass fiber of the present invention, it is preferable that the filament diameter of the glass filaments is less than 3.0 μm.

[0014] The glass fiber fabric and the glass fiber reinforced resin composition of the present invention are characterized by containing the glass fiber of the present invention.

[0015] Next, the embodiment of the present invention will be described in more detail.

[0016] The glass composition for glass fiber of this embodiment contains SiO in the range of 35.00 to 50.00 mass % based on the total amount. ２ and Al in the range of 12.00 to 28.00 mass%. ２ O ３ and B in the range of 10.00 to 25.00 mass% ２ O ３ and 2.00 to 18.00 mass% of MgO and 5.00 to 25.00 mass% of CaO, the total content of MgO and CaO being in the range of 17.09 to 30.00 mass%, and the ratio of the MgO content to the CaO content (MgO / CaO) being in the range of 0.29 to 1.92.

[0017] In the glass composition for glass fiber of this embodiment, SiO ２ If the content of SiO is less than 35.00 mass%, the strength and elastic modulus of the long glass fiber will be reduced, and when the long glass fiber is used in a composite material with a resin, the effect of reinforcing the resin will be insufficient. ２ If the content exceeds 50.00% by mass, the biosolubility may decrease.

[0018] In the glass composition for glass fiber of this embodiment, SiO ２The content is preferably in the range of 35.50 to 49.40 mass%, more preferably in the range of 37.00 to 48.90 mass%, even more preferably in the range of 38.00 to 47.90 mass%, particularly preferably in the range of 39.00 to 47.00 mass%, particularly preferably in the range of 40.00 to 46.00 mass%, particularly preferably in the range of 41.00 to 45.00 mass%, and most preferably in the range of 41.60 to 44.40 mass%.

[0019] In addition, in the glass composition for glass fiber of this embodiment, Al ２ O ３ If the content of Al is less than 12.00 mass %, the strength and elastic modulus of the long glass fiber will be reduced, and when used in a composite material with a resin, the effect of reinforcing the resin will be insufficient. ２ O ３ If the content exceeds 28.00 mass %, the devitrification temperature of the molten glass becomes high, which may make it difficult to produce long fibers.

[0020] In the glass composition for glass fiber of this embodiment, Al relative to the total amount ２ O ３ The content is preferably in the range of 15.10 to 27.00 mass%, more preferably in the range of 16.10 to 26.00 mass%, even more preferably in the range of 17.00 to 25.00 mass%, particularly preferably in the range of 18.00 to 24.00 mass%, particularly preferably in the range of 18.50 to 23.00 mass%, and most preferably in the range of 19.00 to 22.00 mass%.

[0021] In addition, in the glass composition for glass fiber of this embodiment, B ２ O ３ If the content of B is less than 10.00% by mass, the devitrification temperature of the molten glass becomes high, which may make it difficult to produce long fibers, and the biosolubility may decrease. ２ O ３ However, if the content exceeds 25.00 mass %, phase separation occurs in the molten glass, making it difficult to produce long fibers.

[0022] In the glass composition for glass fiber of this embodiment, B relative to the total amount ２ O ３ The content is preferably in the range of 11.10 to 24.00 mass%, more preferably in the range of 12.00 to 21.30 mass%, even more preferably in the range of 12.30 to 18.00 mass%, particularly preferably in the range of 12.50 to 17.50 mass%, particularly preferably in the range of 12.70 to 17.00 mass%, particularly preferably in the range of 12.80 to 16.50 mass%, and most preferably in the range of 13.50 to 16.20 mass%.

[0023] In the glass composition for glass fiber of this embodiment, if the content of MgO is less than 2.00 mass % relative to the total amount, the elastic modulus of the long glass fiber decreases, and when used in a composite material with a resin, the effect of reinforcing the resin becomes insufficient. On the other hand, if the content of MgO exceeds 18.00 mass % relative to the total amount, the strength of the long glass fiber decreases, and when used in a composite material with a resin, the effect of reinforcing the resin becomes insufficient.

[0024] 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 mass%, more preferably in the range of 5.10 to 16.00 mass%, even more preferably in the range of 6.10 to 15.40 mass%, particularly preferably in the range of 8.10 to 15.00 mass%, particularly preferably in the range of 8.40 to 14.00 mass%, especially preferably in the range of 8.60 to 13.00 mass%, especially more preferably in the range of 8.70 to 12.00 mass%, and most preferably in the range of 9.10 to 11.95 mass%.

[0025] In the glass composition for glass fiber of this embodiment, if the CaO content is less than 5.00 mass % relative to the total amount, the elastic modulus of the long glass fiber decreases, and when used in a composite material with a resin, the effect of reinforcing the resin becomes insufficient.On the other hand, if the CaO content exceeds 25.00 mass % relative to the total amount, the strength of the long glass fiber decreases, and when used in a composite material with a resin, the effect of reinforcing the resin becomes insufficient.

[0026] 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 mass%, more preferably in the range of 6.60 to 23.00 mass%, even more preferably in the range of 10.10 to 22.50 mass%, particularly preferably in the range of 13.40 to 22.00 mass%, particularly preferably in the range of 13.80 to 21.90 mass%, and most preferably in the range of 14.00 to 17.90 mass%.

[0027] In the glass composition for glass fiber of this embodiment, if the total content of MgO and CaO relative to the total amount is less than 17.09 mass %, the strength of the glass filaments decreases when the long glass fibers absorb water. On the other hand, if the total content of MgO and CaO relative to the total amount is more than 30.00 mass %, the strength of the long glass fibers decreases, and when used in a composite material with a resin, the effect of reinforcing the resin becomes insufficient.

