Glass composition for glass fiber and glass fiber

Abstract

The present invention provides a glass composition that can be produced with reduced CO2 emissions, imparts water resistance strength to glass fiber reinforced resin molded products, and suppresses color change. The glass composition contains, relative to the total mass, 57.75 to 64.25 mass% of SiO2, 3.51 to 11.80 mass% of Al2O3, 4.01 to 5.80 mass% of B2O3, 9.60 to 20.00 mass% of CaO, 0.55 to 1.94 mass% of MgO, 0.30 to 1.55 mass% of SrO, 0.32 to 1.65 mass% of BaO, 0.05 to 0.94 mass% of Fe2O3, and 0.0 It contains 5 to 0.94 mass% TiO2, 3.05 to 13.80 mass% Na2O, 0.40 to 2.00 mass% K2O, 0.01 to 0.94 mass% ZrO2, and 0.05 to 0.94 mass% F2, the total of CaO, MgO, SrO, and BaO is 12.40 to 21.45 mass%, and the total of Na2O and K2O is 3.50 to 15.80 mass%.

Description

[Technical Field]

[0001] The present invention relates to a glass composition for glass fibers and glass fibers. [Background technology]

[0002] In recent years, there has been a strong demand in industry to reduce environmental impact and ensure sustainable production and consumption patterns.

[0003] In response to this demand, a method has been proposed in which long glass fibers are produced from glass raw materials containing commercially waste glass, and the long glass fibers are used to produce a glass fiber reinforced resin composition or a glass fiber reinforced resin molded product (see, for example, Patent Document 1). The present applicants have also filed a patent application for a glass fiber reinforced resin composition containing long glass fibers obtained by melting and spinning glass raw materials containing more than 50% by mass of commercially waste glass, or a glass fiber material that is cut or crushed from the long glass fibers, which has excellent CO2 reduction efficiency and reinforcement efficiency for glass fiber reinforced resin molded products (see Patent Document 2).

[0004] The term "commercial waste glass" refers to glass recovered from commercial waste (e.g., waste containing 30% or more by mass of undefined-shape glass) without undergoing a heating process at 500°C or higher. Commercial waste includes not only waste discarded after use in the community, but also waste that has been manufactured and completed as a product but discarded without being used or distributed in the community. The term "commercial waste glass" does not include waste glass generated in factories during the manufacturing process of glass or glass-based products. Examples of commercial waste glass include glass cullet recovered by crushing fluorescent tubes, glass cullet recovered by crushing automobile windshields, glass cullet recovered by crushing digital device screens, and glass cullet recovered by crushing glass bottles used for beverages, etc. Such commercial waste glass may be glass composed of a glass composition having a basic composition of SiO2, Al2O3, and BO3, and further containing at least one of CaO, MgO, BaO, and SrO, and at least one of Na2O and KO. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2000-511150 [Patent Document 2] Japanese Patent Application Laid-Open No. 2024-133149 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-030787 [Patent Document 4] Japanese Patent Publication No. 2023-068401 Summary of the Invention [Problem to be solved by the invention]

[0006] However, it is known that glass fiber reinforced resin molded products generally do not have sufficient water resistance (see, for example, Patent Document 3 and Patent Document 4). Glass fiber reinforced resin molded products using long glass fibers produced from glass raw materials including waste glass from the market are excellent in terms of CO2 reduction efficiency and the reinforcing efficiency of glass fiber reinforced resin molded products, but they have the disadvantage of not being able to obtain sufficient water resistance and causing color changes.

[0007] The present invention aims to provide a glass composition for glass fiber that can eliminate such inconveniences, can be produced while realizing a reduction in CO2 emissions, can impart water resistance strength to glass fiber reinforced resin molded products, and can suppress color change of glass fiber reinforced resin molded products. [Means for solving the problem]

[0008] In order to achieve this object, the glass composition for glass fiber of the present invention contains, relative to the total amount of the glass composition for glass fiber, SiO2 in a range of 57.75 to 64.25 mass%, Al2O3 in a range of 3.51 to 11.80 mass%, B2O3 in a range of 4.01 to 5.80 mass%, CaO in a range of 9.60 to 20.00 mass%, MgO in a range of 0.55 to 1.94 mass%, SrO in a range of 0.30 to 1.55 mass%, BaO in a range of 0.32 to 1.65 mass%, and SiO2 in a range of 0.05 to 0.94 mass%. % by mass of Fe2O3, 0.05 to 0.94% by mass of TiO2, 3.05 to 13.80% by mass of Na2O, 0.40 to 2.00% by mass of K2O, 0.01 to 0.94% by mass of ZrO2, and 0.05 to 0.94% by mass of F2, wherein the total content of CaO, MgO, SrO, and BaO is in the range of 12.40 to 21.45% by mass, and the total content of Na2O and K2O is in the range of 3.50 to 15.80% by mass.

[0009] The glass composition for glass fiber of the present invention can be produced while realizing a reduction in CO2 emissions, can impart water resistance strength to glass fiber reinforced resin molded products, and can suppress color change of the glass fiber reinforced resin molded products.

[0010] In the glass composition for glass fiber of the present invention, the ratio of the content of SrO to the content of F2 (SrO / F2) is preferably in the range of 0.50 to 12.50, and the ratio of the content of B2O3 to the content of SrO (B2O3 / SrO) is preferably in the range of 2.51 to 24.40.

[0011] The glass fiber of the present invention is characterized by comprising the glass composition for glass fiber of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] Next, the embodiment of the present invention will be described in more detail.

[0013] The glass composition for glass fiber of this embodiment contains, relative to the total amount of the glass composition for glass fiber, SiO2 in a range of 57.75 to 64.25 mass%, Al2O3 in a range of 3.51 to 11.80 mass%, B2O3 in a range of 4.01 to 5.80 mass%, CaO in a range of 9.60 to 20.00 mass%, MgO in a range of 0.55 to 1.94 mass%, SrO in a range of 0.30 to 1.55 mass%, BaO in a range of 0.32 to 1.65 mass%, and ZnO in a range of 0.05 to 0.94 mass%. range of Fe2O3, TiO2 in the range of 0.05 to 0.94 mass%, Na2O in the range of 3.05 to 13.80 mass%, K2O in the range of 0.40 to 2.00 mass%, ZrO2 in the range of 0.01 to 0.94 mass%, and F2 in the range of 0.05 to 0.94 mass%, the total content of CaO, MgO, SrO, and BaO is in the range of 12.40 to 21.45 mass%, and the total content of Na2O and K2O is in the range of 3.50 to 15.80 mass%.

[0014] In the glass composition for glass fiber of this embodiment, if SiO2 is less than 57.75 mass% relative to the total amount, the skeleton ratio of the network structure formed in the glass will be low, and sufficient mechanical properties will not be obtained. On the other hand, if SiO2 is more than 64.25 mass% relative to the total amount, the melt viscosity will be high and the meltability will be low, making it difficult to obtain uniform glass and to fiberize it stably and continuously for a long period of time.

[0015] The content of SiO2 relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 57.75 to 63.50 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 58.51 to 62.90 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product, and even more preferably in the range of 58.55 to 61.00 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product and there is little change in the hue of the glass fiber reinforced resin molded product.

[0016] Furthermore, in the glass composition for glass fiber of this embodiment, if Al2O3 is less than 3.51 mass% relative to the total amount, the skeleton ratio of the network structure formed in the glass will be low, sufficient mechanical properties will not be obtained, and durability when contacting water or chemicals will decrease. Furthermore, the effect of suppressing crystallization will decrease, and the liquidus temperature will rise, making fiberization difficult. On the other hand, if Al2O3 is more than 11.80 mass% relative to the total amount, the melt viscosity will increase and the meltability will decrease, making it difficult to obtain a uniform glass and to perform fiberization stably and continuously for a long period of time.

[0017] The content of Al2O3 relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 3.55 to 10.00 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 4.20 to 9.94 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product, and even more preferably in the range of 6.35 to 9.50 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product and causes little change in the hue of the glass fiber reinforced resin molded product.

[0018] In addition, in the glass composition for glass fiber of this embodiment, if B2O3 is less than 4.01 mass% relative to the total amount, the melt viscosity increases, making it difficult to perform fiberization stably and continuously for a long period of time. On the other hand, if B2O3 is more than 5.80 mass% relative to the total amount, the generation of volatiles and scum during glass melting increases, making it difficult to perform fiberization stably and continuously for a long period of time.

