Glass composition for glass fibers, glass fibers, glass fiber reinforced resin composition, and molded articles

Abstract

A glass composition for glass fibers, wherein the total amount of Na2O and K2O is 4.10 to 12.85% by mass, the ratio (Na2O / B2O3) is 0.81 to 8.1, the ratio (Na2O / Al2O3) is 0.30 to 4.00, and the ratio (MgO / Al2O3) is 0.16 to 1.44, and satisfies formula (1) when the SiO2 content is S (mass%), the Al2O3 content is A (mass%), the CaO content is C (mass%), and the B2O3 content is B (mass%). 0.010≦B / (S+A+C)≦0.070 (1)

Description

Technical Field

[0001] The present disclosure relates to a glass composition for glass fiber, glass fiber, a glass fiber-reinforced resin composition, and a molded article.

Background Art

[0002] In recent years, there has been a strong demand in the industrial world for reducing environmental load and establishing sustainable production and consumption patterns. One of the initiatives undertaken by the industrial world to achieve these goals is recycling, which involves collecting products that have already been sold and used as final products, and using them as raw materials to manufacture final products again. For example, Patent Document 1 describes a method for producing glass fiber from glass-containing industrial waste, industrial glass waste, and the like.

[0003] As one of the applications of glass fiber, glass fiber-reinforced resin compositions are known. For example, Patent Document 2 describes a flame-retardant polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and a fibrous inorganic compound.

Prior Art Literature

Patent Literature

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problem to be Solved by the Invention

[0005] Using recycled glass can be expected to reduce CO2 emissions during manufacturing. However, using recycled glass may lead to problems such as increased viscosity of the molten glass, raising the required temperature for glass fiber manufacturing, deterioration of the acid resistance of the glass fibers, insufficient strength of the glass fiber reinforced resin composition, color changes in the glass fiber reinforced resin composition, and reduced water resistance of the glass fiber reinforced resin composition.

[0006] This disclosure aims to provide a glass composition for glass fibers that can achieve reduced CO2 emissions during manufacturing, a reduced 1000 poise temperature, excellent acid resistance, sufficiently suppressed hue change, and excellent retention of tensile strength and water resistance. Furthermore, this disclosure aims to provide glass fibers made from the glass composition for glass fibers, a glass fiber reinforced resin composition containing the glass fibers, and a molded article containing the glass fiber reinforced resin composition. [Means for solving the problem]

[0007] This disclosure provides, for example, the following [1] to [5]. [1] A glass composition for glass fibers, The SiO2 content is 56.10 to 70.10% by mass. The Al2O3 content is 2.10 to 12.20% by mass. The CaO content is 8.10 to 20.50% by mass. The MgO content is 0.50 to 5.00% by mass. The B2O3 content is 0.60 to 7.20% by mass. The Na2O content is 3.10 to 12.85% by mass. The F2 content is 0.01 to 1.00 mass%, The Fe2O3 content is 0.01 to 1.00% by mass. The K2O content is 0-0.80% by mass. The Li2O content is 0-0.40% by mass. The TiO2 content is 0-0.90% by mass. The ZnO content is 0-0.40% by mass. The ZrO2 content is 0-0.40% by mass. The P2O5 content is less than 0.10% by mass. The total content of Na2O and K2O is 4.10 to 12.85% by mass. The ratio of Na2O content to B2O3 content (Na2O / B2O3) is between 0.81 and 8.10. The ratio of Na2O content to Al2O3 content (Na2O / Al2O3) is between 0.30 and 4.00. The ratio of MgO content to Al2O3 content (MgO / Al2O3) is between 0.16 and 1.44. A glass composition for glass fibers that satisfies the following formula (1), where S (mass%) is the SiO2 content, A (mass%) is the Al2O3 content, C (mass%) is the CaO content, and B (mass%) is the B2O3 content. 0.010≦B / (S+A+C)≦0.070 (1) [2] The glass composition for glass fibers according to [1], wherein the ratio (Na2O / Al2O3) is 0.53 to 1.38. [3] Glass fiber comprising the glass composition for glass fiber described in [1] or [2]. [4] A glass fiber reinforced resin composition comprising the glass fibers described in [3] and a resin. [5] A molded article comprising the glass fiber reinforced resin composition described in [4]. [Effects of the Invention]

[0008] According to the present disclosure, there is provided a glass composition for glass fibers that can achieve reduction of CO2 emissions during production, has a reduced 1000 poise temperature, is excellent in acid resistance, sufficiently suppresses hue change, and can realize a glass fiber-reinforced resin composition excellent in tensile strength and water-resistant strength retention rate. Further, according to the present disclosure, there are provided a glass fiber formed of the glass composition for glass fibers, a glass fiber-reinforced resin composition containing the glass fiber, and a molded article containing the glass fiber-reinforced resin composition. MODE FOR CARRYING OUT THE INVENTION

[0009] Hereinafter, one embodiment for carrying out the present disclosure will be described, but the present disclosure is not limited to the following embodiment.

[0010] (Glass Composition) The glass composition of the present embodiment is a glass composition for glass fibers.

[0011] The glass composition for glass fibers may be a composition constituting glass fibers, or may be a glass raw material for producing glass fibers. By melting and spinning the glass composition for glass fibers, a glass fiber composed of the glass composition for glass fibers can be obtained.

[0012] Since the glass composition of the present embodiment has the specific composition described later, it can achieve reduction of CO2 emissions during production, has a reduced 1000 poise temperature, and is excellent in acid resistance. Further, since the glass composition of the present embodiment has the specific composition described later, a glass fiber-reinforced resin composition using a glass fiber composed of the glass composition of the present embodiment has hue change sufficiently suppressed, and is excellent in tensile strength and water-resistant strength retention rate.

[0013] In the glass composition of the present embodiment, the content of SiO₂ is 56.10 to 70.10 mass%, the content of Al₂O₃ is 2.10 to 12.20 mass%, the content of CaO is 8.10 to 20.50 mass%, the content of MgO is 0.50 to 5.00 mass%, the content of B₂O₃ is 0.60 to 7.20 mass%, the content of Na₂O is 3.10 to 12.85 mass%, the content of F₂ is 0.01 to 1.00 mass%, the content of Fe₂O₃ is 0.01 to 1.00 mass%, the content of K₂O is 0 to 0.80 mass%, the content of Li₂O is 0 to 0.40 mass%, the content of TiO₂ is 0 to 0.90 mass%, the content of ZnO is 0 to 0.40 mass%, the content of ZrO₂ is 0 to 0.40 mass%, and the content of P₂O₅ is less than 0.10 mass%. The content of P₂O₅ may be 0 mass%.

[0014] Note that "the content of A is 0 mass%" means that A is not contained, or the content of A is below the detection limit.