[0028] 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 mass%, more preferably in the range of 19.00 to 28.00 mass%, even more preferably in the range of 20.00 to 27.00 mass%, particularly preferably in the range of 20.50 to 26.00 mass%, especially preferably in the range of 21.00 to 25.00 mass%, and most preferably in the range of 22.00 to 24.50 mass%.

[0029] In the glass composition for glass fiber of this embodiment, if the ratio of the MgO content to the CaO content (MgO / CaO) is less than 0.29, the strength of the glass filament decreases when the long glass fiber absorbs water. On the other hand, if the ratio of the MgO content to the CaO content (MgO / CaO) exceeds 1.92, the devitrification temperature of the molten glass increases, making it difficult to form long glass fibers.

[0030] In the glass composition for glass fiber of the present embodiment, the ratio of the MgO content to the 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.

[0031] The glass composition for glass fiber of the present embodiment contains SiO ２ , B ２ O ３ , Al ２ O ３ The total content of CaO and MgO is, for example, 91.00% by mass or more, preferably 95.00% by mass or more, more preferably 98.00% by mass or more, even more preferably 99.00% by mass or more, particularly preferably 99.30% by mass or more, particularly preferably 99.50% by mass or more, particularly preferably 99.70% by mass or more, and most preferably 99.90% by mass or more.

[0032] The glass composition for glass fiber of the present embodiment contains Fe from the viewpoint of improving the degassing property of molten glass and increasing the stability of fiber lengthening. ２ O ３ It may contain Fe ２ O ３ The content of is, for example, in the range of 0 to 0.40 mass %, preferably in the range of 0 to 0.30 mass %, more preferably in the range of 0 to 0.20 mass %, even more preferably in the range of 0 to 0.10 mass %, particularly preferably in the range of 0 to 0.05 mass %, and most preferably in the range of 0 to 0.01 mass %, relative to the total amount of the glass composition for glass fiber of the present embodiment.

[0033] In addition, the glass composition for glass fiber of the present embodiment contains ZrO from the viewpoint of reducing the melt viscosity of the molten glass and facilitating the production of long fibers. ２ ZrO ２The content of is, for example, in the range of 0 to 0.60 mass %, preferably in the range of 0 to 0.30 mass %, more preferably in the range of 0 to 0.20 mass %, even more preferably in the range of 0 to 0.10 mass %, particularly preferably in the range of 0 to 0.05 mass %, and most preferably in the range of 0 to 0.01 mass %, relative to the total amount of the glass composition for glass fiber of the present embodiment.

[0034] The glass composition for glass fiber of the present embodiment is, from the viewpoint of improving the degassing property of molten glass and increasing the stability of fiber lengthening, ２ and Cl ２ F ２ and Cl ２ The total content of the glass composition for glass fiber of the present embodiment is, for example, in the range of 0 to 0.40 mass%, preferably in the range of 0 to 0.30 mass%, more preferably in the range of 0 to 0.20 mass%, even more preferably in the range of 0 to 0.10 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%, relative to the total amount of the glass composition for glass fiber of the present embodiment.

[0035] The glass composition for glass fiber of this embodiment may contain SrO from the viewpoint of reducing the melt viscosity of the molten glass and facilitating fiber lengthening. The content of SrO is, for example, in the range of 0 to 0.40 mass%, preferably 0 to 0.30 mass%, more preferably 0 to 0.20 mass%, even more preferably 0 to 0.10 mass%, particularly preferably 0 to 0.05 mass%, and most preferably 0 to 0.01 mass%, relative to the total amount of the glass composition for glass fiber of this embodiment.

[0036] The glass composition for glass fiber of this embodiment may contain ZnO from the viewpoint of suppressing an increase in the devitrification temperature of molten glass and facilitating fiber lengthening. The ZnO content is, for example, in the range of 0 to 0.40 mass%, preferably 0 to 0.30 mass%, more preferably 0 to 0.20 mass%, even more preferably 0 to 0.10 mass%, particularly preferably 0 to 0.05 mass%, and most preferably 0 to 0.01 mass%, relative to the total amount of the glass composition for glass fiber of this embodiment.

[0037] The glass composition for glass fiber of the present embodiment contains SnO from the viewpoint of suppressing an increase in the devitrification temperature of molten glass and facilitating fiber lengthening. ２ It may contain SnO ２ The content of is, for example, in the range of 0 to 0.40 mass %, preferably in the range of 0 to 0.30 mass %, more preferably in the range of 0 to 0.20 mass %, even more preferably in the range of 0 to 0.10 mass %, particularly preferably in the range of 0 to 0.05 mass %, and most preferably in the range of 0 to 0.01 mass %, relative to the total amount of the glass composition for glass fiber of the present embodiment.

[0038] The glass composition for glass fiber of the present embodiment is, from the viewpoint of suppressing an increase in the devitrification temperature of molten glass and facilitating fiber lengthening, ２ O ５ P ２ O ５ From the viewpoint of suppressing the generation of bubbles in the molten glass, the content of is, for example, in the range of less than 2.50 mass %, preferably less than 1.50 mass %, more preferably less than 1.00 mass %, even more preferably less than 0.80 mass %, particularly particularly preferably less than 0.60 mass %, and most preferably less than 0.50 mass %, relative to the total amount of the glass composition for glass fiber of the present embodiment.

[0039] The glass composition for glass fiber of this embodiment contains TiO ２ When containing TiO ２The content of TiO is, for example, in the range of 1.90 mass% or less, preferably in the range of 0 to 0.40 mass%, more preferably in the range of 0 to 0.20 mass%, even more preferably in the range of 0 to less than 0.10 mass%, particularly preferably in the range of 0 to 0.05 mass%, and most preferably in the range of 0 to 0.01 mass%, relative to the total amount of the glass composition for glass fiber of this embodiment. ２ If the content exceeds 1.90 mass %, the biosolubility of the glass fiber may decrease.