[0019] The content of B2O3 relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 4.05 to 5.45 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 4.25 to 5.40 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and even more preferably in the range of 4.70 to 5.30 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and results in little change in the hue of the glass fiber-reinforced resin molded product.

[0020] In addition, in the glass composition for glass fiber of this embodiment, if the CaO content is less than 9.60 mass% relative to the total amount, the tensile strength and tensile modulus of the glass fiber will decrease, making it difficult to satisfy sufficient mechanical properties for composite material applications. On the other hand, if the CaO content is more than 20.00 mass% relative to the total amount, CO2 emissions will increase, making it difficult to ensure a sustainable production and consumption pattern.

[0021] The content of CaO relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 9.61 to 17.65 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 10.40 to 17.00 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product, and even more preferably in the range of 13.10 to 16.60 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product and causes little change in the hue of the glass fiber reinforced resin molded product.

[0022] In addition, in the glass composition for glass fiber of this embodiment, if the MgO content is less than 0.55 mass% relative to the total amount, the melt viscosity increases, making it difficult to perform fiberization stably and continuously for a long period of time. On the other hand, if the MgO content is more than 1.94 mass% relative to the total amount, crystals with other components tend to be formed, making it difficult to perform fiberization stably and continuously for a long period of time.

[0023] The content of MgO relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.60 to 0.94 mass%, more preferably in the range of 0.72 to 0.86 mass%, even more preferably in the range of 0.73 to 0.83 mass% because this provides an excellent rate of reduction in CO2 emissions, particularly preferably in the range of 0.74 to 0.82 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and most preferably in the range of 0.78 to 0.82 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and results in little change in the hue of the glass fiber-reinforced resin molded product.

[0024] In addition, in the glass composition for glass fiber of this embodiment, if the SrO content is less than 0.30 mass% relative to the total amount, the melting property decreases, making it difficult to fiberize stably and continuously for a long period of time. On the other hand, if the SrO content exceeds 1.55 mass% relative to the total amount, the skeleton ratio of the network structure formed in the glass becomes low, and durability when contacting water or chemicals decreases.

[0025] The content of SrO relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.60 to 1.50 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 0.65 to 1.35 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and even more preferably in the range of 0.66 to 1.05 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and causes little change in the hue of the glass fiber-reinforced resin molded product.

[0026] In addition, in the glass composition for glass fiber of this embodiment, if BaO is less than 0.32 mass% relative to the total amount, the melting property decreases, making it difficult to fiberize stably and continuously for a long period of time. On the other hand, if BaO is more than 1.65 mass% relative to the total amount, the skeleton ratio of the network structure formed in the glass becomes low, and durability when contacting water or chemicals decreases.

[0027] The content of BaO relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.60 to 1.60 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 0.65 to 1.40 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and even more preferably in the range of 0.70 to 1.10 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and causes little change in the hue of the glass fiber-reinforced resin molded product.

[0028] In addition, in the glass composition for glass fiber of this embodiment, if Fe2O3 is less than 0.05 mass% relative to the total amount, the melting property decreases, making it difficult to fiberize stably and continuously for a long period of time, and the cost of removing impurities increases, which becomes a factor that puts pressure on production costs. On the other hand, if Fe2O3 is more than 0.94 mass% relative to the total amount, coloration of the glass increases, making it more likely to cause problems when applied to composite materials.

[0029] The content of Fe2O3 relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.10 to 0.44 mass %, more preferably in the range of 0.15 to 0.30 mass %.

[0030] In addition, in the glass composition for glass fiber of this embodiment, if TiO2 is less than 0.05 mass% relative to the total amount, the cost of removing impurities will increase, which will be a factor in putting pressure on production costs. On the other hand, if TiO2 is more than 0.94 mass% relative to the total amount, the high-temperature viscosity of the glass will increase, the melting property will be easily deteriorated, and the glass will be easily colored, which will easily cause problems when applied to composite materials.

[0031] The content of TiO2 relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.10 to 0.44 mass%, more preferably in the range of 0.22 to 0.36 mass%, even more preferably in the range of 0.23 to 0.33 mass% because this provides an excellent rate of reduction in CO2 emissions, particularly preferably in the range of 0.24 to 0.32 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and most preferably in the range of 0.28 to 0.32 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and results in little change in the hue of the glass fiber-reinforced resin molded product.

[0032] Furthermore, in the glass composition for glass fiber of this embodiment, if the Na2O content is less than 3.05 mass% relative to the total amount, the melt viscosity increases and the meltability decreases, making it difficult to obtain uniform glass and to fiberize it stably and continuously for a long period of time. On the other hand, if the Na2O content exceeds 13.80 mass% relative to the total amount, the skeleton ratio of the network structure formed in the glass becomes low, reducing the mechanical properties and durability when contacting water or chemicals, and increasing the erosion of the furnace material, shortening the life of the melting furnace.

[0033] The content of Na2O relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 5.20 to 13.00 mass%, more preferably in the range of 5.60 to 12.00 mass%, because this provides an excellent rate of reduction in CO2 emissions, and is even more preferably in the range of 6.00 to 9.50 mass%, because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water resistance strength of the glass fiber reinforced resin molded product, and the glass fiber reinforced resin molded product has little change in hue.

[0034] Furthermore, in the glass composition for glass fiber of this embodiment, if the amount of K2O is less than 0.40 mass% relative to the total amount, the melt viscosity becomes high and the meltability decreases, making it difficult to obtain uniform glass and to fiberize it stably and continuously for a long period of time. On the other hand, if the amount of K2O exceeds 2.00 mass% relative to the total amount, the skeleton ratio of the network structure formed in the glass becomes low, which reduces the mechanical properties and durability when contacting water or chemicals, and also increases the erosion of the furnace material, shortening the life of the melting furnace.

[0035] The content of K2O relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.75 to 1.90 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 0.80 to 1.75 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and even more preferably in the range of 0.85 to 1.35 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and causes little change in the hue of the glass fiber-reinforced resin molded product.

[0036] In addition, in the glass composition for glass fiber of this embodiment, if ZrO2 is less than 0.01 mass% relative to the total amount, the cost of removing impurities will increase, which will become a factor in putting pressure on production costs. On the other hand, if ZrO2 is more than 0.94 mass% relative to the total amount, the melt viscosity will increase and the meltability will decrease, making it difficult to obtain a uniform glass and to fiberize it stably and continuously for a long period of time.

[0037] The content of ZrO2 relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.05 to 0.44 mass%, more preferably in the range of 0.06 to 0.28 mass%, even more preferably in the range of 0.10 to 0.26 mass% because this provides an excellent rate of reduction in CO2 emissions, particularly preferably in the range of 0.11 to 0.24 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and most preferably in the range of 0.12 to 0.19 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and results in little change in the hue of the glass fiber-reinforced resin molded product.

[0038] In addition, in the glass composition for glass fiber of this embodiment, if F2 is less than 0.05 mass% relative to the total amount, bubbles are generated in large amounts, making it difficult to perform stable fiberization for a long period of time. On the other hand, if F2 is more than 0.94 mass% relative to the total amount, the viscosity of the molten glass decreases significantly, making it difficult to perform stable fiberization for a long period of time.

[0039] The content of F2 relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.06 to 0.66 mass%, more preferably in the range of 0.10 to 0.54 mass% because this provides an excellent rate of reduction in CO2 emissions, even more preferably in the range of 0.16 to 0.50 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and most preferably in the range of 0.30 to 0.49 mass% because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and results in little change in the hue of the glass fiber-reinforced resin molded product.

[0040] In addition, in the glass composition for glass fiber of this embodiment, if the total content of CaO, MgO, SrO and BaO relative to the total amount is less than 12.40 mass%, the melt viscosity increases, making it difficult to perform continuous and stable fiberization. On the other hand, if the total content of CaO, MgO, SrO and BaO relative to the total amount is more than 21.45 mass%, the skeleton ratio of the network structure formed in the glass decreases, and the mechanical properties and chemical durability decrease.

[0041] The total content of CaO, MgO, SrO and BaO relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 13.00 to 19.60 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 13.95 to 19.00 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product, and even more preferably in the range of 16.10 to 18.80 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product and results in little change in hue of the glass fiber reinforced resin molded product.

