Glass composition for glass fibers, glass fiber, glass cloth, and glass-fiber-reinforced resin composition

Abstract

Provided is a glass composition for glass fibers, the composition being able to yield glass fibers with a sufficient working temperature range, a low linear coefficient of thermal expansion, and the ability to suppress precipitation of Group 11 oxides. The glass composition for glass fibers according to the present invention comprises 42.00-62.00% SiO2, 17.00-30.00% Al2O3, 7.00-20.60% P2O5, 0.00-12.00% ZnO, 0.10-10.00% of a Group 11 oxide, and 0.00-4.40% of an alkali metal oxide, relative to the total mass. In the glass composition, the mass ratio of the Group 11 oxide to P2O5 (the Group 11 oxide / P2O5) is 0.0060-0.8000.

Description

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

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

[0002] Glass fibers have traditionally been widely used to improve the strength of resin compositions, and glass fiber-reinforced resin compositions are increasingly being used in housings, components, and printed wiring boards for electronic devices such as servers, smartphones, and laptops. In recent years, as electronic devices have become smaller and lighter, the thickness of the printed wiring boards used in these electronic devices has been reduced, and these printed wiring boards are required to have not only high rigidity but also excellent dimensional stability. Therefore, the glass fibers used to reinforce the printed wiring boards are particularly required to have a low linear expansion coefficient.

[0003] The glass fiber is produced by melting glass raw materials prepared to obtain a glass composition for glass fiber having a desired composition in a glass melting furnace to obtain molten glass (a melt of the glass composition for glass fiber), discharging the molten glass from a container (bushing) made of a noble metal such as platinum having a nozzle plate on which several to several thousand nozzle tips are formed, and winding it up at high speed to cool and solidify it while stretching it into a fibrous form (hereinafter, this operation may be referred to as "spinning").

[0004] As the glass composition for glass fiber, for example, a glass composition for glass fiber in which the content of copper oxide is increased and the content of zinc oxide is decreased compared to a conventional glass composition for glass fiber having a low linear expansion coefficient is known (see, for example, Patent Document 1). According to the glass composition for glass fiber described in Patent Document 1, it is said that the linear expansion coefficient of glass fiber made of the glass composition for glass fiber can be reduced to 3 ppm / °C or less.

[0005] Patent No. 7387790

[0006] However, the glass composition for glass fiber described in Patent Document 1 has a narrow working temperature range, making it difficult to stably carry out the spinning, and also has the disadvantage that, depending on the copper oxide content, the copper oxide may precipitate in a heating step such as a deoiling step after the obtained glass fiber is processed into glass cloth. If the copper oxide precipitates in the glass cloth, there is a concern that the electrical properties, such as insulation reliability, of a printed wiring board including the glass cloth may deteriorate.

[0007] An object of the present invention is to provide a glass composition for glass fiber that eliminates such inconveniences, has a sufficient working temperature range, allows stable spinning of glass fiber, and can provide glass fiber that has a low linear expansion coefficient and can suppress precipitation of oxides of Group 11 elements such as copper oxide.

[0008] In order to achieve this object, the glass composition for glass fiber of the present invention contains SiO in the range of 42.00 to 62.00 mass % based on the total amount. ２ and Al in the range of 17.00 to 30.00 mass% ２ O ３ and P in the range of 7.00 to 20.60 mass% ２ O ５ ZnO in the range of 0.00 to 12.00 wt. %, an oxide of a Group 11 element in the range of 0.10 to 10.00 wt. %, and an alkali metal oxide in the range of 0.00 to 4.40 wt. %, ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５ ) is in the range of 0.0060 to 0.8000.

[0009] According to the glass composition for glass fiber of the present invention, it is possible to obtain glass fiber that has a sufficient working temperature range, allows stable spinning of glass fiber, has a low linear expansion coefficient, and can suppress the precipitation of oxides of Group 11 elements such as copper oxide.

[0010] Here, "having a sufficient working temperature range" means that the working temperature range of the glass composition for glass fiber of the present invention is 0° C. or higher. Furthermore, "having a more sufficient working temperature range" means that the working temperature range of the glass composition for glass fiber of the present invention is 40° C. or higher.

[0011] Furthermore, a low linear expansion coefficient means that the linear expansion coefficient of the glass fiber obtained from the glass composition for glass fiber of the present invention is 2.00 ppm / °C or less.

[0012] Furthermore, being able to suppress the deposition of oxides of Group 11 elements means that no deposition of oxides of Group 11 elements is observed under the following condition 1 or condition 2.

[0013] The condition 1 is as follows.

[0014] First, a molten glass obtained by melting the glass composition for glass fiber of the present invention is air-cooled to room temperature (25°C) at a rate of 100°C / min in air to obtain a glass bulk. Then, the obtained glass bulk is cut, and a region of 3 mm from the surface layer that directly contacted the air is observed with a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0015] Furthermore, condition 2 is as follows:

[0016] First, a molten glass obtained by melting the glass composition for glass fiber of the present invention is air-cooled to room temperature (25°C) at a rate of 100°C / min in air to obtain a glass bulk. Thereafter, the obtained glass bulk is heated from room temperature (25°C) to 750°C over 2 hours, maintained at 750°C for 2 hours, and slowly cooled to room temperature (25°C) over 8 hours. Thereafter, the slowly cooled glass bulk is cut, and a region of 3 mm from the surface layer that directly contacted the air is observed with a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0017] The glass composition for glass fiber of the present invention contains P in the range of 10.40 to 14.70 mass %. ２ O ５ and ZnO in the range of 1.30 to 12.00 mass %, ２ O ５The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５ ) is preferably in the range of 0.02 to 0.60. As a result, the glass composition for glass fiber of the present invention has a more sufficient working temperature range and can further suppress the precipitation of oxides of Group 11 elements.

[0018] In the glass composition for glass fiber of the present invention, examples of the oxide of the Group 11 element include copper oxide and silver oxide.

[0019] In this specification, copper oxide refers to CuO and Cu ２ O. Also, CuO and Cu ２ The total content of CuO and O may be referred to as T-CuO.