[0040] The glass composition for glass fiber of the present embodiment is, from the viewpoint of reducing the melt viscosity of the molten glass and facilitating the production of long fibers, ２ O.K. ２ O and Na ２ It may contain O. ２ O.K. ２ O and Na ２ The total content of O is, for example, in the range of 0 to 0.90 mass %, preferably in the range of 0 to 0.40 mass %, more preferably in the range of 0 to 0.20 mass %, even more preferably in the range of 0 to 0.10 mass %, particularly preferably in the range of 0 to 0.05 mass %, and most preferably in the range of 0 to 0.01 mass %, relative to the total amount of the glass composition for glass fiber of the present embodiment.

[0041] The glass composition for glass fiber of this embodiment may contain, as impurities derived from raw materials, oxides of Ba, Mn, Co, Ni, Cu, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb in a total amount of less than 1.00 mass% relative to the total amount of the glass composition for glass fiber. In particular, the glass composition for glass fiber of this embodiment may contain, as impurities, BaO, CeO ２ , Y ２ O ３ , La ２ O ３ , Bi ２ O ３ , Gd ２ O ３ , Pr ２ O ３ , Sc ２ O ３ , or Yb ２ O３ When these elements are contained, the contents thereof are each independently preferably in the range of less than 0.40% by mass, more preferably in the range of less than 0.20% by mass, even more preferably in the range of less than 0.10% by mass, particularly preferably in the range of less than 0.05% by mass, particularly preferably in the range of less than 0.01% by mass, and most preferably in the range of less than 0.004% by mass.

[0042] In addition, the glass composition for glass fiber of the present embodiment has a higher elastic modulus when made into glass fiber, and therefore, Al ２ O ３ The ratio of the MgO content to the Al content (MgO / Al ２ O ３ ) is preferably 0.28 or more, and from the viewpoint of excellent water resistance when made into glass fiber, it is preferably 0.63 or less. ２ O ３ The ratio of the MgO content to the Al content (MgO / Al ２ O ３ ) is preferably in the range of 0.28 to 0.77, more preferably in the range of 0.41 to 0.63.

[0043] Furthermore, the glass composition for glass fiber of this embodiment has excellent biosolubility when made into glass fiber, and from the viewpoint of facilitating the production of long fibers, the SiO ２ the content S of Al ２ O ３ The content of A and B ２ O ３ The content B of S, the content M of MgO, and the content C of CaO preferably satisfy the following formula (1), and more preferably the following formula (2): 20.8≦S×(C+M) / (A+B)≦34.0 (1) 27.0≦S×(C+M) / (A+B)≦33.0 (2)

[0044] In the formula (1) or (2), as mentioned above, if C+M is too small, the strength of the glass filament tends to decrease when the long glass fiber absorbs water, while if it is too large, the viscosity of the glass decreases, narrowing the working temperature range and making it difficult to form long fibers. ２ O ３ and B ２ O ３ SiO relative to the total content ２ If the content is too small, the mechanical properties of the glass fiber tend to deteriorate, while if the content is too large, the melting property tends to deteriorate and the biosolubility tends to decrease.

[0045] When the lower limit of the formula (1) or (2) is 20.8 or more, preferably 27.0 or more, the glass filaments tend to be less susceptible to deterioration when absorbing water while maintaining the biosolubility of the long glass fiber. When the upper limit of the formula (1) or (2) is 34.0 or less, preferably 33.0 or less, the biosolubility is improved, and the stability of fiber lengthening is improved by widening the working temperature range.

[0046] In the glass composition for glass fiber of this embodiment, the content of each of the above-mentioned components can be measured using an ICP optical emission spectrometer for the light element Li, and using a wavelength dispersive X-ray fluorescence analyzer for the other elements. Specifically, the content of each of the above-mentioned components can be measured as follows.

[0047] First, a glass batch prepared by mixing glass raw materials or glass fiber is placed in a platinum crucible and melted in an electric furnace while stirring at a temperature of 1350 to 1550°C for the glass batch or at a temperature of 1300 to 1450°C for the glass fiber for 6 hours. Here, if organic matter is attached to the surface of the glass fiber or if the glass fiber is contained mainly as a reinforcing material in an organic matter such as a resin, the organic matter is removed before use, for example, by heating in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours.

[0048] Next, the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then crushed and powdered to produce glass powder. The light element Li is quantitatively analyzed using an ICP optical emission spectrometer after the glass powder is thermally decomposed with acid. Other elements are quantitatively analyzed using a wavelength-dispersive X-ray fluorescence spectrometer after the glass powder is formed into a disk shape using a press. Specifically, quantitative analysis using a wavelength-dispersive X-ray fluorescence spectrometer can be performed by preparing a calibration curve sample based on the results measured using the fundamental parameter method and analyzing it using the calibration curve method. The content of each component in the calibration curve sample can be quantitatively analyzed using an ICP optical emission spectrometer.

[0049] The results of these quantitative analyses are converted into oxides to calculate the content and total amount of each component, and the content (mass %) of each component described above can be determined from these values.

[0050] Next, the glass fiber of this embodiment contains glass filaments made of the glass composition for glass fiber of this embodiment. The glass fiber of this embodiment can be produced as follows.

[0051] First, a glass raw material (glass batch) prepared to have the composition of the glass composition for glass fiber of this embodiment based on the components contained in the ore that serves 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 and melted at a temperature in the range of, for example, 1350 to 1550° C. Next, the molten glass batch (molten glass) is drawn out from 1 to 20,000 nozzle tips of a bushing that are controlled to a predetermined temperature, and quenched to form glass filaments.

[0052] Next, a sizing agent or binder is applied to the formed glass filaments using an applicator, which is a coating device, and 1 to 20,000 glass filaments are bundled using a bundling shoe, and then wound at high speed onto a tube using a winding machine, thereby obtaining glass fibers.