[0015] From the viewpoint of achieving a higher skeletal ratio of the network structure formed in the glass and obtaining better mechanical properties, the SiO2 content may be 56.50% by mass or more, 58.10% by mass or more, 59.50% by mass or more, or 60.10% by mass or more. Furthermore, from the viewpoint of lowering the melt viscosity, making it easier to form a uniform glass, and making it easier to stably and continuously fiberize over a long period of time, the SiO2 content may be 68.10% by mass or less, 66.50% by mass or less, 65.80% by mass or less, 65.30% by mass or less, 64.50% by mass or less, or 63.50% by mass or less. In other words, the SiO2 content is, for example, 56.10-70.10% by mass, 56.10-68.10% by mass, 56.10-66.50% by mass, 56.10-65.80% by mass, 56.10-65.30% by mass, 56.10-64.50% by mass, 56.10-63.50% by mass, and 56.50-70.10% by mass. , 56.50~68.10% by mass, 56.50~66.50% by mass, 56.50~65.80% by mass, 56.50~65.30% by mass, 56.50~64 .50% by mass, 56.50~63.50% by mass, 58.10~70.10% by mass, 58.10~68.10% by mass, 58.10~66.50% by mass, 58 .10~65.80% by mass, 58.10~65.30% by mass, 58.10~64.50% by mass, 58.10~63.50% by mass, 59.50~70.10 Mass%, 59.50~68.10 mass%, 59.50~66.50 mass%, 59.50~65.80 mass%, 59.50~65.30 mass%, 59.50 It may be ~64.50 mass%, 59.50~63.50 mass%, 60.10~70.10 mass%, 60.10~68.10 mass%, 60.10~66.50 mass%, 60.10~65.80 mass%, 60.10~65.30 mass%, 60.10~64.50 mass%, or 60.10~63.50 mass%.

[0016] From the viewpoint of obtaining better mechanical properties by increasing the skeletal ratio of the network structure formed in the glass, from the viewpoint of further improving durability when in contact with water and chemicals, and from the viewpoint of further suppressing crystallization and further lowering the liquidus temperature, the Al2O3 content may be 3.10% by mass or more, 3.60% by mass or more, 5.10% by mass or more, 5.60% by mass or more, 6.50% by mass or more, or 7.50% by mass or more. Furthermore, from the viewpoint of lowering the melt viscosity, making it easier to form a uniform glass, and making it easier to stably and continuously fiberize over a long period of time, the Al2O3 content may be 11.90% by mass or less, 11.40% by mass or less, 10.90% by mass or less, or 9.90% by mass or less. That is, the content of Al2O3 is, for example, 2.10-12.20% by mass, 2.10-11.90% by mass, 2.10-11.40% by mass, 2.10-10.90% by mass, 2.10-9.90% by mass, 3.10-12.20% by mass, 3.10-11.90% by mass, 3.10-11.40% by mass. Amount%, 3.10~10.90% by mass, 3.10~9.90% by mass, 3.60~12.20% by mass, 3.60~11.90% by mass, 3.60~1 1.40% by mass, 3.60~10.90% by mass, 3.60~9.90% by mass, 5.10~12.20% by mass, 5.10~11.90% by mass, 5 .10~11.40% by mass, 5.10~10.90% by mass, 5.10~9.90% by mass, 5.60~12.20% by mass, 5.60~11.9 0% by mass, 5.60~11.40% by mass, 5.60~10.90% by mass, 5.60~9.90% by mass, 6.50~12.20% by mass, 6.50 It may be ~11.90% by mass, 6.50-11.40% by mass, 6.50-10.90% by mass, 6.50-9.90% by mass, 7.50-12.20% by mass, 7.50-11.90% by mass, 7.50-11.40% by mass, 7.50-10.90% by mass, or 7.50-9.90% by mass.

[0017] From the viewpoint of further improving the tensile strength and tensile modulus of glass fibers and obtaining better mechanical properties for composite material applications, the CaO content may be 10.50% by mass or more, 11.10% by mass or more, 12.50% by mass or more, 14.50% by mass or more, 15.10% by mass or more, or 15.50% by mass or more. Furthermore, from the viewpoint of further suppressing CO2 emissions and being more effective in ensuring sustainable production and consumption patterns, the CaO content may be 19.90% by mass or less, 18.90% by mass or less, or 17.90% by mass or less. That is, the content of CaO is, for example, 8.10-20.50% by mass, 8.10-19.90% by mass, 8.10-18.90% by mass, 8.10-17.90% by mass, 10.50-20.50% by mass, 10.50-19.90% by mass, 10.50-1 8.90 mass%, 10.50~17.90 mass%, 11.10~20.50 mass%, 11.10~19.90 mass%, 11.10~18.90 mass%, 11.10~17.90 mass%, 12.50~20.50 mass%, 12.50~19.90 quality Amount%, 12.50-18.90 mass%, 12.50-17.90 mass%, 14.50-20.50 mass%, 14.50-19.90 mass%, 14.50-18.90 mass%, 14.50-17.90 mass%, 15.10-20.50 mass%, 15 It may be .10-19.90% by mass, 15.10-18.90% by mass, 15.10-17.90% by mass, 15.50-20.50% by mass, 15.50-19.90% by mass, 15.50-18.90% by mass, or 15.50-17.90% by mass.

[0018] From the viewpoint of further reducing the melt viscosity and facilitating stable and continuous fiber formation over a long period of time, the MgO content may be 0.70% by mass or more, 0.90% by mass or more, 1.10% by mass or more, or 1.30% by mass or more. Furthermore, from the viewpoint of further suppressing the formation of crystals with other components, the MgO content may be 4.90% by mass or less, 4.40% by mass or less, 3.90% by mass or less, 3.40% by mass or less, or 2.90% by mass or less. That is, the content of MgO is, for example, 0.50-5.00% by mass, 0.50-4.90% by mass, 0.50-4.40% by mass, 0.50-3.90% by mass, 0.50-3.40% by mass, 0.50-2.90% by mass, 0.70-5.0 0% by mass, 0.70~4.90% by mass, 0.70~4.40% by mass, 0.70~3.90% by mass, 0.70~3.40% by mass, 0.70~2.90% by mass, 0.90~5.00% by mass, 0.90~4.90% by mass, 0.90~4.4 0% by mass, 0.90~3.90% by mass, 0.90~3.40% by mass, 0.90~2.90% by mass, 1.10~5.00% by mass, 1.10~4.90% by mass, 1.10~4.40% by mass, 1.10~3.90% by mass, 1.10~3.4 It may be 0% by mass, 1.10-2.90% by mass, 1.30-5.00% by mass, 1.30-4.90% by mass, 1.30-4.40% by mass, 1.30-3.90% by mass, 1.30-3.40% by mass, or 1.30-2.90% by mass.

[0019] From the viewpoint of further reducing the melt viscosity and facilitating stable and continuous fiber formation over a long period of time, the B2O3 content may be 1.60% by mass or more, 2.40% by mass or more, 2.90% by mass or more, 3.10% by mass or more, or 4.00% by mass or more. Furthermore, from the viewpoint of further suppressing the generation of volatile substances and scum during glass melting, the B2O3 content may be 6.00% by mass or less, 5.50% by mass or less, or 4.90% by mass or less. That is, the content of B2O3 is, for example, 0.60-7.20% by mass, 0.60-6.00% by mass, 0.60-5.50% by mass, 0.60-4.90% by mass, 1.60-7.20% by mass, 1 .60~6.00% by mass, 1.60~5.50% by mass, 1.60~4.90% by mass, 2.40~7.20% by mass, 2.40~6.00% by mass, 2.40~5.50% by mass, 2.40~4.9 0% by mass, 2.90-7.20% by mass, 2.90-6.00% by mass, 2.90-5.50% by mass, 2.90-4.90% by mass, 3.10-7.20% by mass, 3.10-6.00% by mass, 3 The content may be .10 to 5.50% by mass, 3.10 to 4.90% by mass, 4.00 to 7.20% by mass, 4.00 to 6.00% by mass, 4.00 to 5.50% by mass, or 4.00 to 4.90% by mass.