[0042] In addition, in the glass composition for glass fiber of this embodiment, if the total content of Na2O and K2O relative to the total amount is less than 3.50 mass%, the melt viscosity increases, making it difficult to stably and continuously fiberize. On the other hand, if the total content of Na2O and K2O relative to the total amount is more than 15.80 mass%, corrosion of the melting furnace material increases, shortening the life of the melting furnace.

[0043] The total content of Na2O and K2O relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 7.01 to 15.00 mass% because it provides an excellent rate of reduction in CO2 emissions, more preferably in the range of 7.05 to 13.75 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product, and even more preferably in the range of 7.10 to 10.80 mass% because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product and causes little change in hue of the glass fiber reinforced resin molded product.

[0044] The glass composition for glass fiber of this embodiment is preferably a glass composition for long glass fiber. The long glass fiber is a glass fiber that is formed into a length of at least 1000 m or more in a production process described below, and is composed of a single glass filament or a bundle of multiple glass filaments.

[0045] In the glass composition for glass fiber of this embodiment, the ratio of the content of SrO to the content of F2 (SrO / F2) is preferably in the range of 0.50 to 12.50. The ratio of the content of SrO to the content of F2 (SrO / F2) is more preferably in the range of 1.10 to 12.10 because it provides an excellent rate of reduction in CO2 emissions, even more preferably in the range of 1.20 to 9.20 because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product, and particularly preferably in the range of 1.30 to 4.20 because it provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber reinforced resin molded product and results in little change in hue of the glass fiber reinforced resin molded product.

[0046] In the glass composition for glass fiber of this embodiment, the ratio of the content of B2O3 to the content of SrO (B2O3 / SrO) is preferably in the range of 2.51 to 24.40. The ratio of the content of B2O3 to the content of SrO (B2O3 / SrO) is more preferably in the range of 2.70 to 10.50 because this provides an excellent rate of reduction in CO2 emissions, even more preferably in the range of 3.15 to 9.50 because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product, and particularly preferably in the range of 4.65 to 8.90 because this provides an excellent rate of reduction in CO2 emissions and an excellent rate of retention of water-resistant strength of a glass fiber-reinforced resin molded product and results in little change in hue of the glass fiber-reinforced resin molded product.

[0047] Here, excellent CO2 emission reduction rate means that the value equivalent to the emission intensity on a physical volume basis for "other non-metallic minerals" shown in No. 32, column code 62909 in the "Emission intensity unit based on input-output tables" listed in the "Emission intensity unit database for calculating greenhouse gas emissions, etc. of organizations throughout the supply chain (Ver. 2.5)" is in the range of 0 to 0.0070.

[0048] Furthermore, the term "excellent water resistance strength retention rate" for a glass fiber reinforced resin molded product means that the strength retention rate after PCT treatment (B / A x 100; unit: %) is 30.0% or more, as measured by the method described below, when comparing the tensile strength A of the glass fiber reinforced resin molded product with the tensile strength B of the glass fiber reinforced resin molded product after PCT treatment.

[0049] Furthermore, "little change in hue of a glass fiber reinforced resin molded product" means that when a glass fiber reinforced resin molded product containing glass fibers made from the glass composition for glass fiber of this embodiment is evaluated for L*a*b* values ​​using a spectrocolorimeter SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. and coordinates in the L*a*b* color space are determined, the color difference ΔE value is 0<ΔE≦3 when compared with a glass fiber reinforced resin molded product obtained by the same procedure as this embodiment except that a glass composition for glass fiber using non-recycled raw materials is used.

[0050] The glass composition for glass fiber of the present embodiment may also contain ZnO, Cr2O3, Nb2O5, WO3, Bi2O3, Li2O, and PbO.

[0051] When the glass composition for glass fiber of the present embodiment contains the ZnO, the content of the ZnO relative to the total amount of the glass composition for glass fiber is, for example, in the range of 0.10 mass% or less, preferably in the range of 0.01 to 0.09 mass%, and more preferably in the range of 0.01 to 0.05 mass%.

[0052] Furthermore, when the glass composition for glass fiber of this embodiment contains the Cr2O3, the content of the Cr2O3 relative to the total amount of the glass composition for glass fiber is, for example, in the range of 0.10 mass% or less, preferably in the range of 0.01 to 0.09 mass%, and more preferably in the range of 0.01 to 0.05 mass%.

[0053] Furthermore, when the glass composition for glass fiber of this embodiment contains the Nb2O5, the content of the Nb2O5 relative to the total amount of the glass composition for glass fiber is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0054] Furthermore, when the glass composition for glass fiber of this embodiment contains the WO3, the content of the WO3 relative to the total amount of the glass composition for glass fiber is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0055] Furthermore, when the glass composition for glass fiber of the present embodiment contains Bi2O3, the content of Bi2O3 relative to the total amount of the glass composition for glass fiber is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0056] Furthermore, when the glass composition for glass fiber of the present embodiment contains the LiO, the content of the LiO relative to the total amount of the glass composition for glass fiber is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0057] Furthermore, when the glass composition for glass fiber of the present embodiment contains the PbO, the content of the PbO relative to the total amount of the glass composition for glass fiber is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0058] 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 Li, which is a light element, and a wavelength dispersive X-ray fluorescence analyzer for other elements.

[0059] The measurement method involves first placing a glass batch or glass fiber prepared by mixing glass raw materials in a platinum crucible and melting it in an electric furnace at a temperature of 1350 to 1550°C for the glass batch or 1300 to 1450°C for the glass fiber for 6 hours while stirring, to obtain a homogeneous molten glass. If organic matter is attached to the glass fiber surface or if the glass fiber is primarily contained as a reinforcing material in an organic material such as a resin, the organic matter is removed by heating in a muffle furnace at 300 to 650°C for 0.5 to 24 hours, for example. The resulting molten glass is then poured onto a carbon plate to produce glass cullet, which is then crushed and powdered to obtain glass powder. The light element Li is quantitatively analyzed for Li after the glass powder is thermally decomposed with acid and then quantitatively analyzed using an ICP optical emission spectrometer. The other elements are quantitatively analyzed for Li after the glass powder is formed into a disk shape using a press and then quantitatively analyzed using a wavelength-dispersive X-ray fluorescence spectrometer. Specifically, quantitative analysis using a wavelength-dispersive X-ray fluorescence analyzer can be performed by preparing a calibration curve sample based on the results of measurements using the fundamental parameter method and then analyzing the sample using the calibration curve method. The content of each component in the calibration curve sample can be quantitatively analyzed using an ICP atomic emission spectrometer. These quantitative analysis results can be converted into oxides to calculate the content and total amount of each component, and the content (mass%) of each component can be determined from these values.

[0060] The glass composition for glass fiber of this embodiment has a 1000 poise temperature in the range of, for example, 1135 to 1190°C, preferably a 1000 poise temperature in the range of 1140 to 1180°C, and more preferably a 1000 poise temperature in the range of 1155 to 1175°C.

[0061] The glass composition for glass fiber of the present embodiment has a liquidus temperature in the range of, for example, 920 to 1040°C, preferably 930 to 1005°C, and more preferably 960 to 1000°C.

[0062] The glass composition for glass fiber of this embodiment has a specific gravity in the range of 2.57 to 2.60, for example.

[0063] The glass composition for glass fiber of this embodiment has a monofilament tensile strength in the range of, for example, 2.2 to 3.0 GPa, preferably in the range of 2.3 to 2.9 GPa, and more preferably in the range of 2.6 to 2.8 GPa.

[0064] The glass composition for glass fiber of this embodiment has a monofilament elastic modulus in the range of, for example, 64.0 to 73.4 GPa, preferably a monofilament elastic modulus in the range of 65.0 to 70.8 GPa, and more preferably a monofilament elastic modulus in the range of 67.0 to 70.0 GPa.