[0053] When the glass composition for glass fiber of the present embodiment is melted at a temperature within the above range for producing the glass fiber, the glass composition can be lengthened by setting the working temperature range ΔT (working temperature range ΔT=1000 poise temperature−liquid phase temperature) calculated using the 1000 poise temperature and the liquid phase temperature to 0° C. or higher, and the glass composition can be easily lengthened by setting the working temperature range ΔT to 100° C. or higher.

[0054] Here, the glass single fiber (glass filament) discharged from one nozzle tip or hole and cooled and solidified preferably has a true circular cross-sectional shape and a diameter (filament diameter) of less than 3.0 μm. On the other hand, when the nozzle tip has a non-circular shape and has a protrusion or notch for quenching the molten glass, it is possible to obtain a glass filament having a non-circular cross-sectional shape, such as an ellipse or oval, by controlling the temperature conditions. When the glass filament has an elliptical or oval cross-sectional shape, it is preferable that the converted fiber diameter, which is the fiber diameter when the cross-sectional area is converted to a true circle, is less than 3.0 μm. The lower limit of the filament diameter is, for example, 0.5 μm, preferably 1.0 μm, and more preferably 2.0 μm.

[0055] The filament diameter of the glass filament can be calculated, for example, as follows. First, glass fibers are embedded in a resin such as an epoxy resin and the resin is cured. The cured resin is then cut and its cross section is polished. Next, the cross section of the cured resin is observed using an electron microscope, and for 50 or more glass filaments exposed in the cross section, if the cross section of the glass filament is a perfect circle or a nearly perfect circle, the diameter of the glass filament is measured. If the cross section of the glass filament is other than a perfect circle or a nearly perfect circle, the cross section of the glass filament is calculated, and the equivalent fiber diameter is calculated based on the cross section. Next, the filament diameter of the glass filament is calculated by averaging the measured or calculated diameters or equivalent fiber diameters. Alternatively, the filament diameter of the glass filament can also be measured by image processing of an image obtained from the electron microscope using an automatic analyzer.

[0056] On the other hand, when the glass fiber of this embodiment is contained in a glass fiber reinforced resin molded product, the filament diameter of the glass filament can be measured, for example, as follows. First, the glass fiber reinforced resin molded product is heated at 625°C for 30 minutes to burn off the thermoplastic resin and extract the glass fiber. Next, the filament diameter of the glass filament is measured in the same manner as the method for measuring the filament diameter of the glass filament in the glass fiber described above.

[0057] The glass fiber of this embodiment may be surface-coated with an organic substance for the purposes of improving the bundling of glass filaments, improving the adhesion between the glass fiber and resin, improving the uniform dispersion of the glass fiber in a mixture of the glass fiber and resin or inorganic material, etc. Examples of such organic substances include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene, particularly carboxylic acid-modified polypropylene, and copolymers of (poly)carboxylic acid, particularly maleic acid, with unsaturated monomers.

[0058] The glass fiber of this embodiment may be coated with a resin composition containing, in addition to these resins, a silane coupling agent, a lubricant, a surfactant, etc. Alternatively, the glass fiber of this embodiment may be coated with a treatment composition containing, without containing the above-mentioned resins, a silane coupling agent, a surfactant, etc. Such a resin composition or treatment composition coats the glass fiber in a proportion of 0.03 to 2.0 mass % based on the mass of the glass fiber of this embodiment in a state not coated with the resin composition or treatment composition.

[0059] The coating of glass fibers with the organic substance can be carried out, for example, in the glass fiber manufacturing process by applying a resin solution or a resin composition solution to the glass fibers using a known method such as a roller applicator, and then drying the glass fibers to which the resin solution or the resin composition solution has been applied. The coating of glass fibers with the organic substance can also be carried out by immersing the glass fibers of this embodiment in the form of a woven fabric in a treatment composition solution, and then drying the glass fibers to which the treatment composition has been applied.

[0060] Examples of the silane coupling agent include aminosilane, ureidosilane, chlorosilane, epoxysilane, mercaptosilane, vinylsilane, (meth)acrylicsilane, phenylsilane, styrylsilane, and isocyanatesilane. In this embodiment, the silane coupling agent may be used alone or in combination of two or more.

[0061] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0062] Examples of ureidosilane include γ-ureidopropyltriethoxysilane.

[0063] Examples of chlorosilanes include γ-chloropropyltrimethoxysilane.

[0064] Examples of epoxy silanes include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0065] Examples of mercaptosilane include γ-mercaptotrimethoxysilane and γ-mercaptopropyltrimethoxysilane.

[0066] Examples of vinylsilanes include vinyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, and N-benzyl-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0067] Examples of the (meth)acrylic silane include γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

[0068] Examples of phenylsilane include phenyltrimethoxysilane.

[0069] The styrylsilane may include p-styryltrimethoxysilane.

[0070] Examples of isocyanate silanes include γ-isocyanate propyl triethoxy silane.

[0071] Examples of lubricants include modified silicone oils, animal oils and their hydrogenated products, vegetable oils and their hydrogenated products, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimines, polyalkylpolyamine alkylamide derivatives, fatty acid amides, and quaternary ammonium salts. In this embodiment, the lubricants may be used alone or in combination of two or more.

[0072] Examples of animal oils include beef tallow.

[0073] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, etc.

[0074] Examples of animal waxes include beeswax and lanolin.

[0075] Examples of vegetable waxes include candelilla wax and carnauba wax.

[0076] Examples of mineral waxes include paraffin wax and montan wax.

[0077] Examples of the condensation products of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.

[0078] 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.

[0079] Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0080] Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, the surfactants may be used alone or in combination of two or more.