[0020] From the viewpoint of further reducing the melt viscosity and facilitating stable and continuous fiber formation over a long period, the Na2O content may be 4.10% by mass or more, 4.20% by mass or more, 4.50% by mass or more, 4.80% by mass or more, 5.10% by mass or more, or 6.10% by mass or more. Furthermore, from the viewpoint of increasing the skeletal ratio of the network structure formed in the glass, obtaining better mechanical properties for composite material applications, improving durability when in contact with water and chemicals, and further suppressing erosion of the furnace material during manufacturing, the Na2O content may be 12.40% by mass or less, 11.20% by mass or less, 10.50% by mass or less, 9.50% by mass or less, or 8.80% by mass or less. In other words, the Na2O content is, for example, 3.10-12.85% by mass, 3.10-12.40% by mass, 3.10-11.20% by mass, 3.10-10.50% by mass, 3.10-9.50% by mass, 3.10-8.80% by mass, 4.10-12.85% by mass, 4.10-12.40% by mass, 4.10-11.20% by mass, and 4.10-10% by mass. 50% by mass, 4.10~9.50% by mass, 4.10~8.80% by mass, 4.20~12.85% by mass, 4.20~12.40% by mass, 4.20~11.20% by mass, 4 .20~10.50% by mass, 4.20~9.50% by mass, 4.20~8.80% by mass, 4.50~12.85% by mass, 4.50~12.40% by mass, 4.50~11. 20% by mass, 4.50~10.50% by mass, 4.50~9.50% by mass, 4.50~8.80% by mass, 4.80~12.85% by mass, 4.80~12.40% by mass, 4 .80~11.20% by mass, 4.80~10.50% by mass, 4.80~9.50% by mass, 4.80~8.80% by mass, 5.10~12.85% by mass, 5.10~12. 40% by mass, 5.10-11.20% by mass, 5.10-10.50% by mass, 5.10-9.50% by mass, 5.10-8.80% by mass, 6.10-12.85% by mass, 6 It may be .10 to 12.40% by mass, 6.10 to 11.20% by mass, 6.10 to 10.50% by mass, 6.10 to 9.50% by mass, or 6.10 to 8.80% by mass.

[0021] The Na2O content may be adjusted so that the total content of Na2O and K2O falls within the range described below. For example, when the glass composition of this embodiment contains K2O, the upper limit of the Na2O content may be the value obtained by subtracting the lower limit of the K2O content from the upper limit of the total content of Na2O and K2O.

[0022] From the viewpoint of reducing the generation of bubbles during spinning, the F2 content may be 0.05% by mass or more, 0.1% by mass or more, 0.15% by mass or more, 0.25% by mass or more, or 0.35% by mass or more. Furthermore, from the viewpoint of improving chemical resistance and obtaining better mechanical properties for composite material applications, the F2 content may be 0.90% by mass or less, 0.80% by mass or less, 0.70% by mass or less, 0.60% by mass or less, or 0.50% by mass or less. That is, the content of F2 is, for example, 0.01-1.00 mass%, 0.01-0.90 mass%, 0.01-0.80 mass%, 0.01-0.70 mass%, 0.01-0.60 mass%, 0.01-0.50 mass%, 0.05-1.00 mass%, 0.05-0.90 mass%, 0 .05~0.80 mass%, 0.05~0.70 mass%, 0.05~0.60 mass%, 0.05~0.50 mass%, 0.1~1.00 mass%, 0.1~0.90 mass%, 0.1~0.80 mass%, 0.1~0.70 mass%, 0.1~0.60 mass%, 0.1~0.50 mass% , 0.15-1.00 mass%, 0.15-0.90 mass%, 0.15-0.80 mass%, 0.15-0.70 mass%, 0.15-0.60 mass%, 0.15-0.50 mass%, 0.25-1.00 mass%, 0.25-0.90 mass%, 0.25-0.80 mass%, 0.2 It may be 5-0.70% by mass, 0.25-0.60% by mass, 0.25-0.50% by mass, 0.35-1.00% by mass, 0.35-0.90% by mass, 0.35-0.80% by mass, 0.35-0.70% by mass, 0.35-0.60% by mass, or 0.35-0.50% by mass.

[0023] From the viewpoint of improving meltability and facilitating stable and continuous fiber formation over long periods, the Fe2O3 content may be 0.05% by mass or more, or 0.07% by mass or more. Furthermore, from the viewpoint of further suppressing glass discoloration, the Fe2O3 content may be 0.80% by mass or less, 0.60% by mass or less, 0.40% by mass or less, or 0.30% by mass or less. In other words, the Fe2O3 content may be, for example, 0.01-1.00 mass%, 0.01-0.80 mass%, 0.01-0.60 mass%, 0.01-0.40 mass%, 0.01-0.30 mass%, 0.05-1.00 mass%, 0.05-0.80 mass%, 0.05-0.60 mass%, 0.05-0.40 mass%, 0.05-0.30 mass%, 0.07-1.00 mass%, 0.07-0.80 mass%, 0.07-0.60 mass%, 0.07-0.40 mass%, or 0.07-0.30 mass%.

[0024] From the viewpoint of increasing the skeletal ratio of the network structure formed in the glass, obtaining better mechanical properties for composite material applications, improving durability when in contact with water and chemicals, and further suppressing erosion of the furnace material during manufacturing, the K2O content may be 0.70% by mass or less, 0.60% by mass or less, or 0.50% by mass or less. The K2O content may be 0% by mass, or 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more. In other words, the K2O content may be, for example, 0-0.80% by mass, 0-0.70% by mass, 0-0.60% by mass, 0-0.50% by mass, 0.01-0.80% by mass, 0.01-0.70% by mass, 0.01-0.60% by mass, 0.01-0.50% by mass, 0.1-0.80% by mass, 0.1-0.70% by mass, 0.1-0.60% by mass, 0.1-0.50% by mass, 0.2-0.80% by mass, 0.2-0.70% by mass, 0.2-0.60% by mass, 0.2-0.50% by mass, 0.3-0.80% by mass, 0.3-0.70% by mass, 0.3-0.60% by mass, or 0.3-0.50% by mass.

[0025] From the viewpoint of increasing the skeletal ratio of the network structure formed in the glass, obtaining better mechanical properties for composite material applications, improving durability when in contact with water and chemicals, and further suppressing erosion of the furnace material during manufacturing, the Li2O content may be 0.30% by mass or less, 0.20% by mass or less, or 0.10% by mass or less. Alternatively, the Li2O content may be 0% by mass. That is, the Li2O content may be, for example, 0-0.40% by mass, 0-0.30% by mass, 0-0.20% by mass, or 0-0.10% by mass.

[0026] From the viewpoint of lowering the high-temperature viscosity of the glass and further suppressing the discoloration of the glass, the TiO2 content may be 0.7% by mass or less, 0.5% by mass or less, or 0.3% by mass or less. Furthermore, the TiO2 content may be 0% by mass, and if it is included as an impurity in the glass raw material, from the viewpoint of reducing the cost of removing impurities and lowering manufacturing costs, it may be 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.15% by mass or more, or 0.19% by mass or more. That is, the content of TiO2 is, for example, 0 to 0.90 mass%, 0 to 0.7 mass%, 0 to 0.5 mass%, 0 to 0.3 mass%, 0.01 to 0.90 mass%, 0.01 to 0.7 mass%. Amount%, 0.01~0.5 mass%, 0.01~0.3 mass%, 0.05~0.90 mass%, 0.05~0.7 mass%, 0.05~0.5 mass%, 0.05~0.3 mass%, 0 .10~0.90% by mass, 0.10~0.7% by mass, 0.10~0.5% by mass, 0.10~0.3% by mass, 0.15~0.90% by mass, 0.15~0.7% by mass, 0.15 It may be ~0.5% by mass, 0.15-0.3% by mass, 0.19-0.90% by mass, 0.19-0.7% by mass, 0.19-0.5% by mass, or 0.19-0.3% by mass.