[0020] In this specification, silver oxide refers to Ag ２ Point to O.

[0021] The glass fiber of the present invention is characterized by comprising the glass composition for glass fiber of the present invention. The glass cloth of the present invention is characterized by containing the glass fiber of the present invention, and the glass fiber-reinforced resin composition of the present invention is characterized by containing the glass fiber of the present invention.

[0022] Next, the embodiment of the present invention will be described in more detail.

[0023] The glass composition for glass fiber of this embodiment contains SiO in the range of 42.00 to 62.00 mass% based on the total amount. ２ and Al in the range of 17.00 to 30.00 mass% ２ O ３ and P in the range of 7.00 to 20.60 mass% ２ O ５ ZnO in the range of 0.00 to 12.00 wt. %, an oxide of a Group 11 element in the range of 0.10 to 10.00 wt. %, and an alkali metal oxide in the range of 0.00 to 4.40 wt. %, ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５) is in the range of 0.0060 to 0.8000.

[0024] According to the glass composition for glass fiber of the present embodiment, it is possible to obtain glass fiber that has a sufficient working temperature range, allows stable spinning of glass fiber, has a low linear expansion coefficient, and can suppress precipitation of oxides of Group 11 elements.

[0025] Here, having a sufficient working temperature range means that the working temperature range of the glass composition for glass fiber of this embodiment is a range of 0° C. or higher. The working temperature range is the difference between the spinning temperature (1000 poise temperature) and the liquidus temperature of the glass composition for glass fiber.

[0026] Furthermore, "having a low linear expansion coefficient" means that the linear expansion coefficient of the glass fiber obtained from the glass composition for glass fiber of the present invention is 2.00 ppm / °C or less, and "being able to suppress precipitation of oxides of Group 11 elements" means that no precipitation of oxides of Group 11 elements is observed under the following condition 1 or condition 2.

[0027] The condition 1 is as follows.

[0028] First, a molten glass obtained by melting the glass composition for glass fiber of the present embodiment is air-cooled to room temperature (25°C) at a rate of 100°C / min in air to obtain a glass bulk. Thereafter, the obtained glass bulk is cut, and a region of 3 mm from the surface layer that directly contacted the air is observed with a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0029] Furthermore, condition 2 is as follows:

[0030] First, a molten glass obtained by melting the glass composition for glass fiber of this embodiment is air-cooled to room temperature (25°C) at a rate of 100°C / min in air to obtain a glass bulk. Thereafter, the obtained glass bulk is heated from room temperature (25°C) to 750°C over 2 hours, maintained at 750°C for 2 hours, and slowly cooled to room temperature (25°C) over 8 hours. Thereafter, the slowly cooled glass bulk is cut, and a region of 3 mm from the surface layer that directly contacted the air is observed with a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0031] In the glass composition for glass fiber of this embodiment, SiO ２ If the content of SiO is less than 42.00% by mass relative to the total amount, the working temperature range will be narrow, crystals will be formed during spinning, and the nozzle will be clogged, making spinning impossible. ２ If the content of exceeds 62.00 mass% of the total amount, the 1000 poise temperature becomes high, the melting property deteriorates, and the SiO ２ These particles flow into the nozzle as foreign matter, causing breakage during spinning and reducing productivity.

[0032] In the glass composition for glass fiber of this embodiment, SiO ２ The content is preferably in the range of 43.90 to 58.50 mass%, more preferably in the range of 44.40 to 56.40 mass%, even more preferably in the range of 45.50 to 54.90 mass%, particularly preferably in the range of 47.40 to 53.40 mass%, and especially preferably in the range of 48.90 to 52.00 mass%.

[0033] In the glass composition for glass fiber of this embodiment, Al ２ O ３ If the content of is less than 17.00% by mass relative to the total amount, the 1000 poise temperature becomes high and melting properties deteriorate, whereas if it exceeds 30.00% by mass, the working temperature range becomes narrow and spinnability deteriorates.

[0034] In the glass composition for glass fiber of this embodiment, Al relative to the total amount of the glass composition for glass fiber ２ O ３ The content is preferably in the range of 19.50 to 28.40 mass%, more preferably in the range of 20.90 to 27.80 mass%, even more preferably in the range of 21.40 to 27.20 mass%, particularly preferably in the range of 22.60 to 26.40 mass%, and particularly preferably in the range of 22.90 to 25.80 mass%.

[0035] In the glass composition for glass fiber of this embodiment, P ２ O ５If the content of is less than 7.0 mass % or more than 20.60 mass % based on the total amount, a sufficient working temperature range cannot be obtained, glass fiber spinning cannot be stably carried out, and the linear expansion coefficient of the glass fiber made from the glass composition for glass fiber of the present embodiment cannot be sufficiently reduced.

[0036] In the glass composition for glass fiber of this embodiment, P relative to the total amount of the glass composition for glass fiber ２ O ５ The content is preferably in the range of 8.50 to 17.40 mass%, more preferably in the range of 9.00 to 16.80 mass%, even more preferably in the range of 9.60 to 16.00 mass%, particularly preferably in the range of 10.40 to 14.70 mass%, particularly preferably in the range of 11.00 to 14.20 mass%, and most preferably in the range of 11.50 to 13.90 mass%.

[0037] In the glass composition for glass fiber of this embodiment, if the content of ZnO exceeds 12.0 mass % relative to the total amount, the linear expansion coefficient of the glass fiber made from the glass composition for glass fiber of this embodiment cannot be sufficiently reduced.

[0038] In the glass composition for glass fiber of this embodiment, the content of ZnO relative to the total amount of the glass composition for glass fiber is, from the viewpoint of suppressing precipitation of oxides of Group 11 elements, preferably in the range of 1.30 to 11.30 mass%, more preferably in the range of 1.60 to 10.40 mass%, even more preferably in the range of 1.80 to 8.50 mass%, particularly preferably in the range of 2.00 to 7.40 mass%, particularly preferably in the range of 2.20 to 6.50 mass%, and most preferably in the range of 2.50 to 6.00 mass%.