[0081] Examples of nonionic surfactants 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 castor oil ethers, hydrogenated castor oil ethylene oxide adducts, alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, glycerol fatty acid esters, polyglycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyhydric alcohol alkyl ethers, fatty acid alkanolamides, acetylene glycol, acetylene alcohol, ethylene oxide adducts of acetylene glycol, and ethylene oxide adducts of acetylene alcohol.

[0082] Examples of cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (acetates, hydrochlorides, etc.), ethylene oxide adducts of higher alkylamines, condensates of higher fatty acids and polyalkylenepolyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridinium salts.

[0083] 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-methyltaurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphate salts of higher alcohol ethylene oxide adducts.

[0084] Examples of amphoteric surfactants include amino acid type amphoteric surfactants such as alkali metal salts of alkylaminopropionic acid, betaine type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline type amphoteric surfactants.

[0085] Examples of the form of the glass fiber include woven fabric (glass cloth), knitted fabric, yarn, chopped strand, roving, chopped strand mat, paper, mesh, braided fabric, and milled fiber. Chopped strand, roving, and woven fabric (glass cloth) are preferred, and woven fabric (glass cloth) is more preferred.

[0086] For example, when the glass fiber of this embodiment is a chopped strand, the number of glass filaments constituting the glass fiber of this embodiment is, for example, 10 to 20,000, preferably 50 to 10,000, and more preferably 1,000 to 8,000. The length of the chopped strand, which is the glass fiber of this embodiment, is, for example, 1.0 to 100.0 mm, preferably 1.2 to 51.0 mm, more preferably 1.5 to 30.0 mm, even more preferably 2.0 to 15.0 mm, and particularly preferably 2.3 to 7.8 mm. Here, the chopped strand can be obtained by cutting the glass fiber produced by the above-mentioned method to the predetermined length using a known device such as a long fiber cutting device that cuts the glass fiber by feeding it between a cutter roller having cutters (cutting blades) attached radially at equal intervals and a rubber roller that rotates in contact with the cutter roller and has rubber on its outer circumferential surface.

[0087] When the glass fiber of this embodiment is a roving, the number of glass filaments constituting the glass fiber of this embodiment is, for example, 200 to 30,000. The roving, which is the glass fiber of this embodiment, has a mass per unit length of 0.5 to 10,000 tex (g / 1,000 m).

[0088] The glass fiber fabric of this embodiment is made of the glass fiber of this embodiment. The glass fiber fabric of this embodiment can be obtained by weaving the glass fiber of this embodiment as warp and weft using a known loom. Examples of the loom include a jet loom such as an air jet or water jet loom, a shuttle loom, and a rapier loom. Examples of weaving methods used with the loom include plain weave, satin weave, sash weave, and twill weave, with plain weave being preferred from the viewpoint of manufacturing efficiency.

[0089] The glass fibers of this embodiment contained in the glass fiber fabric of this embodiment are made 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 / 1000 m), more preferably have a mass of 0.5 to 70.0 tex (g / 1000 m); they are made of glass filaments having a filament diameter of 2.0 μm or more and less than 3.0 μm, and preferably have a mass of 0.35 to 1.5 tex, and particularly preferably have a mass of 0.5 to 1.5 tex.

[0090] Here, the filament diameter of the glass fiber of this embodiment contained in the glass fiber fabric of this embodiment is the average value of measured values ​​obtained by measuring the diameters of the glass filaments constituting the glass fiber at at least 50 points on a cross section of the glass fiber using a scanning electron microscope (manufactured by JEOL Ltd., product name: JSM-IT800, magnification: 3000 times).

[0091] The glass fiber fabric of this embodiment is preferably made 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.

[0092] The weave density of the warp yarns can be determined by counting the number of warp yarns within a 25 mm range in the warp direction using a fabric speculum in accordance with JIS R 3420. The weave density of the weft yarns can be determined by counting the number of weft yarns within a 25 mm range in the weft direction using a fabric speculum in accordance with JIS R 3420.

[0093] After being woven, the glass fiber fabric of this embodiment may be subjected to a de-oiling treatment, a surface treatment, and a fiber-opening treatment.

[0094] The deoiling treatment may involve placing the glass fiber fabric 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 fibers.

[0095] The surface treatment may include a treatment in which a glass fiber fabric is immersed in a solution containing the silane coupling agent or the silane coupling agent and the surfactant, excess water is squeezed out, and the fabric is then heated and dried at a temperature in the range of 80 to 180°C for 1 to 30 minutes.

[0096] Examples of the opening treatment include a process in which the warp and weft widths are widened by applying a tension of 20 to 200 N to the warp yarns of a glass fiber fabric, such as opening by water jet pressure, opening by high-frequency vibration using a liquid as a medium, opening by pressure of a fluid having a surface pressure, or opening by pressure using a roll.

[0097] The glass fiber fabric of this embodiment has a fiber density of 2.5 to 220 g / m ２ and preferably has a mass in the range of 5.0 to 220 g / m ２ It is more preferable that the thickness of the conductive film be in the range of 4.0 to 200.0 μm.

[0098] The glass fiber fabric of the present embodiment may also have a surface treatment layer containing the silane coupling agent, or the silane coupling agent and the surfactant. When the glass fiber fabric of the present embodiment includes the surface treatment layer, the surface treatment layer may have a mass of, for example, 0.03 to 1.50 mass% relative to the total mass of the glass fiber fabric including the surface treatment layer.

[0099] 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 contains a resin (thermoplastic resin or thermosetting resin), glass fiber, and other additives, and contains 10 to 90 mass% of glass fiber based on the total amount of the glass fiber reinforced resin composition. Furthermore, the glass fiber reinforced resin composition of this embodiment contains 90 to 10 mass% of resin based on the total amount of the glass fiber reinforced resin composition, and contains other additives in the range of 0 to 40 mass%.