[0027] From the viewpoint of further reducing manufacturing costs, the ZnO content may be 0.2% by mass or less, 0.1% by mass or less, or 0.05% by mass or less. Alternatively, the ZnO content may be 0% by mass. That is, the ZnO content may be, for example, 0 to 0.40% by mass, 0 to 0.2% by mass, 0 to 0.1% by mass, or 0 to 0.05% by mass.

[0028] From the viewpoint of lowering the melt viscosity and improving meltability, which makes it easier to obtain uniform glass and to stably and continuously fiberize over a long period of time, the ZrO2 content may be 0.2% by mass or less, 0.1% by mass or less, or 0.05% by mass or less. Alternatively, the ZrO2 content may be 0% by mass. That is, the ZrO2 content may be, for example, 0 to 0.40% by mass, 0 to 0.2% by mass, 0 to 0.1% by mass, or 0 to 0.05% by mass.

[0029] From the viewpoint of further improving the water resistance of the glass fibers, the P2O5 content may be 0.05% by mass or less, 0.03% by mass or less, or 0.01% by mass or less. Alternatively, the P2O5 content may be 0% by mass. That is, the P2O5 content may be, for example, 0% by mass or more and less than 0.10% by mass, 0 to 0.05% by mass, 0 to 0.03% by mass, or 0 to 0.01% by mass.

[0030] In the glass composition of this embodiment, the total content of Na2O and K2O is 4.10 to 12.85% by mass. If the total content of Na2O and K2O is less than 4.10% by mass, the reduction rate of CO2 emissions decreases, and if the total content of Na2O and K2O exceeds 12.85% by mass, the tensile strength and hue of the glass fiber reinforced resin composition deteriorate.

[0031] From the viewpoint of further improving the reduction rate of CO2 emissions, the total content of Na2O and K2O may be 4.20% by mass or more, 4.50% by mass or more, 4.80% by mass or more, 5.10% by mass or more, or 6.10% by mass or more. Furthermore, from the viewpoint of further improving the tensile strength and hue of the glass fiber reinforced resin composition, the total content of Na2O and K2O may be 12.40% by mass or less, 11.20% by mass or less, 10.50% by mass or less, 9.50% by mass or less, or 8.80% by mass or less. That is, the total content of Na2O and K2O is, for example, 4.10-12.85% by mass, 4.10-12.40% by mass, 4.10-11.20% by mass, 4.10-10.50% by mass, 4.10-9.50% by mass, 4.10-8.80% by mass, 4.20-12.85% by mass, 4.20-12.40% by mass. Mass%, 4.20~11.20 mass%, 4.20~10.50 mass%, 4.20~9.50 mass%, 4.20~8.80 mass%, 4.50~12 .85% by mass, 4.50~12.40% by mass, 4.50~11.20% by mass, 4.50~10.50% by mass, 4.50~9.50% by mass, 4.50 ~8.80% by mass, 4.80~12.85% by mass, 4.80~12.40% by mass, 4.80~11.20% by mass, 4.80~10.50% by mass, 4.80~9.50 mass%, 4.80~8.80 mass%, 5.10~12.85 mass%, 5.10~12.40 mass%, 5.10~11.20 mass% %, 5.10~10.50% by mass, 5.10~9.50% by mass, 5.10~8.80% by mass, 6.10~12.85% by mass, 6.10~12.40 % by mass, 6.10-11.20% by mass, 6.10-10.50% by mass, 6.10-9.50% by mass, or 6.10-8.80% by mass.

[0032] Furthermore, when the glass composition of this embodiment contains K2O, the lower limit of the total content of Na2O and K2O may be the sum of the lower limit of the Na2O content and the lower limit of the K2O content.

[0033] In the glass composition of this embodiment, the ratio of the Na2O content to the B2O3 content (Na2O / B2O3) is between 0.81 and 8.10. If the ratio (Na2O / B2O3) is less than 0.81, the reduction rate of CO2 emissions decreases, and if the ratio (Na2O / B2O3) exceeds 8.10, the tensile strength and hue of the glass fiber reinforced resin composition deteriorate.

[0034] From the viewpoint of further improving the reduction rate of CO2 emissions, the ratio (Na2O / B2O3) may be 0.85 or higher, 0.90 or higher, or 0.99 or higher. Furthermore, from the viewpoint of further improving the tensile strength and hue of the glass fiber reinforced resin composition, the ratio (Na2O / B2O3) may be 7.00 or lower, 5.00 or lower, 3.50 or lower, 2.90 or lower, or 2.72 or lower. That is, the ratio (Na2O / B2O3) may be, for example, 0.81~8.10, 0.81~7.00, 0.81~5.00, 0.81~3.50, 0.81~2.90, 0.81~2.72, 0.85~8.10, 0.85~7.00, 0.85~5.00, 0.85~3.50, 0.85~2.90, 0.8 The values ​​may be 5-2.72, 0.90-8.10, 0.90-7.00, 0.90-5.00, 0.90-3.50, 0.90-2.90, 0.90-2.72, 0.99-8.10, 0.99-7.00, 0.99-5.00, 0.99-3.50, 0.99-2.90, or 0.99-2.72.

[0035] Furthermore, the upper limit of the ratio (Na2O / B2O3) may be the ratio of the upper limit of the Na2O content to the lower limit of the B2O3 content mentioned above. Also, the lower limit of the ratio (Na2O / B2O3) may be the ratio of the lower limit of the Na2O content to the upper limit of the B2O3 content mentioned above.

[0036] In the glass composition of this embodiment, the ratio of the Na2O content to the Al2O3 content (Na2O / Al2O3) is 0.30 to 4.00. If the ratio (Na2O / Al2O3) is less than 0.30, the reduction rate of CO2 emissions decreases, and if the ratio (Na2O / Al2O3) exceeds 4.00, the tensile strength and hue of the glass fiber reinforced resin composition deteriorate.

[0037] From the viewpoint of further improving the reduction rate of CO2 emissions, the ratio (Na2O / Al2O3) may be 0.35 or higher, 0.40 or higher, 0.45 or higher, or 0.53 or higher. Furthermore, from the viewpoint of further improving the tensile strength and hue of the glass fiber reinforced resin composition, the ratio (Na2O / Al2O3) may be 3.00 or lower, 2.50 or lower, 2.00 or lower, 1.50 or lower, or 1.38 or lower. That is, the ratio (Na2O / Al2O3) is, for example, 0.30~4.00, 0.30~3.00, 0.30~2.50, 0.30~2.00, 0.30~1.50, 0.30~1.38, 0.35~4.00, 0.35~3.00, 0.35~2.50, 0.35~2.00, 0.35~1.50, 0.35~1.38, 0.40~4.00, 0.40~3.00, 0. The values ​​may be 40-2.50, 0.40-2.00, 0.40-1.50, 0.40-1.38, 0.45-4.00, 0.45-3.00, 0.45-2.50, 0.45-2.00, 0.45-1.50, 0.45-1.38, 0.53-4.00, 0.53-3.00, 0.53-2.50, 0.53-2.00, 0.53-1.50, or 0.53-1.38.