[0065] The glass composition for glass fiber of this embodiment has, for example, a dielectric constant in the range of 6.4 to 7.2 and a dielectric dissipation factor in the range of 0.0055 to 0.0065 at a measurement frequency of 1 GHz, preferably a dielectric constant in the range of 6.6 to 7.0 and a dielectric dissipation factor in the range of 0.0057 to 0.0063, and more preferably a dielectric constant in the range of 6.7 to 6.9 and a dielectric dissipation factor in the range of 0.0059 to 0.0061. Furthermore, the glass composition for glass fiber of this embodiment has, for example, a dielectric constant in the range of 6.3 to 7.1 and a dielectric dissipation factor in the range of 0.0053 to 0.0064 at a measurement frequency of 1 MHz, preferably a dielectric constant in the range of 6.5 to 5.9 and a dielectric dissipation factor in the range of 0.0056 to 0.0061, and more preferably a dielectric constant in the range of 6.6 to 6.8 and a dielectric dissipation factor in the range of 0.0057 to 0.0059.

[0066] Next, the glass fiber of this embodiment includes glass filaments made of the glass composition for glass fiber of this embodiment.

[0067] In one aspect, the glass fiber of this embodiment is produced as follows. First, based on the components contained in the waste glass and the content of each component, the amount of volatilization of each component during the melting process, and the components contained in the ore serving as the glass raw material and the content of each component, and the amount of volatilization of each component during the melting process, a glass raw material (glass batch) is obtained by blending the waste glass and the ore serving as the glass raw material to obtain the composition of the glass composition for glass fiber of this embodiment. The glass batch is supplied to a melting furnace and melted at a temperature in the range of 1350 to 1550°C, for example. Next, the molten glass batch (molten glass) is drawn out from 1 to 20,000 nozzle tips of a bushing controlled at a predetermined temperature and quenched to form glass filaments.

[0068] 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 to obtain glass fibers.

[0069] When the glass composition for glass fiber of this embodiment is melted at a temperature within the above range for producing the glass fiber, fiber lengthening is possible if the working temperature range ΔT is 0° C. or higher, and fiber lengthening is facilitated if ΔT is 100° C. or higher. The working temperature range ΔT is calculated by the following formula using the 1000 poise temperature and the liquidus temperature. Working temperature range ΔT = 1000 poise temperature - liquidus temperature

[0070] Here, a glass single fiber (glass filament) discharged from one nozzle tip or hole and cooled and solidified preferably has a perfectly circular cross-sectional shape and a diameter (filament diameter) of 3.0 to 30.0 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 glass filaments 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 into that of a perfect circle, is 3.0 to 30.0 μm.

[0071] 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.

[0072] 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 in the method for measuring the filament diameter of the glass filament in the glass fiber described above.

[0073] 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, 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, (poly)carboxylic acid, particularly a copolymer of maleic acid and an unsaturated monomer or a copolymer of acrylic acid and an unsaturated monomer. 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. The 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 where it is not coated with the resin composition or treatment composition. Here, the coating ratio based on the mass of the glass fiber is substantially the same as the coating ratio based on the mass of a glass monofilament (sometimes referred to as a monofilament), which typically comprises a plurality of fibers constituting the glass fiber. Coating of glass fiber with an 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 fiber using a known method such as a roller applicator, and then drying the glass fiber to which the resin solution or resin composition solution has been applied. Alternatively, coating can be carried out by immersing the glass fiber of this embodiment in the form of a woven fabric in a treatment composition solution, and then drying the glass fiber to which the treatment composition has been applied.

[0074] Examples of the urethane resin include polyether-based urethane resin and polyester-based urethane resin.

[0075] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, biphenyl type bifunctional epoxy resins, biphenyl modified novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, tetraphenylethane type epoxy resins, and naphthol novolac type epoxy resins.

[0076] 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.

[0077] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0078] Examples of ureidosilane include γ-ureidopropyltriethoxysilane.

[0079] Examples of chlorosilanes include γ-chloropropyltrimethoxysilane.

[0080] Examples of epoxy silanes include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0081] Examples of mercaptosilane include γ-mercaptotrimethoxysilane and γ-mercaptopropyltrimethoxysilane.

[0082] Examples of vinylsilanes include vinyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, and N-benzyl-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0083] Examples of the (meth)acrylic silane include γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

[0084] Examples of phenylsilane include phenyltrimethoxysilane.

[0085] An example of the styrylsilane is p-styryltrimethoxysilane.

[0086] Examples of the isocyanate silane include γ-isocyanate propyl triethoxy silane.

[0087] 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.

[0088] Examples of animal oils include beef tallow.

[0089] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, etc.

[0090] Examples of animal waxes include beeswax and lanolin.

[0091] Examples of vegetable waxes include candelilla wax and carnauba wax.

[0092] Examples of mineral waxes include paraffin wax and montan wax.

[0093] Examples of the condensation products of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.

[0094] 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.

[0095] Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] When the organic material that coats the surface of the glass fiber contains the urethane resin, the ratio of the urethane resin to the epoxy resin in the organic material (epoxy resin content / urethane resin content) is, for example, in the range of 0 / 100 to 1000 / 100, and preferably in the range of 10 / 100 to 700 / 100.

[0102] Examples of the form of the glass fiber include glass fabric (glass cloth), knitted fabric, yarn, chopped strand, roving, chopped strand mat, paper, mesh, braided fabric, and milled fiber. Chopped strand, roving, and glass fabric (glass cloth) are preferred, and glass fabric (glass cloth) is more preferred.

[0103] 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. The chopped strand can be obtained by cutting the glass fiber produced by the above-described method to the predetermined length using a known device such as a long fiber cutting device that includes a cutter roller equipped with cutters (cutting blades) radially spaced apart and a rubber roller that rotates in contact with the cutter roller and has rubber on its outer circumferential surface, thereby feeding and cutting the glass strand.

[0104] 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 30000. The roving, which is the glass fiber of this embodiment, has a mass per unit length of 0.5 to 10000 tex (g / 1000 m).

[0105] When the glass fiber of this embodiment is a glass woven fabric, the glass woven fabric 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 the weaving method used with the loom include plain weave, satin weave, sash weave, and twill weave, with plain weave being preferred from the viewpoint of production efficiency.

[0106] The glass fibers of this embodiment contained in the glass fiber fabric preferably consist of glass filaments having a filament diameter of 2.0 μm or more and 9.0 μm or less, and have a mass of 0.5 to 70.0 tex (g / 1000 m).

[0107] Here, the filament diameter of the glass fiber of this embodiment contained in the glass fiber fabric is the average value of the measured values ​​when the diameters of the glass filaments constituting the glass fiber are measured at at least 50 points on the cross section of the glass fiber using a scanning electron microscope (manufactured by JEOL Ltd., product name: JSM-IT800, magnification: 3000 times).

[0108] The glass fiber fabric preferably comprises 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. The weave density of the warp yarns can be determined in accordance with Japanese Industrial Standards (JIS) R 3420 by using a fabric speculum to count the number of warp yarns within a 25 mm range in the warp direction. The weave density of the weft yarns can be determined in accordance with Japanese Industrial Standards (JIS) R 3420 by using a fabric speculum to count the number of weft yarns within a 25 mm range in the weft direction.

[0109] After being woven, the glass fiber fabric may be subjected to a de-oiling treatment, a surface treatment, and a fiber-opening treatment.

[0110] 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.

[0111] The surface treatment may involve immersing a glass fiber fabric in a solution containing the silane coupling agent or the silane coupling agent and the surfactant, squeezing out excess water, and then heating and drying the fabric at a temperature in the range of 80 to 180°C for 1 to 30 minutes.

[0112] Examples of the opening treatment include a process in which the warp and weft widths are expanded by applying a tension of 20 to 200 N to the warp yarns of a glass fiber fabric while performing opening by water flow pressure, opening by high-frequency vibration using a liquid as a medium, opening by pressure of a fluid having surface pressure, opening by applying pressure with a roll, or the like.

[0113] The glass fiber fabric has a density of 5.0 to 220 g / m 2 It is preferable that the thickness of the film be in the range of 4.0 to 200.0 μm.

[0114] The glass fiber fabric 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 this 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.

[0115] The glass fiber of this embodiment can be used to produce a glass fiber reinforced resin molded product.

[0116] Specifically, the glass fiber reinforced resin molded product 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 molded product. The glass fiber reinforced resin molded product also contains 90 to 10 mass % of resin based on the total amount of the glass fiber reinforced resin molded product, and contains other additives in the range of 0 to 40 mass %.

[0117] 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), Examples of suitable polymers include 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), and polybutylene adipate terephthalate (PBAT).

[0118] 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.