[0100] 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), polytrimethylene terephthalate (PTT), polycarbonate, polyarylene sulfide, polyethersulfone (PES), polyphenylsulfone (PPS), and the like. U), 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, polybutylene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, polyvinyl alcohol (PVA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), and the like.

[0101] Specific 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.

[0102] Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0103] Examples of polystyrene include general-purpose polystyrene (GPPS), which is an atactic polystyrene having an atactic structure, high impact polystyrene (HIPS), which is GPPS with a rubber component added, and syndiotactic polystyrene having a syndiotactic structure.

[0104] Examples of methacrylic resins include a homopolymer of one of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and a fatty acid vinyl ester, or a copolymer of two or more of them.

[0105] Examples of polyvinyl chloride include vinyl chloride homopolymers polymerized by conventional methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization; copolymers of vinyl chloride monomers with copolymerizable monomers; and graft copolymers obtained by graft-polymerizing vinyl chloride monomers onto polymers.

[0106] Examples of polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), and polydecamethylene adipamide (nylon 410). Polyethylene sebacamide (Nylon 1010), polydecamethylene dodecamide (Nylon 1012), polyundecane amide (Nylon 11), polyundecamethylene adipamide (Nylon 116), polydodecanamide (Nylon 12), polyxylene adipamide (Nylon XD6), polyxylene sebacamide (Nylon XD10), polymeta-xylylene adipamide (Nylon MXD6), polypara-xylylene adipamide (Nylon PXD6), polytetramethylene terephthalamide (Nylon 4T), polypentamethylene terephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), polytetramethylene isophthalamide (nylon 4I), polybis( Examples of the copolymer include one or a copolymer of two or more of the following components: polybis(3-methyl-4-aminohexyl)methane terephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methane isophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methaneandodecamide (nylon PACM12), polybis(3-methyl-4-aminohexyl)methane tetradecamide (nylon PACM14), and the like, as well as mixtures thereof.

[0107] Examples of polyacetals include homopolymers having oxymethylene units as the main repeating units, and copolymers that are mainly composed of oxymethylene units and contain oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0108] Examples of polyethylene terephthalate include polymers obtainable by polycondensing terephthalic acid or a derivative thereof with ethylene glycol.

[0109] Examples of polybutylene terephthalate include polymers obtainable by polycondensation of terephthalic acid or a derivative thereof with 1,4-butanediol.

[0110] Examples of polytrimethylene terephthalate include polymers obtainable by polycondensation of terephthalic acid or a derivative thereof with 1,3-propanediol.

[0111] Examples of polycarbonates include polymers obtainable by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate in a molten state, and polymers obtainable by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

[0112] Examples of polyarylene sulfide include linear polyphenylene sulfide, crosslinked polyphenylene sulfide which has been polymerized and then subjected to a curing reaction to increase the molecular weight, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.

[0113] 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-1,4-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.

[0114] 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, the polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxy groups, and styryl groups have been introduced into the polymer chain terminals, and the polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxy groups, styryl groups, and methacrylic groups have been introduced into the polymer chain side chains.

[0115] Examples of polyaryletherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).

[0116] Examples of the liquid crystal polymer (LCP) include a (co)polymer, which is a thermotropic liquid crystal polyester, comprising one or more structural units selected from an aromatic hydroxycarbonyl unit, an aromatic dihydroxy unit, an aromatic dicarbonyl unit, an aliphatic dihydroxy unit, an aliphatic dicarbonyl unit, and the like.

[0117] Examples of fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0118] Examples of ionomer (IO) resins include copolymers of olefin or styrene with unsaturated carboxylic acid, in which a portion of the carboxyl groups is neutralized with metal ions.

[0119] Examples of the olefin / vinyl alcohol resin include an ethylene / vinyl alcohol copolymer, a propylene / vinyl alcohol copolymer, a saponified ethylene / vinyl acetate copolymer, and a saponified propylene / vinyl acetate copolymer.

[0120] Examples of the cyclic olefin resin include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0121] Examples of polylactic acid include poly-L-lactic acid, which is a homopolymer of the L-form, poly-D-lactic acid, which is a homopolymer of the D-form, and stereocomplex polylactic acid, which is a mixture thereof.

[0122] Examples of the cellulose resin include methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0123] Examples of the thermosetting resin include unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenolic resin (PF), urethane resin (PU), polyisocyanate, polyisocyanurate, modified polyimide (PI) resin, urea (UF) resin, silicone (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleimide triazine (BT) resin, and diallyl phthalate resin (PDAP).

[0124] Specifically, the unsaturated polyester resin may be a resin obtainable by esterifying an aliphatic unsaturated dicarboxylic acid with an aliphatic diol.

[0125] Examples of vinyl ester resins include bis-based vinyl ester resins and novolac-based vinyl ester resins.

[0126] 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-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexidienebisphenol type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, and the like. Examples of epoxy resins include epoxy resins, novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure, biphenyl-type epoxy resins, aralkyl-type epoxy resins such as xylylene-type epoxy resins and phenylaralkyl-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins, difunctional to tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalenearalkyl-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, and fluorene-type epoxy resins.

[0127] The melamine resin may be a polymer obtained by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0128] Examples of the phenolic resin include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol A-type novolac resin; resole-type phenolic resins such as methylol-type resole resin and dimethylene ether-type resole resin; and aryl alkylene-type phenolic resins, and examples thereof include one or a combination of two or more of these.

[0129] Examples of urea resins include resins obtainable by condensation of urea and formaldehyde.

[0130] The thermoplastic resins or thermosetting resins may be used alone or in combination of two or more.

[0131] Examples of the 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, antiblocking agents, lubricants, nucleating agents, antibacterial agents, and pigments.