[0039] In the glass composition for glass fiber of this embodiment, if the content of the oxide of the Group 11 element is less than 0.1 mass % relative to the total amount, the linear expansion coefficient of the glass fiber made of the glass composition for glass fiber of this embodiment cannot be sufficiently reduced, and if it exceeds 10 mass %, precipitation of the oxide of the Group 11 element cannot be suppressed.

[0040] In the glass composition for glass fiber of this embodiment, the content of the oxide of Group 11 element relative to the total amount of the glass composition for glass fiber is, from the viewpoint of simultaneously achieving a reduction in the linear expansion coefficient and suppression of precipitation of the oxide of Group 11 element, preferably in the range of 0.10 to 9.40 mass%, more preferably in the range of 0.19 to 8.90 mass%, even more preferably in the range of 0.24 to 7.90 mass%, particularly preferably in the range of 0.29 to 7.40 mass%, particularly preferably in the range of 0.34 to 6.90 mass%, and most preferably in the range of 0.40 to 6.40 mass%.

[0041] Furthermore, from the viewpoint of more reliably suppressing the precipitation of the oxide of the Group 11 element, the content of the oxide of the Group 11 element relative to the total amount of the glass composition for glass fiber of the present invention is preferably in the range of 0.10 to 8.40 mass%, more preferably in the range of 0.30 to 6.90 mass%, even more preferably in the range of 0.50 to 5.40 mass%, particularly preferably in the range of 0.70 to 3.90 mass%, particularly preferably in the range of 0.80 to 3.40 mass%, and most preferably in the range of 0.90 to 3.20 mass%.

[0042] Furthermore, from the viewpoint of more reliably reducing the linear expansion coefficient, the content of the oxide of the Group 11 element relative to the total amount of the glass composition for glass fiber of the present invention is preferably in the range of 0.40 to 9.50 mass%, more preferably in the range of 1.20 to 8.40 mass%, even more preferably in the range of 1.90 to 7.70 mass%, particularly preferably in the range of 2.40 to 7.40 mass%, especially preferably in the range of 2.90 to 6.90 mass%, and most preferably in the range of 3.90 to 6.40 mass%.

[0043] As the Group 11 element, copper or silver is preferred from the viewpoint of raw material cost and ease of dissolution in molten glass, and copper is more preferred because it precipitates less in molten glass.

[0044] Furthermore, when the glass composition for glass fiber of this embodiment contains oxides of multiple types of Group 11 elements, the content of the oxides of the Group 11 elements represents the total content of the oxides of the respective Group 11 elements.

[0045] In the glass composition for glass fiber of this embodiment, if the content of alkali metal oxide exceeds 4.4 mass% relative to the total amount, the linear expansion coefficient of the glass fiber made from the glass composition for glass fiber of this embodiment cannot be sufficiently reduced.

[0046] In the glass composition for glass fiber of this embodiment, the content of alkali metal oxides relative to the total amount of the glass composition for glass fiber is preferably in the range of 0.90 mass % or less, more preferably in the range of 0.40 mass % or less, even more preferably in the range of 0.10 mass % or less, and particularly preferably in the range of 0.04 mass % or less, from the viewpoint of further reducing the linear expansion coefficient.

[0047] The alkali metal oxides include Li ２ O, Na ２ O or K ２ The glass composition for glass fiber of this embodiment can include Li ２ O, Na ２ O.K. ２ O may be contained alone, Li ２ O, Na ２ O.K. ２ O may contain two or more alkali metal oxides selected from the group consisting of:

[0048] In the glass composition for glass fiber of this embodiment, P ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５ ) below 0.0060, a sufficient working temperature range cannot be obtained, and above 0.8000, the deposition of oxides of Group 11 elements cannot be suppressed.

[0049] In addition, in the glass composition for glass fiber of this embodiment, P ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５) is preferably in the range of 0.0100 to 0.7400, more preferably in the range of 0.0150 to 0.6600, even more preferably in the range of 0.0200 to 0.6000, particularly preferably in the range of 0.0300 to 0.5500, especially preferably in the range of 0.0340 to 0.5000, and most preferably in the range of 0.0400 to 0.4400, from the viewpoint of providing a sufficient working temperature range and suppressing precipitation of oxides of Group 11 elements.

[0050] Furthermore, the glass composition for glass fiber of this embodiment contains B in the range of 0.0 to 8.0 mass % based on the total amount. ２ O ３ may include:

[0051] Here, B relative to the total amount of the glass composition for glass fiber ２ O ３ From the viewpoint of lowering the liquidus temperature and lowering the linear expansion coefficient, the content of is preferably in the range of 6.40 mass% or less, more preferably in the range of 2.40 mass% or less, even more preferably in the range of 1.90 mass% or less, particularly preferably in the range of 1.40 mass% or less, and particularly preferably in the range of 0.90 mass% or less.

[0052] Furthermore, the glass composition for glass fibers of this embodiment may contain MgO in a range of 0.0 to 5.0 mass % based on the total amount.

[0053] Here, the content of MgO relative to the total amount of the glass composition for glass fiber is preferably in the range of 2.00 mass% or less, more preferably in the range of 1.90 mass% or less, and even more preferably in the range of 1.40 mass% or less, from the viewpoint of improving the meltability of the glass while lowering the linear expansion coefficient.

[0054] The glass composition for glass fiber of this embodiment is Al ２ O ３ B relative to the content of ２ O ３ The ratio of the contents of (B ２ O ３ / Al ２ O ３ ) is, for example, in the range of 0.34 or less.

[0055] Also, Al ２ O ３ B relative to the content of ２ O ３ The ratio of the contents of (B ２ O ３ / Al ２ O ３ From the viewpoint of achieving a good balance between the working temperature range and the linear expansion coefficient and obtaining a better working temperature range and linear expansion coefficient, the coefficient of linear expansion is preferably in the range of 0.20 or less, more preferably in the range of 0.16 or less, even more preferably in the range of 0.14 or less, particularly preferably in the range of 0.10 or less, and most preferably in the range of 0.08 or less.