[0038] Furthermore, the upper limit of the ratio (Na2O / Al2O3) may be the ratio of the upper limit of the Na2O content to the lower limit of the Al2O3 content mentioned above. Also, the lower limit of the ratio (Na2O / Al2O3) may be the ratio of the lower limit of the Na2O content to the upper limit of the Al2O3 content mentioned above.

[0039] In the glass composition of this embodiment, the ratio of MgO content to Al2O3 content (MgO / Al2O3) is 0.16 to 1.44. If the ratio (MgO / Al2O3) is less than 0.16, the reduction rate of CO2 emissions decreases, and if the ratio (MgO / Al2O3) exceeds 1.44, the tensile strength and hue of the glass fiber reinforced resin composition deteriorate.

[0040] From the viewpoint of further improving the reduction rate of CO2 emissions, the ratio (MgO / Al2O3) may be 0.17 or higher, 0.18 or higher, or 0.19 or higher. Furthermore, from the viewpoint of further improving the tensile strength and hue of the glass fiber reinforced resin composition, the ratio (MgO / Al2O3) may be 1.10 or lower, 0.90 or lower, 0.70 or lower, 0.50 or lower, or 0.45 or lower. That is, the ratio (MgO / Al2O3) may be, for example, 0.16~1.44, 0.16~1.10, 0.16~0.90, 0.16~0.70, 0.16~0.50, 0.16~0.45, 0.17~1.44, 0.17~1.10, 0.17~0.90, 0.17~0.70, 0.17~0.50, 0.1 It may be 7-0.45, 0.18-1.44, 0.18-1.10, 0.18-0.90, 0.18-0.70, 0.18-0.50, 0.18-0.45, 0.19-1.44, 0.19-1.10, 0.19-0.90, 0.19-0.70, 0.19-0.50, or 0.19-0.45.

[0041] Furthermore, the upper limit of the ratio (MgO / Al2O3) may be the ratio of the upper limit of the MgO content to the lower limit of the Al2O3 content mentioned above. Also, the lower limit of the ratio (MgO / Al2O3) may be the ratio of the lower limit of the MgO content to the upper limit of the Al2O3 content mentioned above.

[0042] The glass composition of this embodiment satisfies the following formula (1) when the SiO2 content is S (mass%), the Al2O3 content is A (mass%), the CaO content is C (mass%), and the B2O3 content is B (mass%). 0.010≦B / (S+A+C)≦0.070 (1)

[0043] If B / (S+A+C) is less than 0.010, the meltability of the glass composition decreases, and if B / (S+A+C) exceeds 0.070, the acid resistance of the glass composition decreases.

[0044] From the viewpoint of further improving melting properties, B / (S+A+C) may be 0.013 or higher, 0.015 or higher, or 0.017 or higher. Also, from the viewpoint of further improving acid resistance, B / (S+A+C) may be 0.060 or lower, 0.050 or lower, 0.040 or lower, or 0.035 or lower. That is, B / (S+A+C) may be, for example, 0.010~0.070, 0.010~0.060, 0.010~0.050, 0.010~0.040, 0.010~0.035, 0.013~0.070, 0.013~0.060, 0.013~0.050, 0.013~0.040, 0.013~ It may be 0.035, 0.015~0.070, 0.015~0.060, 0.015~0.050, 0.015~0.040, 0.015~0.035, 0.017~0.070, 0.017~0.060, 0.017~0.050, 0.017~0.040, or 0.017~0.035.

[0045] Furthermore, the upper limit of B / (S+A+C) may be the value obtained when S is the lower limit of the SiO2 content, A is the lower limit of the Al2O3 content, C is the lower limit of the CaO content, and B is the upper limit of the B2O3 content. Also, the lower limit of B / (S+A+C) may be the value obtained when S is the upper limit of the SiO2 content, A is the upper limit of the Al2O3 content, C is the upper limit of the CaO content, and B is the lower limit of the B2O3 content.

[0046] The glass composition of this embodiment may contain oxides of Sr, Ba, Co, Ni, Cu, Cr, Mo, W, Y, La, Bi, Gd, Pr, Sc, Pb, Cd, Nb, Eu, Tb, Dy, Ce, Sn, Tm, or Yb as impurities originating from the raw materials, in a total amount of less than 3.00% by mass (preferably less than 2.00% by mass, more preferably less than 1.00% by mass) of the total amount of the glass composition.

[0047] If the glass composition of this embodiment contains SrO, BaO, Nb2O5, WO3, Cr2O3, Bi2O3, or PbO as impurities, their content may be, independently, less than 0.90% by mass, less than 0.40% by mass, less than 0.20% by mass, less than 0.10% by mass, or less than 0.05% by mass.

[0048] Furthermore, if the glass composition of this embodiment contains Eu2O5, Tb2O3, Dy2O3, CeO2, Sn2O3, or Tm2O3 as impurities, their content may be, independently, less than 0.40% by mass, less than 0.10% by mass, less than 0.05% by mass, or less than 0.01% by mass.

[0049] In the glass composition of this embodiment, the content of each component can be measured by the method described in the examples. If organic matter is attached to the surface of the glass fibers, or if the glass fibers are mainly included as a reinforcing material in an organic substance such as a resin, the organic matter can be removed by, for example, heating in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours before the content can be measured.

[0050] The glass composition of this embodiment may be a molten and solidified product of glass raw materials including waste glass. Examples of waste glass include waste glass from the city.

[0051] "Waste glass in the city" refers to glass recovered from waste in the city (for example, waste containing 30% or more by mass of glass of unspecified shape relative to the total amount) without a process involving heating to 500°C or higher. "Waste in the city" includes not only waste discarded after being used in the city, but also waste that has been manufactured and completed as a product but has been discarded without being used or distributed to the city. "Waste glass in the city" does not include waste glass generated at factories, etc., during the manufacturing process of glass or products using glass. Examples of waste glass in the city include glass cullet recovered by crushing plate glass for building materials, glass cullet recovered by crushing glass for solar panels, glass cullet recovered by crushing fluorescent tubes, glass cullet recovered by crushing automobile windshields, glass cullet recovered by crushing screens of digital devices, and glass cullet recovered by crushing glass bottles used as containers for beverages, etc. Such waste glass from the city may be glass made from a glass composition having SiO2, Al2O3, and B2O3 as its basic composition, and further containing at least one of CaO and MgO, at least one of BaO and SrO, and at least one of Na2O and K2O.

[0052] Waste glass from the city may be glass recovered from city waste by methods commonly used by those skilled in the art. The recovery of waste glass from the city may be carried out, for example, by separating the recovered waste from the glass portion that can be recycled as glass raw material and the other portion. Alternatively, the waste may be crushed during the separation process to recover the glass as glass cullet. Furthermore, if necessary, organic matter derived from the non-glass portion of the waste may be removed by dissolving it in a solvent such as benzyl alcohol.

[0053] Heating waste materials in the city to over 500°C can increase carbon dioxide emissions. Therefore, using recycled glass waste that has not undergone heating processes above 500°C as a raw material for glass can reduce carbon dioxide (CO2) emissions during the manufacturing of glass compositions, thereby mitigating the environmental impact.