[0119] Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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. 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 components selected from the following: 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 mixtures thereof.

[0124] 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.

[0125] Examples of polyethylene terephthalate include polymers obtainable by polycondensing terephthalic acid or a derivative thereof with ethylene glycol.

[0126] Examples of polybutylene terephthalate include polymers obtainable by polycondensation of terephthalic acid or a derivative thereof with 1,4-butanediol.

[0127] Examples of polytrimethylene terephthalate include polymers obtainable by polycondensation of terephthalic acid or a derivative thereof with 1,3-propanediol.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] Examples of modified polyphenylene ethers include polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / maleic anhydride copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polyamide, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene / acrylonitrile copolymer, polyphenylene ethers having functional groups such as amino groups, epoxy groups, carboxy groups, and styryl groups introduced into the polymer chain terminals, and polyphenylene ethers having functional groups such as amino groups, epoxy groups, carboxy groups, styryl groups, and methacrylic groups introduced into the polymer chain side chains.

[0132] Examples of polyaryletherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).

[0133] Examples of liquid crystal polymers (LCPs) include thermotropic liquid crystal polyesters, such as (co)polymers composed of one or more structural units selected from aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, and aliphatic dicarbonyl units.

[0134] 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).

[0135] 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.

[0136] 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.

[0137] Examples of the cyclic olefin resin include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0138] 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.

[0139] 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.

[0140] 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).

[0141] Specifically, the unsaturated polyester resin may be a resin obtainable by esterifying an aliphatic unsaturated dicarboxylic acid with an aliphatic diol.

[0142] Examples of vinyl ester resins include bis-based vinyl ester resins and novolac-based vinyl ester resins.

[0143] Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexydiene bisphenol type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane novolac type epoxy resin. 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.

[0144] The melamine resin may be a polymer obtained by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0145] 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.

[0146] Examples of urea resins include resins obtainable by condensation of urea and formaldehyde.

[0147] The thermoplastic resins or thermosetting resins may be used alone or in combination of two or more.

[0148] 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, hydrolysis resistance improvers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, and pigments.

[0149] Examples of the flame retardant include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, pentabromobenzyl polyacrylate, antimony trioxide, antimony pentoxide, sodium antimonate, phosphate ester, polyphosphoric acid, melamine polyphosphate, ammonium polyphosphate, metal phosphinate, red phosphorus, melamine cyanurate, phosphazene, aluminum hydroxide, magnesium hydroxide, silicon compounds, and boron compounds.

[0150] Examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5' -di-tert-butyl-phenyl)-5-chlorobenzotriazole), 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1 ,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-triazine, and 2-(alkylidene)malonic acid esters.

[0151] Examples of the heat stabilizer include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], ethylene bis(oxyethylene)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,6-bis(octylthiomethyl)-o-cresol, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6 Examples of suitable bis(2,4-di-tert-butylphenyl)tri-p-cresol, benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyalkyl ester, tris(2,4-di-tert-butylphenyl)phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4-diylbisphosphite, bis(2,4-tert-butylphenyl)pentaerthritol diphosphite, tris(mononylphenyl)phosphite, etc. Particularly preferred substances include bis(2,4-di-tert-butylphenyl)phosphite, bis(2,4-tert-butylphenyl)pentaerthritol diphosphite, and the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene.

[0152] Examples of the hydrolysis resistance improver include diphenylcarbodiimide, dicyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, Di-2,5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-di-cyclohexylcarbodiimide, N,N'-di-o-triylcarbodiimide, N,N'-diphenylcarbodiimide, N,N '-Dioctyldecylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, N,N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-di-cyclohexylcarbodiimide , N,N'-di-p-toluylcarbodiimide, N,N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N,N'-di-o-ethylphenylcarbodiimide, N,N'-di-p-ethylphenylcarbodiimide, N,N'-di-o-isopropylphenylcarbodiimide, N,N'-di-p-isopropylphenylcarbodiimide, N,N'-di-o-isobutylphenylcarbodiimide, N,N'-di-p-isobutylphenylcarbodiimide, N,N'-di-2,6-diethylphenylcarbodiimide, N,N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N,N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N,N'-di-2,4,6-trimethylphenylcarbodiimide, N,N'-di-2,4,6-triisopropylphenylcarbodiimide, N,N'-di-2,4 Mono- or dicarbodiimide compounds such as 1,6-triisobutylphenylcarbodiimide, poly(1,6-hexamethylenecarbodiimide), poly(4,4'-methylenebiscyclohexylcarbodiimide), poly(1,3-cyclohexylenecarbodiimide), poly(1,4-cyclohexylenecarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), Poly(phenylene carbodiimide), poly(tolylcarbodiimide), poly(diisopropylcarbodiimide), poly(methyl-diisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauric alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis-(4-hydroxyphenyl)propane, 2,2-Bis-(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester Diglycidyl ester, naphthalenedicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid Tetraglycidyl ester, tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidyl aniline, diglycidyl toluidine, tetraglycidyl metaxylenediamine, diglycidyl tribromoaniline, tetraglycidyl bisaminomethylcyclohexane, triglycidyl cyanurate, triglycidyl isocyanurate, N-glycidyl phthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl N-glycidyl-3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N-glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N-glycidyl-α,β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene diepoxide, N-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-Dicarboxylic acid imide, 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2-decyloxy-2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline Phosphorus, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline, 2-phenoxy-2-oxazoline, 2-cresyl-2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m-ethylphenoxy-2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2 -oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-cyclopentyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propylphenyl phenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p-phenylphenyl-2-oxazoline, 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(4,4'-dimethyl-2-oxazoline), 2,2'-bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4'-diethyl-2-oxazoline), 2,2'-bis(4-propyl-2-oxazoline), 2,2'-bis(4-butyl-2-oxazoline), 2,2'-bis(4-hexyl-2-oxazoline), 2,2'-bis(4-phenyl-2-oxazoline), 2,2'-bis(4-cyclohexyl-2-oxazoline), 2,2'-bis(4-benzyl-2-oxazoline), 2,2'-p-phenylenebis(2-oxazoline), 2,2'-m-phenylenebis(2-oxazoline), 2,2'-o-phenylenebis(2-o) oxazoline), 2,2'-p-phenylenebis(4-methyl-2-oxazoline), 2,2'-p-phenylenebis(4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis(4-methyl-2-oxazoline), 2,2'-m-phenylenebis(4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2'-hexa Methylenebis(2-oxazoline), 2,2'-octamethylenebis(2-oxazoline), 2,2'-decamethylenebis(2-oxazoline), 2,2'-ethylenebis(4-methyl-2-oxazoline), 2,2'-tetramethylenebis(4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethanebis(2-oxazoline), 2,2'-cyclohexylenebis(2-oxazoline), 2,2'-diphenyl Phenylenebis(2-oxazoline), 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6-dihydro-4H-1,3-oxazine, 2-propoxy-5,6-dihydro-4H-1,3-oxazine, 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy-5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3-oxazine, 2-octyloxy-5,6-dihydro-4H-1,3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclopentyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclo Examples of the oxazine derivatives include hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-methallyloxy-5,6-dihydro-4H-1,3-oxazine, and 2-crotyloxy-5,6-dihydro-4H-1,3-oxazine. Examples of the oxazine derivatives include 2,2'-bis(5,6-dihydro-4H-1,3-oxazine), 2,2'-methylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-ethylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-propylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-butylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-hexamethylenebis(5,6-dihydro-4H-1,3- oxazine), 2,2'-p-phenylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-P,P'-diphenylenebis(5,6-dihydro-4H-1,3-oxazine), and the like.

[0153] The glass fiber reinforced resin molded product may 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.

[0154] The glass fiber reinforced resin molded article 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.

[0155] 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.

[0156] When the glass fiber of this embodiment is contained in a glass fiber reinforced resin molded product, or when it is for a glass fiber reinforced resin molded product, the glass fiber of this embodiment includes one or more types of glass fibers obtained by the above-mentioned method from a glass raw material containing commercially available waste glass as all or a part of the glass raw material, and one or more types of glass fibers obtained by the above-mentioned method from a glass raw material consisting of ore, and the glass fiber reinforced resin molded product is heated in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours, and the resin is removed to obtain the whole glass fibers. The glass composition calculated by the above-mentioned method may correspond to the glass composition of the glass composition for glass fiber of this embodiment.