[0056] Furthermore, the glass composition for glass fiber of this embodiment has a more sufficient working temperature range, further suppresses the precipitation of oxides of Group 11 elements, and further reduces the linear expansion coefficient, and therefore, contains SiO in the range of 42.00 to 62.00 mass% based on the total amount. ２ and Al in the range of 17.00 to 30.00 mass% ２ O ３ and P in the range of 10.40 to 14.70 mass%. ２ O ５ ZnO in the range of 1.30 to 12.00 mass %, an oxide of a Group 11 element in the range of 0.10 to 10.00 mass %, and B in the range of 0.00 to 2.40 mass %. ２ O ３ and an alkali metal oxide in the range of 0.00 to 4.40 mass %, ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５ ) is preferably in the range of 0.02 to 0.60, and in this case, B is preferably in the range of 0.00 to 1.90 mass%. ２ O ３ It is more preferred that the composition contains:

[0057] Here, "lower linear expansion coefficient" means that the linear expansion coefficient of the glass fiber obtained from the glass composition for glass fiber of the present invention is 1.60 ppm / °C or less. "Even lower linear expansion coefficient" means that the linear expansion coefficient of the glass fiber obtained from the glass composition for glass fiber of the present invention is 1.50 ppm / °C or less.

[0058] The glass composition for glass fiber of the present embodiment contains ZrO from the viewpoint of improving the linear expansion coefficient while adjusting the devitrification temperature and viscosity during glass formation. ２ or HfO ２ ZrO relative to the total amount of the glass composition for glass fiber. ２ or HfO ２ From the viewpoint of preventing a deterioration in the working temperature range due to an increase in the liquidus temperature, the content of each element is preferably in the range of 2.00% by mass or less, more preferably in the range of 0.90% by mass or less, even more preferably in the range of 0.50% by mass or less, particularly preferably in the range of 0.40% by mass or less, and especially preferably in the range of 0.10% by mass or less.

[0059] The glass composition for glass fiber of the present embodiment contains TiO from the viewpoint of improving the linear expansion coefficient while adjusting the devitrification temperature and viscosity during glass formation. ２ The amount of TiO relative to the total amount of the glass composition for glass fiber may be ２ From the viewpoint of ensuring the meltability of the raw material and suppressing the occurrence of striae, and from the viewpoint of preventing a deterioration in the working temperature range due to an increase in the liquidus temperature, the content of is preferably in the range of 4.00% by mass or less, more preferably in the range of 2.50% by mass or less, even more preferably in the range of 1.5% by mass or less, particularly preferably in the range of 0.90% by mass or less, particularly preferably in the range of 0.50% by mass or less, and most preferably in the range of 0.10% by mass or less.

[0060] The glass composition for glass fiber of the present embodiment may contain, as impurities derived from raw materials, oxides of Sr, Ba, Mn, Co, Ni, Cr, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, Mo, Pt, Rh, or Yb in a total amount of less than 3.00 mass%, preferably less than 2.00 mass%, and more preferably less than 1.00 mass%, based on the total amount of the glass composition for glass fiber.

[0061] In particular, the glass composition for glass fiber of this embodiment contains SrO, BaO, CeO as impurities. 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 O ３ When the glass composition for glass fiber contains the above, the contents thereof are preferably each independently in the range of less than 0.40 mass%, more preferably in the range of less than 0.20 mass%, even more preferably in the range of less than 0.10 mass%, particularly preferably in the range of less than 0.05 mass%, particularly preferably in the range of less than 0.01 mass%, and most preferably in the range of less than 0.001 mass%, relative to the total amount of the glass composition for glass fiber.

[0062] The content of each component of the glass composition for glass fiber can be measured using an ICP optical emission spectrometer for the light element Li, and a wavelength dispersive X-ray fluorescence analyzer for the other elements.

[0063] The content of each of the components can be measured, for example, as follows: First, a glass batch is placed in a platinum crucible and melted in an electric furnace at a temperature of 1650°C for 6 hours while stirring, thereby obtaining a homogeneous molten glass. Alternatively, glass fibers are placed in a platinum crucible and melted in an electric furnace at a temperature of 1650°C for 6 hours while stirring, thereby obtaining a homogeneous molten glass.

[0064] The glass batch is prepared by mixing glass raw materials. 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 material (resin), the glass fiber is used after removing the organic matter by, for example, heating in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours.

[0065] Next, the obtained molten glass is poured onto a carbon plate to produce glass cullet, and then the glass cullet is crushed and powdered to obtain glass powder.

[0066] Next, the glass powder is thermally decomposed with acid, and then quantitatively analyzed for Li, a light element, using an ICP optical emission spectrometer. For other elements, the glass powder is molded into a disk shape using a press to obtain a measurement sample, and then the measurement sample is quantitatively analyzed using a wavelength-dispersive X-ray fluorescence spectrometer. Quantitative analysis using a wavelength-dispersive X-ray fluorescence spectrometer can be performed by the following method. First, the content of each component in the measurement sample is measured using the fundamental parameter method. Next, based on the measurement results, at least three calibration curve samples are prepared and analyzed by the calibration curve method. The content of each component in the calibration curve samples can be quantitatively analyzed, for example, using an ICP optical emission spectrometer. The results of these quantitative analyses are converted into oxides to calculate the content and total amount of each component, and from these values, the content (mass%) of each component and P described above are calculated. ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５ ) and Al ２ O ３ B relative to the content of ２O ３ The ratio of the contents of (B ２ O ３ / Al ２ O ３ ) can be obtained.

[0067] The glass fiber of this embodiment is made of the glass composition for glass fiber of this embodiment described above.

[0068] The glass fiber of this embodiment can be formed from the glass composition for glass fiber of this embodiment, for example, as follows. First, glass raw materials are blended to obtain 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. Next, the blended glass raw materials (glass batch) are supplied to a melting furnace and melted at a temperature range of 1000 poise temperature or higher, specifically, at a temperature in the range of 1450 to 1650°C. Next, the glass batch (molten glass) melted at a temperature in this range is discharged from 100 to 8000 nozzle tips or holes in a bushing controlled at a predetermined temperature, and is cooled and solidified while being stretched by being wound up at high speed, thereby forming glass single fibers (glass filaments).