[0054] The waste glass used may be, for example, a composition having an SiO2 content of 65.00 to 72.50 mass%, an Al2O3 content of 1.50 to 3.50 mass%, a B2O3 content of 0 to 3.00 mass%, a total CaO and MgO content of 10.00 to 15.00 mass%, a total BaO and SrO content of 0 to 3.40 mass%, and a total Na2O and K2O content of 10.00 to 17.30 mass%.

[0055] The proportion of waste glass in the glass raw materials may be, for example, 1% by mass or more, and may also be 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more. A higher proportion of waste glass tends to result in a composition that improves the reduction rate of CO2 emissions. Alternatively, the proportion of waste glass in the glass raw materials may be, for example, 98% by mass or less, and may also be 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less, 50% by mass or less, or 40% by mass or less. A lower proportion of waste glass tends to result in a composition that improves the tensile strength and hue of the glass fiber reinforced resin composition. In other words, the proportion of waste glass in the glass raw material is, for example, 1-98% by mass, 1-95% by mass, 1-90% by mass, 1-80% by mass, 1-70% by mass, 1-60% by mass, 1-50% by mass, 1-40% by mass, 5-98% by mass, 5-95% by mass, 5-90% by mass, 5-80% by mass, 5-70% by mass, 5-60% by mass, 5-50% by mass, 5 ~40% by mass, 10-98% by mass, 10-95% by mass, 10-90% by mass, 10-80% by mass, 10-70% by mass, 10-60% by mass, 10-50% by mass, 10-4 0% by mass, 15-98% by mass, 15-95% by mass, 15-90% by mass, 15-80% by mass, 15-70% by mass, 15-60% by mass, 15-50% by mass, 15-40% by mass %, 20-98 mass%, 20-95 mass%, 20-90 mass%, 20-80 mass%, 20-70 mass%, 20-60 mass%, 20-50 mass%, 20-40 mass%, 25-98% by mass, 25-95% by mass, 25-90% by mass, 25-80% by mass, 25-70% by mass, 25-60% by mass, 25-50% by mass, 25-40% by mass, 30- 98% by mass, 30-95% by mass, 30-90% by mass, 30-80% by mass, 30-70% by mass, 30-60% by mass, 30-50% by mass, 30-40% by mass, 35-98 The content may be 35-95% by mass, 35-90% by mass, 35-80% by mass, 35-70% by mass, or 35-60% by mass, 35-50% by mass, or 35-40% by mass.

[0056] The glass raw materials may include glass raw materials other than waste glass. Examples of glass raw materials other than waste glass include known glass raw materials designed for the manufacture of glass fibers. Examples of glass compositions that glass raw materials other than waste glass can take include E-glass, high-strength, high-modulus glass, high-modulus, easily manufacturable glass, and low-dielectric constant, low-dielectric loss-tangent glass.

[0057] E glass may be a glass having a composition in which the SiO2 content is 52.0 to 56.0 mass%, the Al2O3 content is 12.0 to 16.0 mass%, the total MgO and CaO content is 20.0 to 25.0 mass%, and the B2O3 content is 5.0 to 10.0 mass%.

[0058] High-strength, high-modulus glass may be glass having a composition in which the SiO2 content is 60.0 to 70.0 mass%, the Al2O3 content is 20.0 to 30.0 mass%, the MgO content is 5.0 to 15.0 mass%, the Fe2O3 content is 0 to 1.5 mass%, and the total content of Na2O, K2O, and Li2O is 0 to 0.2 mass%.

[0059] High modulus easy-to-manufacture glass may be glass having a composition in which the SiO2 content is 57.0 to 60.0 mass%, the Al2O3 content is 17.5 to 20.0 mass%, the MgO content is 8.5 to 12.0 mass%, the CaO content is 10.0 to 13.0 mass%, and the B2O3 content is 0.5 to 1.5 mass%, and the total content of SiO2, Al2O3, MgO, and CaO is 98.0 mass or more.

[0060] Low dielectric constant low dielectric loss tangent glass may be a glass having a composition in which the SiO2 content is 48.0 to 62.0 mass%, the B2O3 content is 17.0 to 26.0 mass%, the Al2O3 content is 9.0 to 18.0 mass%, the CaO content is 0.1 to 9.0 mass%, the MgO content is 0 to 6.0 mass%, the total content of Na2O, K2O and Li2O is 0.05 to 0.5 mass%, the TiO2 content is 0 to 5.0 mass%, the SrO content is 0 to 6.0 mass%, the total content of F2 and Cl2 is 0 to 3.0 mass%, and the P2O5 content is 0 to 6.0 mass%.

[0061] Other glass raw materials besides waste glass can be silica sand, feldspar, clay, limestone, silica powder, dolomite, talc, clay, alumina, soda ash, or mixtures thereof.

[0062] As glass raw materials, multiple glass raw materials may be used in appropriate combinations to satisfy the composition of the glass composition described above.

[0063] The glass composition of this embodiment can be obtained by melting and solidifying glass raw materials. The melting conditions are not particularly limited. The melting temperature may be, for example, 1200°C to 1650°C. The solidification method is not particularly limited, and may be a method in which molten glass obtained by melting glass raw materials is molded into a predetermined shape and then solidified. For example, a block-shaped glass composition can be obtained by pouring molten glass onto a support and cooling it. Alternatively, a glass fibrous glass composition can be obtained, for example, by solidifying molten glass into a thread-like shape.

[0064] Glass fibers can be obtained by melting the glass composition of this embodiment, or the glass raw material for obtaining the glass composition of this embodiment, and spinning the molten material (molten glass). The spinning method is not particularly limited as long as it is a method commonly used by those skilled in the art. For example, glass fibers composed of glass monofilaments can be obtained by drawing the molten material (molten glass) in a melting furnace through a range of 1 to 30,000 nozzle tips of a platinum bushing controlled to a predetermined temperature, and then rapidly cooling it.

[0065] In the spinning process, a sizing agent may be applied to the glass monofilament. This results in glass fibers in which multiple glass monofilaments are bundled together. The sizing agent can be applied, for example, by providing an applicator between the nozzle tip and the winding device and supplying the sizing agent from the applicator. As a result, the glass fibers collected in the winding device are coated with the sizing agent, and glass fibers in which multiple glass monofilaments are bundled together are obtained on the tube of the winding device. Furthermore, by using a nozzle tip with a non-circular shape and having protrusions or notches for rapidly cooling the molten glass, and by controlling the temperature conditions, glass fibers composed of glass filaments with a flattened cross-sectional shape can be obtained.

[0066] The sizing agent may be, for example, a sizing agent comprising at least one selected from the group consisting of a silane coupling agent, a urethane resin, and an epoxy resin, or a sizing agent comprising a silane coupling agent and a urethane resin, or a sizing agent comprising a silane coupling agent, a urethane resin, and an epoxy resin. Furthermore, the glass fibers of this embodiment may be coated with a silane coupling agent and a urethane resin, for example, aminosilane and a urethane resin.

[0067] Examples of silane coupling agents include aminosilanes, chlorosilanes, epoxysilanes, mercaptosilanes, vinylsilanes, and acrylicsilanes. These silane coupling agents may be used individually or in combination of two or more. Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. Examples of chlorosilanes include γ-chloropropyltrimethoxysilane. Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Examples of mercaptosilanes include γ-mercaptotrimethoxysilane. Examples of vinylsilanes include vinyltrimethoxysilane and N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane. Examples of acrylicsilanes include γ-methacryloxypropyltrimethoxysilane.