[0132] The glass fiber reinforced resin composition of this embodiment may be a prepreg obtained by impregnating the glass fiber fabric of this embodiment with the resin by a method known per se and semi-curing the impregnated resin.

[0133] The glass fiber reinforced resin composition of this embodiment can be molded by a known molding method to obtain various glass fiber reinforced resin molded articles. Examples of known molding methods include injection molding, injection compression molding, two-color molding, blow molding, foam molding using a supercritical fluid, insert molding, in-mold coating molding, autoclave molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, blow molding, stamping molding, infusion molding, hand layup, spray-up, low-pressure RIM molding, resin transfer molding, sheet molding compounding, bulk molding compounding, pultrusion, and filament winding. Glass fiber reinforced resin molded articles can also be obtained by curing the prepreg.

[0134] Examples of uses of such molded articles include electronic components such as printed wiring boards and connectors, housings for electronic devices, interior and exterior vehicle components, housings for electronic devices such as antennas and radars, and separators for fuel cells.

[0135] Next, examples of the present invention and comparative examples will be described.

[0136] [Examples 1 to 4, Comparative Examples 1 to 4, Reference Example] First, glass raw materials were mixed to obtain glass batches so that the glass compositions after melting and solidifying would be the compositions of Examples 1 to 4, Comparative Examples 1 to 4, and Reference Example shown in Table 2.

[0137] The resulting glass batch was placed in a platinum crucible, and the platinum crucible was held in an electric furnace for 4 hours at a temperature in the range of 1350 to 1550°C, which was suitable for melting the glass batches of the Examples, Comparative Examples, and Reference Examples. The glass batch was melted while being stirred, thereby obtaining a homogeneous molten glass. The resulting molten glass was then poured onto a carbon plate and cooled to obtain a lump of glass cullet.

[0138] The obtained glass cullets were then used to evaluate their biosolubility, fiber lengthening potential, and water-absorbed strength by the following methods. The results are shown in Table 2.

[0139] The total elution rate of Si, B, Al and Ca of the glass fiber obtained from the glass composition for glass fiber of Example 1 was 106 μg / h, the working temperature range was 159° C. and the linear expansion coefficient was 5.5 ppm / K.

[0140] [Biosolubility] First, the glass cullet was placed in a platinum container equipped with a nozzle tip at the bottom, and the platinum container was heated to a temperature in the range of 1150 to 1350 ° C. to melt the glass cullet and obtain molten glass. Next, the molten glass was drawn out from the nozzle tip and wound around a winding device. Next, the heating temperature of the platinum container and the winding speed of the winding device were adjusted, and the glass fiber was wound around the winding device at a heating temperature in the range of 1150 to 1350 ° C. suitable for the glass composition of each Example, Comparative Example, and Reference Example, and at a winding speed in the range of 600 to 1200 rpm suitable for the glass composition of each Example, Comparative Example, and Reference Example, to obtain a glass fiber sample having a filament diameter of 13.0 μm.

[0141] Next, an elution test of the glass fiber sample was conducted in accordance with K. Sebastian et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2002). Specifically, reagents No. 1 to 12 shown in Table 1 were sequentially added to approximately 800 mL of distilled water kept at 37°C. The pH was adjusted to 4.5 using hydrochloric acid (No. 13) until the final volume reached 1 L. This prepared artificial lung fluid had the composition shown in Table 1 and a pH of 4.5, simulating the intrapulmonary environment. The prepared artificial lung fluid was then allowed to stand for 24 hours. Since the pH of the artificial lung fluid had risen after standing due to the release of carbon dioxide, the pH of the artificial lung fluid kept at 37°C was readjusted to 4.5 using hydrochloric acid.

[0142] It is known that when fibers are taken up into the lungs, they are taken up by macrophages. Since the pH around macrophages is 4.5, fibers that are highly soluble in artificial lung fluid with a pH of 4.5 are expected to dissolve in the lungs.

[0143]

[0144] Next, the glass fiber sample was cut into lengths of 1 to 3 mm, which were lengths that could fit into an in-line filter holder, to prepare glass fiber samples for elution tests. The glass fiber samples for elution tests were placed on a membrane filter with a pore size of 0.2 μm installed in an in-line filter holder, and the artificial lung fluid heated to 37°C was pumped into the in-line filter holder at a flow rate of 140 to 170 mL / day. The filtrate that passed through the test glass fiber sample and the filter holder was collected in a container, and an elution test was performed. At this time, the flow rate of the artificial lung fluid (unit: μm 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 the flow rate of the artificial lung fluid to the surface area of ​​the sample was 0.030±0.005 μm / s.

[0145] After 24 hours, the filtrate was collected from the container, and the eluted ion components in the filtrate were quantified using inductively coupled plasma atomic emission spectrometry (IPC-AES) with Si, Al, B, and Ca as the analytes. The ICP-AES quantification results (μg) for Si, Al, B, and Ca were converted to oxides and divided by 24 hours to calculate the elution rate (μg / h) of each component. When the total elution rate (μg / h) of each component was 100 μg / h or more, the biosolubility was evaluated as "OK", and when the total elution rate (μg / h) of each component was less than 100 μg / h, the biosolubility was evaluated as "NG". The results are shown in Table 2.

[0146] [Possibility of Fiber Lengthening] The glass cullet described above was melted in a platinum crucible using a high-temperature electric furnace equipped with a rotational viscometer (manufactured by Motoyama Corporation), and the viscosity of the molten glass was continuously measured using the rotational viscometer while changing the melting temperature. The temperature corresponding to the rotational viscosity of 1000 poise was measured, thereby determining the 1000 poise temperature.