[0069] When forming the glass fiber of this embodiment, the glass filament discharged from one nozzle tip or hole and cooled and solidified typically has a perfect circular cross-sectional shape and a diameter in the range of 2.0 to 35.0 μm. For applications requiring a low linear expansion coefficient, the glass filament preferably has a diameter in the range of 3.0 to 6.0 μm, more preferably 3.0 to 4.5 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, glass filaments having a non-circular cross-sectional shape (e.g., elliptical or oval) can be obtained by controlling the temperature conditions. When the glass filament has an elliptical or oval cross-sectional shape, the ratio of the major axis to the minor axis of the cross-sectional shape (major axis / minor axis) is, for example, in the range of 2.0 to 10.0, and the fiber diameter (equivalent fiber diameter) when the cross-sectional area is converted to that of a perfect circle is, for example, in the range of 2.0 to 35.0 μm.

[0070] The glass fiber of this embodiment usually takes the form of a glass fiber bundle (glass strand) in which the glass filaments are bundled in the range of 10 to 8,000, and has a weight in the range of 0.3 to 10,000.0 tex (g / km).

[0071] The glass fiber of this embodiment has a linear expansion coefficient in the range of 2.00 ppm / ° C. or less. The linear expansion coefficient can be measured by the measurement method described later, and is preferably in the range of 1.60 ppm / ° C. or less, more preferably in the range of 1.50 ppm / ° C. or less, even more preferably in the range of 1.40 ppm / ° C. or less, particularly preferably in the range of 1.30 ppm / ° C. or less, and particularly preferably in the range of 1.20 ppm / ° C. or less.

[0072] The glass fiber of the present embodiment can take various forms, such as yarn, woven fabric (glass cloth), knitted fabric, nonwoven fabric (chopped strand mat, multiaxial nonwoven fabric, etc.), chopped strand, roving, powder, etc., obtained by further processing the glass strand in various ways.

[0073] The glass fiber of this embodiment may be coated on its surface with an organic substance for the purposes of improving the bundling of glass filaments, improving the adhesion between the glass fiber and resin, and improving the uniform dispersion of the glass fiber in a mixture of the glass fiber and resin or inorganic material. 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) and unsaturated monomers. The glass fiber of this embodiment may also be coated with a resin composition containing, in addition to these resins, a silane coupling agent, a lubricant, a surfactant, and the like. The glass fiber of this embodiment may also be coated with a treatment composition containing, without the resin, a silane coupling agent, a surfactant, and the like.

[0074] Such a resin composition or treatment composition coats the glass fiber in a proportion ranging from 0.1 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. Coating the glass fiber with the organic substance can be achieved, for example, by applying a resin solution or a resin composition solution to the glass fiber using a known method such as a roller applicator during the glass fiber manufacturing process, and then drying the glass fiber to which the resin solution or resin composition solution has been applied. Coating the glass fiber of this embodiment in the form of a woven fabric with the organic substance can be achieved by immersing the glass fiber in a treatment composition solution, and then drying the glass fiber to which the treatment composition has been applied.

[0075] Examples of the silane coupling agent include aminosilane, chlorosilane, epoxysilane, mercaptosilane, vinylsilane, acrylicsilane, and cationic silane. These compounds can be used alone or in combination of two or more.

[0076] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0077] Examples of chlorosilane include γ-chloropropyltrimethoxysilane.

[0078] Examples of epoxy silanes include γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0079] Examples of mercaptosilane include γ-mercaptotrimethoxysilane.

[0080] Examples of vinylsilanes include vinyltrimethoxysilane and N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane.

[0081] Examples of the acrylic silane include γ-methacryloxypropyltrimethoxysilane.

[0082] Examples of cationic silanes include N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and N-phenyl-3-aminopropyltrimethoxysilane hydrochloride.

[0083] Examples of the lubricant include modified silicone oil, animal oil and its hydrogenated product, vegetable oil and its hydrogenated product, animal wax, vegetable wax, mineral wax, condensation product of higher saturated fatty acid and higher saturated alcohol, polyethyleneimine, polyalkyl polyamine alkyl amide derivative, fatty acid amide, and quaternary ammonium salt.The lubricant can be used alone or in combination of two or more kinds.

[0084] Examples of animal oils include beef tallow.

[0085] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, etc.

[0086] Examples of animal waxes include beeswax and lanolin.

[0087] Examples of vegetable waxes include candelilla wax and carnauba wax.

[0088] Examples of mineral waxes include paraffin wax and montan wax.

[0089] Examples of the condensation products of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.

[0090] 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.

[0091] Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0092] Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. These surfactants can be used alone or in combination of two or more.

[0093] 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.

[0094] Examples of cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine acetate, higher alkylamine hydrochloride, 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.

[0095] 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.

[0096] Examples of amphoteric surfactants include amino acid type amphoteric surfactants such as alkali metal salts of alkylaminopropionic acid, betaine type surfactants such as alkyldimethylbetaine, and imidazoline type amphoteric surfactants.

[0097] The glass cloth of this embodiment contains the glass fiber of this embodiment described above. Specifically, the glass cloth of this embodiment can be obtained by weaving the glass fiber of this embodiment described above as at least a part of the warp or weft using a loom known per se. 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 the weaving method used on the loom include plain weave, satin weave, sash weave, and twill weave, with plain weave being preferred from the viewpoint of production efficiency.

[0098] In the glass cloth of this embodiment, the glass fiber of this embodiment described above preferably comprises glass filaments having a diameter in the range of 3.0 to 21.0 μm bundled together in a range of 35 to 20,000 pieces, having a twist in the range of 0 to 1.0 turns / 25 mm, and having a mass in the range of 0.9 to 600.0 tex (g / km).