[0157] When the glass fiber of the present embodiment is for glass fiber reinforced resin molded products and contains one or more types of glass fiber obtained by the above-mentioned method from glass raw materials containing commercially waste glass as all or part of the glass raw materials, and one or more types of glass fiber obtained by the above-mentioned method from glass raw materials consisting of ore, the glass fiber of the present embodiment may be in a form in which chopped strands which are one or more types of glass fiber obtained by the above-mentioned method from glass raw materials containing commercially waste glass as all or part of the glass raw materials and chopped strands which are one or more types of glass fiber obtained by the above-mentioned method from glass raw materials consisting of ore are mixed in one bag, for example.

[0158] Next, examples of the present invention and comparative examples will be described. [Example]

[0159] [Examples 1 to 5, Comparative Examples 1 and 2] By mixing a glass raw material A derived from commercial waste glass and having the composition shown in Table 1 as Comparative Example 1 with an ore-derived glass raw material B containing, relative to the total amount, SiO2 in the range of 52.0 to 56.0 mass%, Al2O3 in the range of 12.0 to 16.0 mass%, MgO and CaO in the range of 20.0 to 25.0 mass%, and B2O3 in the range of 5.0 to 10.0 mass%, in a predetermined ratio, glass raw materials were obtained that, when glass fibers were produced from the glass raw materials, could give glass compositions for glass fiber having the compositions of Examples 1 to 5 and Comparative Example 2.

[0160] Next, for the glass compositions for glass fiber of Examples 1 to 5 and Comparative Examples 1 and 2, the 1000 poise temperature, liquidus temperature, specific gravity, monofilament tensile strength, monofilament modulus, dielectric constant and dielectric loss tangent at a measurement frequency of 1 GHz or 1 MHz, tensile strength of glass fiber reinforced resin molded products after PCT treatment, flexural strength of glass fiber reinforced resin molded products, flexural modulus of glass fiber reinforced resin molded products, and strength retention rate after PCT treatment were measured or calculated by the methods shown below, and the CO2 emission reduction rate, water resistance strength of glass fiber reinforced resin molded products, and color change of glass fiber reinforced resin molded products were evaluated. The results are shown in Table 1.

[0161] [Method for measuring 1000 poise temperature] First, a glass batch obtained by mixing glass raw materials so that the glass composition after melting and solidifying would be the composition of each of Examples 1 to 5 and Comparative Examples 1 and 2 shown in Table 1 was placed in a platinum crucible, and this platinum crucible was held in an electric furnace for 4 hours at a temperature range of 1350 to 1550°C, which was suitable for melting the glass batch of each Example and Comparative Example, and the glass batch was melted while stirring, thereby obtaining a homogeneous molten glass. Next, the obtained molten glass was poured onto a carbon plate and cooled to obtain a lump-shaped glass cullet.

[0162] Next, the glass cullet 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 while changing the melting temperature using the rotational viscometer. The 1000 poise temperature was determined by measuring the temperature corresponding to the rotational viscosity of 1000 poise.

[0163] [Method for measuring liquidus temperature] 40 g of glass particles with a particle size of 0.5 to 1.5 mm obtained by crushing glass cullet obtained in the same manner as in the measurement method of 1000 poise temperature was placed in a platinum boat of 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, it 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. Next, the temperature inside the tubular electric furnace was measured using a B thermocouple, and the temperature at the position where precipitation began was taken as the liquidus temperature.

[0164] [Method for measuring specific gravity] Molten glass was obtained in the same manner as in the measurement method for monofilament tensile strength. Next, the platinum crucible containing the molten glass was removed from the electric furnace, and the molten glass was cooled. Next, the molten glass was tapped out of the platinum crucible, heated at a strain-removing temperature (660 to 750°C) for 2 hours to remove distortion from the glass, and cooled to room temperature (20 to 25°C) over 8 hours to obtain a glass gob. Using the obtained glass gob, the specific gravity of the glass composition for glass fiber was measured by specific gravity measurement using Archimedes' principle. Specifically, the weight A of the glass gob in air (density ρ1) and the weight B in ion-exchanged water (density ρ0) as a replacement liquid were measured using a specific gravity meter (manufactured by Mettler Toledo), and the specific gravity (ρ) was calculated from the following formula (α) to measure the specific gravity of the glass composition for glass fiber. ρ=ρ1+A((ρ0-ρ1) / (AB))···(α)

[0165] [Method for measuring monofilament tensile strength] The glass raw materials of Examples 1 to 5 and Comparative Examples 1 and 2 were each placed in a platinum vessel equipped with 200 nozzle tips at the bottom, and the platinum vessel was heated to 1000°C to 1200°C to melt the glass raw materials to obtain molten glass. Next, the molten glass was drawn out from the nozzle tips of each platinum vessel and wound around a winding device. Next, monofilaments were collected one by one from between the nozzle tips and the winding device. From the monofilaments thus obtained, those that were not deteriorated by contact or friction were selected, and at least 30 monofilaments were selected as measurement samples for each Example and Comparative Example.

[0166] At least 10 measurement samples for each of the Examples and Comparative Examples were observed with a scanning electron microscope (Hitachi High-Tech Corporation, product name: S-3400N) to measure the fiber diameter. Of the obtained measurements, the two largest and two smallest measurements were excluded, and the number average of the remaining measurements was taken as the average fiber diameter. The cross-sectional shape was considered to be circular, and the fiber cross-sectional area was calculated.

[0167] Next, each measurement sample from Examples 1 to 5 and Comparative Examples 1 to 4 was adhered to a predetermined mount with a rectangular hole in the center, measuring 25 mm on the long side and 10 mm on the short side, so that the fiber length within the hole was 25 mm, to prepare a test specimen. At a temperature of 23°C, the obtained test specimen was set in the gripper of a tensile tester (manufactured by A&D Co., Ltd., product name: Single Column Tensile Tester STB-1225S). After cutting off the edge of the mount, a tensile test was performed at a crosshead speed of 5 mm / min, and the maximum load at break was measured. Test specimens in which threads had come loose or broken during the test were excluded.

[0168] The maximum load value thus obtained was divided by the cross-sectional area of ​​the fiber to calculate the monofilament tensile strength (GPa) at a pulling rate of 5 mm / min at 23° C. Of the valid calculated values ​​obtained, the two largest and two smallest measured values ​​were excluded, and the number average of the remaining calculated values ​​was used as the measured value of the monofilament tensile strength.

[0169] [Method for measuring monofilament elastic modulus] Measurement samples were selected in the same manner as in the measurement of monofilament tensile strength.

[0170] Next, each measurement sample from Examples 1 to 5 and Comparative Examples 1 and 2 was bonded to a predetermined mount with a rectangular hole in the center, measuring 50 mm on the long side and 10 mm on the short side, so that the fiber length within the hole was 50 mm to prepare a test piece. The test piece was set in the gripper of the tensile tester, and after cutting off the edge of the mount, a tensile test was performed at a crosshead speed of 5 mm / min, and the elastic modulus (GPa) was calculated from the slope of the stress versus strain of 0.05 to 0.025%. Test pieces in which thread loss occurred during the measurement were excluded, and of the valid calculated values ​​obtained, the two largest and two smallest measured values ​​were excluded. The number average of the remaining calculated values ​​was used as the measured value of the monofilament elastic modulus.

[0171] [Method for measuring dielectric constant and dielectric loss tangent] The glass raw materials of Examples 1 to 5 and Comparative Examples 1 and 2 were placed in an 80 mm diameter platinum crucible and melted by heating at 1550°C for 6 hours. They were then removed from the platinum crucible to obtain homogeneous glass bulks or glass cullets. The resulting glass bulks or glass cullets were then annealed at 750°C for 8 hours to obtain test pieces. The test pieces were then polished to prepare polished test pieces measuring 80 mm x 3 mm (1 mm thick). The polished test pieces were then dried and stored in a room at 23°C and 60% humidity for 24 hours. The dielectric constant and dielectric loss tangent of the polished test pieces at 1 GHz were measured using a cavity resonator dielectric constant measuring device ADMS01Oc1 (product name) manufactured by AET Corporation in accordance with JIS C 2565:1992. Furthermore, the dielectric constant and dielectric loss tangent at 1 MHz of the obtained polished test pieces were measured in accordance with IEC 62631-2-1 using an LCR meter 4284A (trade name) manufactured by Keysight Technologies.