[0068] Examples of urethane resins include polyether-based urethane resins and polyester-based urethane resins.

[0069] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, biphenyl type bifunctional epoxy resin, biphenyl-modified novolac type epoxy resin, naphthol-cresol cocondensation novolac type epoxy resin, naphthol-phenol cocondensation novolac type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenylethane type epoxy resin, naphthol novolac type epoxy resin, and the like.

[0070] The amount of sizing agent applied may be, for example, 0.03 parts by mass or more, or 2.0 parts by mass or less, per 100 parts by mass of glass fiber. In other words, the amount of sizing agent applied may be, for example, 0.03 to 2.0 parts by mass per 100 parts by mass of glass fiber.

[0071] In the glass composition of this embodiment, the melting temperature at which the viscosity becomes 1000 poise (also called the 1000 poise temperature) may be, for example, 1215°C or lower, and from the viewpoint of superior meltability, it may be 1210°C or lower, 1200°C or lower, 1180°C or lower, or 1170°C or lower. The lower limit of the 1000 poise temperature is not particularly limited, but may be, for example, 1100°C or higher, 1130°C or higher, or 1150°C or higher. That is, the 1000 poise temperature may be, for example, 1100°C to 1215°C, 1100°C to 1210°C, 1100°C to 1200°C, 1100°C to 1180°C, 1100°C to 1170°C, 1130°C to 1215°C, 1130°C to 1210°C, 1130°C to 1200°C, 1130°C to 1180°C, 1130°C to 1170°C, 1150°C to 1215°C, 1150°C to 1210°C, 1150°C to 1200°C, 1150°C to 1180°C, or 1150°C to 1170°C.

[0072] In this specification, the 1000 poise temperature is measured by the following method: Using a high-temperature electric furnace with a rotational viscometer (manufactured by Motoyama Co., Ltd.), the glass composition is melted in a platinum crucible, and the viscosity of the molten glass is continuously measured while changing the melting temperature using a rotational viscometer. The temperature at which the rotational viscosity reaches 1000 poise is defined as the 1000 poise temperature.

[0073] The liquidus temperature of the glass composition in this embodiment may be, for example, 1040°C or lower, and from the viewpoint of further suppressing crystal precipitation during spinning, it may be 1020°C or lower, 1000°C or lower, or 990°C or lower. The lower limit of the liquidus temperature is not particularly limited, but may be, for example, 900°C or higher, 930°C or higher, or 950°C or higher. That is, the liquidus temperature may be, for example, 900°C to 1040°C, 900°C to 1020°C, 900°C to 1000°C, 900°C to 990°C, 930°C to 1040°C, 930°C to 1020°C, 930°C to 1000°C, 930°C to 990°C, 950°C to 1040°C, 950°C to 1020°C, 950°C to 1000°C, or 950°C to 990°C.

[0074] In this specification, the liquidus temperature is measured by the following method. First, a lump of glass composition is crushed to obtain glass particles with a particle size of 0.5 to 1.5. 40 g of these glass particles are placed in a platinum boat measuring 180 × 20 × 15 mm and heated in a tubular electric furnace with a temperature gradient of 900 to 1300°C for more than 8 hours. After being removed from the tubular electric furnace, the material is observed with a polarizing microscope to identify the position where crystals derived from devitrified glass have begun to precipitate. Next, the temperature inside the tubular electric furnace is measured using a Type B thermocouple, and the temperature at the position where precipitation has begun is defined as the liquidus temperature.

[0075] In the glass composition of this embodiment, the difference between the 1000 poise temperature and the liquidus temperature (also called the working temperature range) may be, for example, 100°C or higher, and from the viewpoint of enabling stable spinning of glass fibers, it may be 120°C or higher, 150°C or higher, or 170°C or higher. Furthermore, the working temperature range of the glass composition of this embodiment may be, for example, 300°C or lower, or 250°C or lower. That is, the working temperature range may be, for example, 100°C to 300°C, 100°C to 250°C, 120°C to 300°C, 120°C to 250°C, 150°C to 300°C, 150°C to 250°C, 170°C to 300°C, or 170°C to 250°C.

[0076] (Glass fiber) The glass fibers of this embodiment are composed of the glass composition described above.

[0077] The glass fibers in this embodiment may be glass long fibers (also called glass fiber bundles or glass strands) obtained by melting and spinning a glass composition (or glass raw material for obtaining a glass composition), or they may be glass fiber material which is a cut or crushed product of said glass long fibers.

[0078] Long glass fibers are glass fibers that have a length of 1000m or more during the manufacturing process, and are composed of a single glass monofilament or multiple glass monofilaments bundled together. Such long glass fibers are prepared, for example, by a process called spinning, in which molten glass is flowed through a platinum nozzle called a bushing, stretched, and continuously formed into fibers, and then bundled as needed. Long glass fibers are clearly distinguished from short glass fibers such as glass wool, which are glass fibers prepared without spinning.

[0079] The fiber diameter of the glass monofilament in the glass fiber of this embodiment may be, for example, 3.0 μm or more, and may also be 4.0 μm or more, 5.0 μm or more, 6.0 μm or more, 7.0 μm or more, 8.0 μm or more, 9.0 μm or more, 10.0 μm or more, or 10.5 μm or more. Alternatively, the fiber diameter of the glass monofilament in the glass fiber of this embodiment may be, for example, 100.0 μm or less, and may also be 80.0 μm or less, 70.0 μm or less, 50.0 μm or less, 30 μm or less, 20 μm or less, or 16.0 μm or less. In other words, the fiber diameter of the glass monofilament in the glass fiber of this embodiment is, for example, 3.0~100.0μm, 3.0~80.0μm, 3.0~70.0μm, 3.0~50.0μm, 3.0~30μm, 3.0~20μm, 3.0~16.0μm, 4.0~100.0μm, 4.0~80.0μm, 4.0~70.0μm, 4.0~50.0μm, 4.0~30μm, 4.0~20μm, 4.0~1 6.0μm, 5.0~100.0μm, 5.0~80.0μm, 5.0~70.0μm, 5.0~50.0μm, 5.0~30μm, 5.0~20μm, 5.0~16.0μm, 6.0~100.0μm , 6.0~80.0μm, 6.0~70.0μm, 6.0~50.0μm, 6.0~30μm, 6.0~20μm, 6.0~16.0μm, 7.0~100.0μm, 7.0~80.0μm, 7.0~7 0.0μm, 7.0~50.0μm, 7.0~30μm, 7.0~20μm, 7.0~16.0μm, 8.0~100.0μm, 8.0~80.0μm, 8.0~70.0μm, 8.0~50.0μm, 8.0~30μm, 8.0~20μm, 8.0~16.0μm, 9.0~100.0μm, 9.0~80.0μm, 9.0~70.0μm, 9.0~50.0μm, 9.0~30μm, 9.0~20μm The particle size may be 9.0-16.0 μm, 10.0-100.0 μm, 10.0-80.0 μm, 10.0-70.0 μm, 10.0-50.0 μm, 10.0-30 μm, 10.0-20 μm, 10.0-16.0 μm, 10.5-100.0 μm, 10.5-80.0 μm, 10.5-70.0 μm, 10.5-50.0 μm, 10.5-30 μm, 10.5-20 μm, or 10.5-16.0 μm.