[0099] In the glass cloth of the present embodiment, when the above-described glass fiber of the present embodiment is used as a warp or a weft, the warp weave density is preferably in the range of 10 to 120 threads / 25 mm, and the weft weave density is preferably in the range of 10 to 120 threads / 25 mm.

[0100] After being woven, the glass cloth of the present embodiment may be subjected to a deoiling treatment, a surface treatment, and a fiber-opening treatment.

[0101] The deoiling treatment may be, for example, a treatment in which the glass cloth is placed in a heating furnace at an atmospheric temperature in the range of 350°C to 400°C for a period in the range of 40 to 80 hours, to thermally decompose organic matter adhering to the glass fibers.

[0102] The surface treatment can include a treatment in which the glass cloth 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 glass cloth is then heated and dried at a temperature in the range of 80 to 180°C for a time in the range of 1 to 30 minutes.

[0103] Examples of the opening treatment include a process for expanding the yarn width of the warp and weft yarns by applying a tension in the range of 30 to 200 N to the warp yarns of the glass cloth using water jet pressure, a process for opening using high-frequency vibrations using a liquid as a medium, a process for opening using the pressure of a fluid having a surface pressure, and a process for opening using pressure with a roll.

[0104] In a glass cloth containing glass fibers made of a glass composition containing an oxide of a Group 11 element, when the glass cloth is cooled after being heated by the deoiling treatment or the like, the oxide of the Group 11 element contained in the glass filaments constituting the glass fibers may precipitate on the surface of the glass filaments. The precipitation of the oxide of the Group 11 element is a phenomenon in which the oxide of the Group 11 element contained in the glass filaments precipitates on the surface of the glass filaments, and therefore tends to be more pronounced when the glass cloth is slowly cooled rather than when it is rapidly cooled after the heating.

[0105] However, the glass cloth of the present embodiment, containing the glass fiber of the present embodiment described above, can suppress the precipitation of the oxides of the Group 11 elements. Specifically, the glass cloth of the present embodiment is one in which the precipitation of the oxides of the Group 11 elements is not observed under the following condition 1 or condition 2.

[0106] The condition 1 is as follows.

[0107] First, a molten glass, which is the glass composition for glass fiber of the present embodiment, is air-cooled in air at a rate of 100°C / min to room temperature (25°C) to obtain a glass bulk. Then, the obtained glass bulk is cut, and a region of 3 mm from the surface layer that directly contacted the air is observed with a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0108] Condition 2 is as follows:

[0109] First, a molten glass, which is the glass composition for glass fiber of this embodiment, is air-cooled in air at a rate of 100°C / min to room temperature (25°C) to obtain a glass bulk. Thereafter, the obtained glass bulk is heated from room temperature (25°C) to 750°C over 2 hours, maintained at 750°C for 2 hours, and slowly cooled to room temperature (25°C) over 8 hours. Thereafter, the slowly cooled glass bulk is cut, and a region of 3 mm from the surface layer that was directly in contact with air is observed with a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0110] The glass cloth of this embodiment has a density of 7.0 to 750.0 g / m ２ It is preferable that the thickness of the film be in the range of 8.0 to 500.0 μm and that the mass per unit area be in the range of 8.0 to 500.0 μm.

[0111] The yarn width of the warp yarns of the glass cloth of this embodiment is preferably in the range of 110 to 600 μm, and the yarn width of the weft yarns is preferably in the range of 110 to 600 μm.

[0112] The glass cloth of the present embodiment may have a surface treatment layer containing the silane coupling agent, or the silane coupling agent and the surfactant. When the glass cloth of the present embodiment has 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 cloth including the surface treatment layer.

[0113] 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, for example, 10 to 90 mass% of glass fiber relative to the total amount of the glass fiber reinforced resin composition. Furthermore, the glass fiber reinforced resin composition of this embodiment contains, for example, 90 to 10 mass% of resin and 0 to 40 mass% of other additives relative to the total amount of the glass fiber reinforced resin composition.

[0114] Examples of thermoplastic resins that form the glass fiber reinforced resin composition of this embodiment 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 (P TT), polycarbonate, polyarylene sulfide, polyethersulfone (PES), polyphenylsulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryletherketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate (PEN), ethylene / vinyl acetate (EVA) resin, ionomer (IO) resin, polybutadiene, styrene / butadiene resin, polybutylene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, and the like can be mentioned.

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

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

[0117] Examples of the 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.

[0118] Examples of the methacrylic resin include a polymer obtained by homopolymerizing 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 polymer obtained by copolymerizing two or more of them.

[0119] Examples of the polyvinyl chloride include a vinyl chloride homopolymer polymerized by a conventionally known method such as emulsion polymerization, suspension polymerization, microsuspension polymerization, or bulk polymerization; a copolymer of a vinyl chloride monomer with a copolymerizable monomer; and a graft copolymer obtained by graft-polymerizing a vinyl chloride monomer onto a polymer.

[0120] Examples of the polyamide include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polytetramethylene sebacamide (polyamide 410), polypentamethylene adipamide (polyamide 56), polypentamethylene sebacamide (polyamide 510), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene adipamide (polyamide 106), polydecamethylene adipamide (polyamide 107), polydecamethylene adipamide (polyamide 109), polydecamethylene adipamide (polyamide 110), polydecamethylene adipamide (polyamide 111), polydecamethylene adipamide (polyamide 112), polydecamethylene adipamide (polyamide 113), polydecamethylene adipamide (polyamide 114), polydecamethylene adipamide (polyamide 115), polydecamethylene adipamide (polyamide 116), polydecamethylene adipamide (polyamide 117), polydecamethylene adipamide (polyamide 118), polydecamethylene adipamide (polyamide 119 ... Polymethylene sebacamide (Polyamide 1010), Polydecamethylene dodecamide (Polyamide 1012), Polyundecaneamide (Polyamide 11), Polyundecamethylene adipamide (Polyamide 116), Polydodecanamide (Polyamide 12), Polyxylene adipamide (Polyamide XD6), Polyxylene sebacamide (Polyamide XD10), Polymeta-xylylene adipamide (Polyamide MXD6), Polypara-xylylene adipamide (Polyamide PXD6), Polytetramethylene terephthalamide (Po Polyamide 4T), Polypentamethylene terephthalamide (Polyamide 5T), Polyhexamethylene terephthalamide (Polyamide 6T), Polyhexamethylene isophthalamide (Polyamide 6I), Polynonamethylene terephthalamide (Polyamide 9T), Polydecamethylene terephthalamide (Polyamide 10T), Polyundecamethylene terephthalamide (Polyamide 11T), Polydodecamethylene terephthalamide (Polyamide 12T), Polytetramethylene isophthalamide (Polyamide 4I), Poly Examples include copolymers of one or more of the following components, such as bis(3-methyl-4-aminohexyl)methane terephthalamide (polyamide PACMT), polybis(3-methyl-4-aminohexyl)methane isophthalamide (polyamide PACMI), polybis(3-methyl-4-aminohexyl)methaneandodecamide (polyamide PACM12), and polybis(3-methyl-4-aminohexyl)methane tetradecamide (polyamide PACM14), as well as mixtures thereof.