[0172] [Method for measuring tensile strength of glass fiber reinforced resin molded products] The glass raw materials of Examples 1 to 5 and Comparative Examples 1 and 2 were each placed in a platinum vessel equipped with 200 nozzle tips at the bottom, and the platinum vessel was heated to 1000°C to 1200°C to melt the glass raw materials to obtain molten glass. Next, the molten glass was drawn out from the nozzle tips of each platinum vessel and wound around a winding device. The winding device was rotated to wind the molten glass at a rotation speed of 1000 rpm, thereby performing spinning. Furthermore, using an applicator provided between the nozzle tips and the winding device, a sizing agent containing aminosilane, urethane resin, and bisphenol A-type epoxy resin was applied to the monofilaments in a proportion of 1.0 mass% relative to the monofilaments, thereby producing a long glass fiber having a bundle of 200 monofilaments and a number-average fiber diameter of 15 μm.

[0173] The obtained long glass fibers were cut to a length of 3 mm to obtain chopped strands. The obtained chopped strands were then kneaded with polybutylene terephthalate resin (manufactured by Polyplastics Co., Ltd., product name: DURANEX 2000) in a twin-screw kneader (manufactured by Shibaura Machine Co., Ltd., product name: TEM-26SS) at a screw rotation speed of 100 rpm to produce resin pellets (glass fiber reinforced resin pellets) with a glass content of 30.0 mass%.

[0174] The obtained glass fiber reinforced resin pellets were injection molded using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., product name: NEX80) at a mold temperature of 140°C and an injection temperature of 260°C to produce glass fiber reinforced resin molded products, which are dumbbell test pieces in accordance with Japanese Industrial Standards (JIS) K 7161-1:2014.

[0175] The obtained glass fiber reinforced resin molded product was subjected to a static tensile test in accordance with Japanese Industrial Standards (JIS) K 7161-1, 2:2014 using a precision universal testing machine (manufactured by Shimadzu Corporation, product name: Precision Universal Testing Machine AG-50kNXplus) at a test temperature of 23°C, and the tensile strength (MPa) of the glass fiber reinforced resin molded product was measured.

[0176] [Method for measuring the tensile strength of glass fiber reinforced resin molded products after PCT treatment] A glass fiber reinforced resin molded article was prepared in the same manner as in the above method for measuring the tensile strength of a glass fiber reinforced resin molded article.

[0177] The obtained glass fiber reinforced resin molded article was treated for 24 hours in a saturated steam environment at 2 atmospheres and 121°C to obtain a PCT-treated glass fiber reinforced resin molded article. Next, a static tensile test was performed on the obtained PCT-treated glass fiber reinforced resin molded article in accordance with Japanese Industrial Standards (JIS) K 7161-1, 2:2014 using a precision universal testing machine (manufactured by Shimadzu Corporation, product name: Precision Universal Testing Machine AG-50kNXplus) at a test temperature of 23°C to measure the tensile strength (MPa) of the glass fiber reinforced resin molded article.

[0178] [Method for measuring bending strength of glass fiber reinforced resin molded products] A glass fiber reinforced resin molded article was prepared in the same manner as in the above method for measuring the tensile strength of a glass fiber reinforced resin molded article.

[0179] The obtained glass fiber reinforced resin molded product was subjected to a static bending test in accordance with Japanese Industrial Standards (JIS) K 7171:2016 using a precision universal testing machine (manufactured by Shimadzu Corporation, product name: Precision Universal Testing Machine AG-50kNXplus) at a test temperature of 23°C, and the bending strength (MPa) of the glass fiber reinforced resin molded product was measured.

[0180] [Method for measuring the flexural modulus of glass fiber reinforced resin molded products] A glass fiber reinforced resin molded article was prepared in the same manner as in the above method for measuring the tensile strength of a glass fiber reinforced resin molded article.

[0181] The obtained glass fiber reinforced resin molded product was subjected to a static bending test in accordance with Japanese Industrial Standards (JIS) K 7171:2016 using a precision universal testing machine (manufactured by Shimadzu Corporation, product name: Precision Universal Testing Machine AG-50kNXplus) at a test temperature of 23°C, and the flexural modulus (GPa) of the glass fiber reinforced resin molded product was measured.

[0182] [Calculation method for strength retention rate after PCT treatment] The ratio of the tensile strength B of the glass fiber reinforced resin molded product after the PCT treatment to the tensile strength A of the glass fiber reinforced resin molded product (B / A×100; unit: %) was calculated.

[0183] [Method for evaluating CO2 emission reduction rate] For the glass compositions for glass fiber of Examples 1 to 5 and Comparative Examples 1 and 2, a value equivalent to the emission intensity on a physical volume basis for "other non-metallic minerals" shown in No. 32, column code 62909 in the "Emission intensity unit based on input-output tables" described in the "Emission intensity unit database for calculating greenhouse gas emissions, etc. of organizations throughout the supply chain (Ver. 2.5)" was calculated from the usage ratio of other non-metallic minerals in the raw materials. Then, values ​​equivalent to the emission intensity in the range of 0 to 0.0070 were evaluated as "A," values ​​in the range of 0.0070 to 0.0085 as "B," and values ​​of 0.0085 or more as "C."

[0184] [Method for evaluating color change in glass fiber reinforced resin molded products] A glass fiber reinforced resin molded article was prepared in the same manner as in the above method for measuring the tensile strength of a glass fiber reinforced resin molded article.

[0185] For glass fiber reinforced resin molded products containing glass fibers made from the glass fiber glass compositions of Examples 1 to 5 and Comparative Examples 1 and 2, the L*a*b* values ​​were evaluated using a spectrocolorimeter SE6000 manufactured by Nippon Denshoku Industries Co., Ltd., and the coordinates in the L*a*b* color space were determined. When the color difference ΔE value was compared with a glass fiber reinforced resin molded product obtained by the same procedure as in the present Examples or Comparative Examples except for using a glass fiber glass composition using non-recycled raw materials, if the value of 0<ΔE≦3, it was evaluated as "A", if 3<ΔE≦7, it was evaluated as "B", and if 7<ΔE, it was evaluated as "C".

[0186] [Table 1]

[0187] It is clear from Table 1 that the glass compositions for glass fiber of Examples 1 to 5 can be produced with reduced CO2 emissions, can impart water resistance to glass fiber reinforced resin molded articles, and can suppress color change. On the other hand, it is clear from Table 1 that the glass composition for glass fiber of Comparative Example 1, which is glass composition A for glass fiber derived from commercial waste glass, can produce glass fiber reinforced resin molded articles with reduced CO2 emissions, but cannot sufficiently suppress color change in the glass fiber reinforced resin molded articles. It is also clear from Table 1 that the glass fiber composition of Comparative Example 2, in which the contents of BaO and Na2O relative to the total amount of the glass composition for glass fiber are below the ranges of the present invention and the content of K2O exceeds the range of the present invention, can suppress color change in the glass fiber reinforced resin molded articles, but cannot produce glass fiber reinforced resin molded articles with reduced CO2 emissions.

[0188] [Example 6] The same glass raw materials as in Example 1 were placed in a platinum vessel equipped with 200 nozzle tips at the bottom, and the platinum vessel was heated to 1200°C to melt the glass raw materials and obtain molten glass. Next, the molten glass was drawn out from the nozzle tips of the platinum vessel and wound around a winding device. The winding device was rotated to wind the molten glass at a rotation speed of 1000 rpm, thereby performing spinning. Furthermore, using an applicator provided between the nozzle tips and the winding device, a sizing agent containing aminosilane, urethane resin, and phenol novolac epoxy resin was applied to the monofilaments in a proportion of 1.5 mass% relative to the monofilaments, thereby producing a long glass fiber having a bundle of 200 monofilaments and a number average fiber diameter of 15 μm.

[0189] A glass fiber reinforced resin molded product containing the glass fiber of this example, which is a dumbbell test piece in accordance with Japanese Industrial Standards (JIS) K 7161-1:2014, was prepared in exactly the same manner as in Examples 1 to 5, except that the long glass fiber obtained in this example was used.

[0190] The glass fiber reinforced resin molded article containing the glass fiber of this example was measured for tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) in exactly the same manner as in Examples 1 to 5. The results are shown in Table 2.