[0147] Next, 40 g of glass particles having a particle size of 0.5 to 1.5 mm obtained by crushing the glass cullet was placed in a platinum boat measuring 180 × 20 × 15 mm, and heated for 8 hours or more in a tubular electric furnace with a temperature gradient of 900 to 1300 ° C. After that, the boat was removed from the tubular electric furnace and observed with a polarizing microscope to identify the position where crystals derived from the devitrified glass began to precipitate. The temperature inside the tubular electric furnace was measured using a B thermocouple, and the temperature at the position where precipitation began was determined and taken as the liquidus temperature.

[0148] Next, the working temperature range ΔT (ΔT = 1000 poise temperature - liquidus temperature) was calculated from the 1000 poise temperature and liquidus temperature measured by the above method. When ΔT was 100°C or more, the possibility of fiber formation was evaluated as "A", when ΔT was 0°C or more and less than 100°C, the possibility of fiber formation was evaluated as "B", and when ΔT was less than 0°C, the possibility of fiber formation was evaluated as "C". The results are shown in Table 2.

[0149] [Strength upon water absorption] The glass cullet obtained above was placed in a platinum container equipped with a single nozzle tip at the bottom, and the platinum container was heated to a temperature in the range of 1150 to 1350°C to melt the glass cullet and obtain molten glass. Next, the molten glass was drawn out from the nozzle tip and wound around a winding device. Next, the heating temperature of the platinum container and the winding speed of the winding device were adjusted, and the glass fiber was wound around the winding device at a heating temperature in the range of 1150 to 1350°C suitable for the glass composition of each Example, Comparative Example, and Reference Example, and at a winding speed in the range of 600 to 1200 rpm suitable for the glass composition of each Example, Comparative Example, and Reference Example, to obtain a glass fiber having a filament diameter of 13.0 μm.

[0150] Next, a single fiber (monofilament) between the nozzle tip and the winding device was collected and used as a sample without any deterioration due to contact or friction.

[0151] Next, the monofilament was adhered to a specified mount with a 25 mm diameter hole in the center. It was then completely immersed in distilled water at 25°C. After immersion for 3 hours, it was removed from the distilled water and dried in a dryer set at 50°C for 1 hour to prepare a test specimen. The test specimen was set in the gripper of a tensile tester (manufactured by Orientec Co., Ltd.), and the end of the mount was cut off. A tensile test was performed at a crosshead speed of 5 mm / min, and the water-absorbed strength was calculated from the maximum load at break and the fiber cross-sectional area. The fiber cross-sectional area was calculated from the fiber diameter obtained by observing the monofilament with a scanning electron microscope (manufactured by JEOL Ltd., product name: JSM-IT800). Test specimens that experienced thread loss during measurement were excluded, and the average value of n = 12 was used as the measured water-absorbed strength. The results are shown in Table 2.

[0152] [Linear expansion coefficient] To remove distortion from the glass cullet, the glass cullet was heated at a slow cooling temperature (550-750°C) for 2 hours and then cooled to room temperature over 8 hours to obtain a test specimen. The test specimen was then machined into a 4 mm x 4 mm x 20 mm test specimen for measuring the linear expansion coefficient using a cutting machine, such as a diamond cutter and a polishing machine. The resulting test specimen for measuring the linear expansion coefficient was then heated at a heating rate of 10°C / min, and the elongation was measured at temperatures ranging from 50 to 200°C using a thermal expansion measuring device (manufactured by NETZSCH, product name: DIL402). The linear expansion coefficient was calculated from the elongation.

[0153]

[0154] From Table 2, it is clear that the glass compositions for glass fibers of Examples 1 to 4 can provide glass filaments that are biosoluble, can be lengthened, and have sufficiently high strength when absorbing water.

[0155] On the other hand, it is clear that the glass filaments obtained from the glass compositions for glass fiber of Comparative Examples 1 and 2, in which the ratio of the MgO content to the CaO content (MgO / CaO) is less than 0.29, are biosoluble but are unable to obtain sufficiently high strength upon water absorption. Also, it is clear that the glass filaments obtained from the glass composition for glass fiber of Comparative Example 3, in which the ratio of the MgO content to the CaO content (MgO / CaO) is more than 1.92 and the total content of MgO and CaO is less than 17.09 mass%, are biosoluble but are unable to obtain sufficiently high strength upon water absorption and are also low in fiber lengthening potential. Furthermore, although the ratio of the MgO content to the CaO content (MgO / CaO) is within the range of the present invention, it is clear that the glass filament obtained from the glass composition for glass fiber of Comparative Example 4, in which the total content of MgO and CaO is less than 17.09 mass%, is biosoluble but is unable to obtain sufficiently high strength upon water absorption.

[0156] Furthermore, SiO ２It is clear that the glass filaments obtained from the glass composition for glass fiber of Reference Example, in which the content of SiO2 exceeds 50.00 mass% and the content of MgO is less than 2.00 mass%, do not have biosolubility. The glass composition of the glass composition for glass fiber of Reference Example is an E-glass composition, which is considered to be the most commonly used glass composition for glass fiber.

Claims

1. A glass composition for glass fiber, comprising 35.00 to 50.00 mass% of SiO ２ and Al in the range of 12.00 to 28.00 mass%. ２ O ３ and B in the range of 10.00 to 25.00 mass%. ２ O ３ % to 25.00% by mass, wherein the total content of MgO and CaO is in the range of 17.09 to 30.00% by mass, and the ratio of the MgO content to the CaO content (MgO / CaO) is in the range of 0.29 to 1.

92.

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

68.

3. A glass fiber comprising glass filaments made of the glass composition for glass fiber according to claim 1.

4. The glass fiber according to claim 3, wherein the filament diameter of the glass filaments is less than 3.0 μm.

5. A glass fiber fabric comprising the glass fiber according to claim 3 or 4.

6. A glass fiber reinforced resin composition comprising the glass fiber according to claim 3 or 4.

Images