[0121] Examples of the polyacetal include a homopolymer having an oxymethylene unit as the main repeating unit, and a copolymer mainly composed of oxymethylene units and containing an oxyalkylene unit having 2 to 8 adjacent carbon atoms in the main chain.

[0122] Examples of the polyethylene terephthalate include a polymer obtained by polycondensing terephthalic acid or a derivative thereof with ethylene glycol.

[0123] Examples of the polybutylene terephthalate include a polymer obtained by polycondensing terephthalic acid or a derivative thereof with 1,4-butanediol.

[0124] Examples of the polytrimethylene terephthalate include a polymer obtained by polycondensing terephthalic acid or a derivative thereof with 1,3-propanediol.

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

[0126] Examples of the 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.

[0127] Examples of the modified polyphenylene ether include a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / butadiene copolymer, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / maleic anhydride copolymer, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a polyamide, and a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / butadiene / acrylonitrile copolymer.

[0128] Examples of the polyaryletherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).

[0129] 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.

[0130] Examples of the fluororesin 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).

[0131] Examples of the ionomer (IO) resin include a copolymer of an olefin or styrene with an unsaturated carboxylic acid, in which a portion of the carboxyl groups is neutralized with a metal ion.

[0132] Examples of the olefin / vinyl alcohol resin include ethylene / vinyl alcohol copolymer, propylene / vinyl alcohol copolymer, saponified ethylene / vinyl acetate copolymer, and saponified propylene / vinyl acetate copolymer.

[0133] Examples of the cyclic olefin resin include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0134] Examples of the 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.

[0135] 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.

[0136] Examples of the thermosetting resin that forms the glass fiber reinforced resin composition of this embodiment include unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenolic resin (PF), urethane resin (PU), polyisocyanate, polyisocyanurate, polyimide (PI), urea (UF) resin, silicone (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleimide triazine (BT) resin, diallyl phthalate resin (PDAP), and thermosetting polyphenylene ether resin.

[0137] Specifically, the unsaturated polyester resin may be a resin obtainable by esterifying an aliphatic unsaturated dicarboxylic acid with an aliphatic diol.

[0138] Examples of vinyl ester resins include bis-based vinyl ester resins and novolac-based vinyl ester resins.

[0139] 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.

[0140] The melamine resin may be a polymer obtained by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0141] 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.

[0142] Urea resins include resins obtained by condensation of urea and formaldehyde.

[0143] The thermoplastic resins or thermosetting resins may be used alone or in combination of two or more.

[0144] Examples of the other additives include reinforcing fibers other than glass fibers (e.g., carbon fibers and metal fibers), fillers other than glass fibers (e.g., 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.

[0145] The glass fiber reinforced resin composition of the present embodiment can be obtained, for example, by kneading the chopped strands and the resin in a twin-screw kneader and then performing injection molding using the obtained resin pellets.

[0146] The glass fiber reinforced resin composition may be obtained by a known molding method such as injection compression molding, two-color molding, blow molding, foam molding (including supercritical fluid foam molding), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, blow molding, stamping molding, infusion, hand layup, spray-up, resin transfer molding, sheet molding compound method, bulk molding compound method, pultrusion method, or filament winding method.

[0147] The glass fiber reinforced resin composition of the present embodiment may also be a prepreg obtained by impregnating the glass fiber fabric of the present embodiment with the resin by a method known per se and semi-curing the impregnated resin.

[0148] Examples of uses of molded articles made from the glass fiber reinforced resin composition of the present embodiment include electronic device housings, electronic components, vehicle exterior components, vehicle interior components, vehicle engine peripheral components, muffler-related components, high-pressure tanks, and composite materials for wind energy.

[0149] Next, examples of the present invention and comparative examples will be described.

[0150] [Examples 1 to 11, Comparative Examples 1 to 6] For each glass batch prepared to have the composition of each glass composition for glass fiber of Examples 1 to 10 shown in Table 1, Comparative Examples 1 to 6 shown in Table 2, or Example 11 shown in Table 3, the 1000 poise temperature, liquidus temperature, and linear expansion coefficient were measured by the measurement methods described later, and the working temperature range (working temperature range = 1000 poise temperature - liquidus temperature) was calculated as the difference between the 1000 poise temperature and the liquidus temperature.

[0151] The working temperature range was rated as "C" when it was below 0°C, "B" when it was 0°C or higher but lower than 40°C, and "A" when it was 40°C or higher. Each glass batch was also evaluated by the evaluation method described below to determine whether or not the precipitation of copper oxide or silver oxide as an oxide of a Group 11 element was suppressed. The results are shown in Tables 1, 2, and 3.