[0191] Furthermore, for the glass fiber reinforced resin molded article containing the glass fiber of this example, the tensile strength of the glass fiber reinforced resin molded article after PCT treatment was measured, the strength retention rate after PCT treatment was calculated, and the color change of the glass fiber reinforced resin molded article was evaluated in exactly the same manner as in Examples 1 to 5. The results are shown in Table 2.

[0192] Table 2 also shows the sizing agent used to prepare the glass fibers in Example 1, the resin used to prepare the glass fiber reinforced resin molded product, the tensile strength of the glass fiber reinforced resin molded product in Example 1, the tensile strength of the glass fiber reinforced resin molded product after PCT treatment, the flexural strength of the glass fiber reinforced resin molded product, the flexural modulus of the glass fiber reinforced resin molded product, the strength retention rate after PCT treatment, and the change in color.

[0193] [Example 7] A glass fiber reinforced resin molded product containing the glass fiber of this example was prepared in exactly the same manner as in Examples 1 to 5, except that a sizing agent containing aminosilane, urethane resin, phenol novolac epoxy resin, and bisphenol A epoxy resin was applied to the monofilament in a proportion of 1.8% by mass relative to the monofilament, and the tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) of the glass fiber reinforced resin molded product were measured. The results are shown in Table 2.

[0194] Furthermore, for the glass fiber reinforced resin molded article containing the glass fiber of this example, the tensile strength of the glass fiber reinforced resin molded article after PCT treatment was measured, the strength retention rate after PCT treatment was calculated, and the color change of the glass fiber reinforced resin molded article was evaluated in exactly the same manner as in Examples 1 to 5. The results are shown in Table 2.

[0195] [Example 8] A glass fiber reinforced resin molded product containing the glass fiber of this example was prepared in exactly the same manner as in Examples 1 to 5, except that a sizing agent containing aminosilane, urethane resin, and bisphenol A-type epoxy resin was applied to the monofilament in a proportion of 0.25% by mass relative to the monofilament, and the tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) of the glass fiber reinforced resin molded product were measured. The results are shown in Table 2.

[0196] Furthermore, for the glass fiber reinforced resin molded article containing the glass fiber of this example, the tensile strength of the glass fiber reinforced resin molded article after PCT treatment was measured, the strength retention rate after PCT treatment was calculated, and the color change of the glass fiber reinforced resin molded article was evaluated in exactly the same manner as in Examples 1 to 5. The results are shown in Table 2.

[0197] [Example 9] The same glass raw materials as in Example 1 were placed in a platinum vessel equipped with 200 nozzle tips at the bottom, and the platinum vessel was heated to 1200°C to melt the glass raw materials and obtain molten glass. Next, the molten glass was drawn out from the nozzle tips of the platinum vessel and wound around a winding device. The winding device was rotated to wind the molten glass at a rotation speed of 1000 rpm, thereby performing spinning. Furthermore, using an applicator provided between the nozzle tips and the winding device, a sizing agent containing aminosilane and a urethane resin was applied to the monofilaments in a proportion of 0.6% by mass relative to the monofilaments, thereby producing long glass fibers having a bundle of 200 monofilaments and a number-average fiber diameter of 15 µm.

[0198] The obtained long glass fibers were cut to a length of 3 mm to obtain chopped strands. The obtained chopped strands were then kneaded with polyamide 6 resin (manufactured by UBE Corporation, product name: 1015B, indicated as "PA6" in Table 2) in a twin-screw kneader (manufactured by Shibaura Machine Co., Ltd., product name: TEM-26SS) at a screw rotation speed of 100 rpm to produce resin pellets (glass fiber reinforced resin pellets) with a glass content of 30.0 mass%.

[0199] The obtained glass fiber reinforced resin pellets were injection molded using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., product name: NEX80) at a mold temperature of 90°C and an injection temperature of 260°C to produce a glass fiber reinforced resin molded product containing the glass fiber of this example, which is a dumbbell test piece in accordance with Japanese Industrial Standards (JIS) K 7161-1:2014.

[0200] The glass fiber reinforced resin molded product containing the glass fiber of this example was measured for tensile strength (MPa), bending strength (MPa), and bending modulus (GPa) of the glass fiber reinforced resin molded product in exactly the same manner as in Examples 1 to 5.

[0201] Furthermore, for the glass fiber reinforced resin molded article containing the glass fiber of this example, the tensile strength of the glass fiber reinforced resin molded article after PCT treatment was measured, the strength retention rate after PCT treatment was calculated, and the color change of the glass fiber reinforced resin molded article was evaluated in exactly the same manner as in Examples 1 to 5. The results are shown in Table 2.

[0202] [Example 10] A glass fiber reinforced resin molded product containing the glass fiber of this example was prepared in exactly the same manner as in Example 9, except that a sizing agent containing aminosilane, urethane resin, and acrylic acid copolymer was applied to the monofilament in a proportion of 1.0 mass% based on the monofilament, and the tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) of the glass fiber reinforced resin molded product were measured. The results are shown in Table 2.

[0203] Furthermore, for the glass fiber reinforced resin molded article containing the glass fiber of this example, the tensile strength of the glass fiber reinforced resin molded article after PCT treatment was measured, the strength retention rate after PCT treatment was calculated, and the color change of the glass fiber reinforced resin molded article was evaluated in exactly the same manner as in Example 6. The results are shown in Table 2.

[0204] [Example 11] A glass fiber reinforced resin molded product containing the glass fiber of this example was prepared in exactly the same manner as in Example 9, except that a sizing agent containing aminosilane, urethane resin, and maleic acid copolymer was applied to the monofilament in a proportion of 1.1% by mass based on the monofilament, and the tensile strength, flexural strength, and flexural modulus of the glass fiber reinforced resin molded product were measured. The results are shown in Table 2.

[0205] Furthermore, for the glass fiber reinforced resin molded article containing the glass fiber of this example, the tensile strength of the glass fiber reinforced resin molded article after PCT treatment was measured, the strength retention rate after PCT treatment was calculated, and the color change of the glass fiber reinforced resin molded article was evaluated in exactly the same manner as in Example 6. The results are shown in Table 2.

[0206] [Table 2]

[0207] From Table 2, it is clear that according to the glass compositions for glass fiber of Examples 6 to 11, even when the sizing agent used in producing the glass fibers, the sizing agent attachment rate (rate of application to monofilaments), and the resin used in producing the glass fiber reinforced resin molded product are changed, CO2 emissions can be reduced and the glass fiber reinforced resin molded product can be imparted with water resistance and hue change can be suppressed, just like the glass compositions for glass fiber of Examples 1 to 5.

Claims

1. A glass composition for glass fibers, comprising: SiO in the range of 57.75 to 64.25 mass% based on the total amount of the glass composition for glass fiber ２ and, Al in the range of 3.51 to 11.80 mass% ２ O ３ and, B in the range of 4.01 to 5.80 mass% ２ O ３ and, CaO in the range of 9.60 to 20.00% by weight; MgO in the range of 0.55 to 1.94 wt. %; SrO in the range of 0.30 to 1.55 wt. %; BaO in the range of 0.32 to 1.65 wt. %; Fe in the range of 0.05 to 0.94 mass% ２ O ３ and, TiO in the range of 0.05 to 0.94 mass % ２ and, Na in the range of 3.05 to 13.80 mass% ２ O and K in the range of 0.40 to 2.00 mass% ２ O and ZrO in the range of 0.01 to 0.94 mass % ２ and, F in the range of 0.05 to 0.94 mass% ２ and the total content of CaO, MgO, SrO, and BaO is in the range of 12.40 to 21.45 mass%, The Na ２ O and K ２ A glass composition for glass fiber, characterized in that the total content of O is in the range of 3.50 to 15.80 mass%.

2. 2. The glass composition for glass fiber according to claim 1, wherein the F ２ The ratio of the content of SrO to the content of SrO (SrO / F ２ ) is in the range of 0.50 to 12.

50.

3. 2. The glass composition for glass fiber according to claim 1, wherein the ratio of the B content to the SrO content is ２ O ３ The ratio of the content of (B ２ O ３ / SrO) is in the range of 2.51 to 24.

40.

4. A glass fiber comprising the glass composition for glass fiber according to any one of claims 1 to 3.

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