[0152] [Method for measuring the 1000 poise temperature] First, the glass batch is placed in an 80 mm diameter platinum crucible and held in an electric furnace at a temperature in the range of 1500 to 1650°C for 4 hours, and the glass batch is melted while being stirred to obtain a homogeneous molten glass. Next, the obtained molten glass is poured onto a carbon plate and cooled to obtain a lump of glass cullet. Next, the glass cullet is melted, and the viscosity of the molten glass is continuously measured using a Brookfield viscometer while changing the melting temperature, and the temperature at which the rotational viscosity is 1000 poise is defined as the 1000 poise temperature.

[0153] [Method for measuring liquidus temperature] The glass cullet was crushed, and 40 g of glass particles having a particle size of 0.5 to 1.5 mm were placed in a platinum boat measuring 180 × 20 × 15 mm. The boat was heated for 8 hours or more in a tubular electric furnace with a temperature gradient of 900 to 1600°C. The boat was then removed from the tubular electric furnace and observed under a polarizing microscope to identify the position where crystals (devitrification) derived from the glass began to precipitate. The temperature inside the tubular electric furnace was then measured using a type B thermocouple, and the temperature at the position where precipitation began was taken as the liquidus temperature.

[0154] [Method for Measuring Linear Expansion Coefficient] First, the glass batch is placed in an 80 mm diameter platinum crucible and melted by heating at 1650°C for 6 hours. The glass batch is then removed from the platinum crucible to obtain a homogeneous glass bulk or glass cullet. The resulting glass bulk or glass cullet is then annealed by heating at 750°C for 8 hours to obtain a test piece. The test piece is then machined into a 4 mm x 4 mm x 20 mm test piece for measuring the linear expansion coefficient using a cutting machine, such as a diamond cutter and a polishing machine. The resulting test piece for measuring the linear expansion coefficient is then heated at a heating rate of 10°C / min, and the elongation is 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 is calculated from the elongation.

[0155] [Method for evaluating copper oxide or silver oxide precipitation as oxides of Group 11 elements] Glass bulks obtained under the following conditions 1 or 2 were observed, and glass bulks obtained under condition 1 in which crystals believed to be copper oxide or silver oxide had precipitated on the surface layer that was in direct contact with air were evaluated as "C," glass bulks obtained under condition 2 in which crystals believed to be copper oxide had precipitated on the surface layer that was in direct contact with air were evaluated as "B," and glass bulks obtained under condition 2 in which crystals believed to be copper oxide or silver oxide had not precipitated on the surface layer that was in direct contact with air were evaluated as "A."

[0156] The condition 1 is as follows.

[0157] The glass batch was placed in an 80 mm diameter platinum crucible, and the glass was melted at 1650°C for 6 hours. The glass was then air-cooled to room temperature (25°C) at a rate of 100°C / min in air and removed from the crucible to obtain a glass bulk. This glass bulk was then cut, and a 3 mm area from the surface that had directly come into contact with air was observed using a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0158] Furthermore, condition 2 is as follows:

[0159] The glass batch was placed in an 80 mm diameter platinum crucible, and the glass melted at 1650°C for 6 hours was air-cooled to room temperature (25°C) at a rate of 100°C / min in air and removed from the crucible to obtain a glass bulk. The glass bulk was heated from room temperature (25°C) to 750°C over 2 hours, maintained at 750°C for 2 hours, and slowly cooled to room temperature (25°C) over 8 hours. The slowly cooled glass bulk was then cut, and a 3 mm area from the surface that had directly come into contact with air was observed using a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX).

[0160]

[0161]

[0162]

[0163] From Table 1 or Table 3, it is clear that the glass compositions for glass fiber of Examples 1 to 11 have a sufficient working temperature range, can suppress the precipitation of copper oxide or silver oxide, and have a low linear expansion coefficient.

[0164] On the other hand, from Table 2, the content of T-CuO is more than 10.0 mass %, and T-CuO / P ２ O ５ It is clear that the glass composition for glass fiber of Comparative Example 1, in which the content of T-CuO is less than 0.1 mass % and the content of ZnO is more than 12.0 mass %, is unable to suppress the precipitation of copper oxide. It is also clear that the glass composition for glass fiber of Comparative Example 2, in which the content of T-CuO is less than 0.1 mass % and the content of ZnO is more than 12.0 mass %, is unable to obtain a sufficient working temperature range and is unable to sufficiently lower the linear expansion coefficient. It is also clear that the glass composition for glass fiber of Comparative Example 3, in which the content of ZnO is more than 12.0 mass %, ... ２ O ５ It is clear that the glass composition for glass fiber of Comparative Example 4, in which the content of P is less than 7.0 mass %, is unable to obtain a sufficient working temperature range and is unable to sufficiently reduce the linear expansion coefficient. ２ O ５It is clear that the glass composition for glass fiber of Comparative Example 5, in which the content of T-CuO / P exceeds 18.0 mass %, is unable to obtain a sufficient working temperature range. ２ O ５ It is clear that the glass composition for glass fiber of Comparative Example 6, in which the value is less than 0.0060, cannot obtain a sufficient working temperature range.

Claims

1. SiO in the range of 42.00 to 62.00 mass% based on the total amount ２ and Al in the range of 17.00 to 30.00 mass% ２ O ３ and P in the range of 7.00 to 20.60 mass% ２ O ５ ZnO in the range of 0.00 to 12.00 wt. %, an oxide of a Group 11 element in the range of 0.10 to 10.00 wt. %, and an alkali metal oxide in the range of 0.00 to 4.40 wt. %, ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５ ) is in the range of 0.0060 to 0.8000.

2. The glass composition for glass fiber according to claim 1, wherein P is in the range of 10.40 to 14.70 mass %. ２ O ５ and ZnO in the range of 1.30 to 12.00 mass %, ２ O ５ The ratio of the content of the oxide of the Group 11 element to the content of the oxide of the Group 11 element (Oxide of the Group 11 element / P ２ O ５ ) is in the range of 0.02 to 0.

60.

3. A glass composition for glass fiber according to claim 1, characterized in that the oxide of the Group 11 element is copper oxide or silver oxide.

4. Glass fiber characterized by comprising the glass composition for glass fiber according to claim 1.

5. A glass cloth comprising the glass fiber according to claim 4.

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

Images