[0080] The glass fibers in this embodiment may be glass long fibers that have been appropriately processed, or glass fiber material obtained by cutting or crushing appropriately processed glass long fibers. The glass fibers in this embodiment may be, for example, roving, chopped strands, cut fibers, etc.

[0081] If the glass fibers are in the form of roving, the number of glass monofilaments that make up the roving (the number of bundled fibers) may be, for example, 10 to 30,000.

[0082] In this embodiment, if the glass fiber is a chopped strand, the number of glass monofilaments constituting it (number of bundled strands) may be, for example, one or more, 50 or more, 100 or more, or 200 or more. Also, in this embodiment, if the glass fiber is a chopped strand, the number of glass monofilaments constituting it (number of bundled strands) may be, for example, 20,000 or less, 10,000 or less, 9,000 or less, or 8,000 or less. That is, the number of bundled strands may be, for example, 1 to 20,000 strands, 1 to 10,000 strands, 1 to 9,000 strands, 1 to 8,000 strands, 50 to 20,000 strands, 50 to 10,000 strands, 50 to 9,000 strands, 50 to 8,000 strands, 100 to 20,000 strands, 100 to 10,000 strands, 100 to 9,000 strands, 100 to 8,000 strands, 200 to 20,000 strands, 200 to 10,000 strands, 200 to 9,000 strands, or 200 to 8,000 strands. If the glass fibers in this embodiment are chopped strands, their length may be, for example, 1.0 mm or more, 1.2 mm or more, 1.5 mm or more, 2.0 mm or more, or 2.3 mm or more. Furthermore, if the glass fiber in this embodiment is a chopped strand, its length may be, for example, 100.0 mm or less, 51.0 mm or less, 30.0 mm or less, 15.0 mm or less, or 7.8 mm or less. That is, the length of the chopped strand may be, for example, 1.0~100.0 mm, 1.0~51.0 mm, 1.0~30.0 mm, 1.0~15.0 mm, 1.0~7.8 mm, 1.2~100.0 mm, 1.2~51.0 mm, 1.2~30.0 mm, 1.2~15.0 mm, 1.2~7.8 mm, 1.5~100.0 mm, or 1.5~51.0 mm. mm, 1.5~30.0 mm, 1.5~15.0 mm, 1.5~7.8 mm, 2.0~100.0 mm, 2.0~51.0 mm, 2.0~30.0 mm, 2.0~15.0 mm, 2.0~7.8 mm, 2.3~100.0 mm, 2.3~51.0 mm, 2.3~30.0 mm, 2.3~15.0 mm, or 2.3~7.8 mm may be used.

[0083] If the glass fiber in this embodiment is a cut fiber, the number of glass monofilaments constituting it (number of bundled fibers) may be, for example, 1 to 20,000. The cut fiber may be crushed to a length of 0.001 to 0.900 mm by known methods such as a ball mill or a Henschil mixer.

[0084] The glass fibers in this embodiment may be coated with a sizing agent. Examples of sizing agents include those described above.

[0085] The amount of sizing agent applied may be, for example, 0.03 parts by mass or more, or 2.0 parts by mass or less, per 100 parts by mass of glass fiber. In other words, the amount of sizing agent applied may be, for example, 0.03 to 2.0 parts by mass per 100 parts by mass of glass fiber.

[0086] In the glass fiber of this embodiment, the tensile strength of the glass monofilament constituting the glass fiber at a tensile speed of 5 mm / min at 23°C may be, for example, 1.5 GPa or more, 2.0 GPa or more, 2.2 GPa or more, or 2.5 GPa or more. Furthermore, the above tensile strength may be, for example, 5.0 GPa or less, 4.0 GPa or less, 3.5 GPa or less, or 3.0 GPa or less. In other words, the above tensile strength may be, for example, 1.5~5.0 GPa, 1.5~4.0 GPa, 1.5~3.5 GPa, 1.5~3.0 GPa, 2.0~5.0 GPa, 2.0~4.0 GPa, 2.0~3.5 GPa, 2.0~3.0 GPa, 2.2~5.0 GPa, 2.2~4.0 GPa, 2.2~3.5 GPa, 2.2~3.0 GPa, 2.5~5.0 GPa, 2.5~4.0 GPa, 2.5~3.5 GPa, or 2.5~3.0 GPa.

[0087] In the glass fiber of this embodiment, the elastic modulus of the glass monofilament constituting the glass fiber may be, for example, 60.0 GPa or more, 63.0 GPa or more, 65.0 GPa or more, or 67.0 GPa or more. Furthermore, the above elastic modulus may be, for example, 100.0 GPa or less, 85.0 GPa or less, 80.0 GPa or less, or 75.0 GPa or less. In other words, the above modulus of elasticity may be, for example, 60.0~100.0 GPa, 60.0~85.0 GPa, 60.0~80.0 GPa, 60.0~75.0 GPa, 63.0~100.0 GPa, 63.0~85.0 GPa, 63.0~80.0 GPa, 63.0~75.0 GPa, 65.0~100.0 GPa, 65.0~85.0 GPa, 65.0~80.0 GPa, 65.0~75.0 GPa, 67.0~100.0 GPa, 67.0~85.0 GPa, 67.0~80.0 GPa, or 67.0~75.0 GPa.

[0088] In this specification, the tensile strength and modulus of the glass monofilament are those measured by the method described in the Examples.

[0089] When the glass fibers of this embodiment are included in a glass fiber reinforced resin composition, or when they are for use in a glass fiber reinforced resin composition, the glass fibers of this embodiment include one or more types of glass fibers obtained by the method described above from a glass raw material that includes waste glass in the market as all or part of the glass raw material, and one or more types of glass fibers obtained by the method described above from a glass raw material consisting of ore. Furthermore, the glass composition calculated by the method described above using the entire glass fiber obtained by heating the glass fiber reinforced resin composition in a muffle furnace at 300 to 650°C for about 0.5 to 24 hours to remove the resin may correspond to the glass composition of the glass fiber glass composition of this embodiment.

[0090] When the glass fibers of this embodiment are for use in a glass fiber reinforced resin composition and include one or more types of glass fibers obtained by the method described above from a glass raw material containing waste glass as all or part of the glass raw material, and one or more types of glass fibers obtained by the method described above from a glass raw material consisting of ore, the glass fibers of this embodiment may be in a form in which one or more types of glass fibers obtained by the method described above from a glass raw material containing waste glass as all or part of the glass raw material, and one or more types of glass fibers obtained by the method described above from a glass raw material consisting of ore are mixed in a single bag. Specifically, for example, the glass fibers of this embodiment may be in a form in which chopped strands, which are one or more types of glass fibers obtained by the method described above from a glass raw material containing waste glass as all or part of the glass raw material, and chopped strands, which are one or more types of glass fibers obtained by the method described above from a glass raw material consisting of ore are mixed in a single bag.

[0091] The glass fibers of this embodiment can be suitably used, for example, in applications such as glass fiber reinforced resin compositions.

[0092] The glass fibers of this embodiment are composed of the glass composition described above. Therefore, by using the glass fibers of this embodiment, it is possible to form a glass fiber reinforced resin composition in which hue change is sufficiently suppressed and which has excellent tensile strength and water resistance retention.

[0093] (Glass fiber reinforced resin composition) The glass fiber reinforced resin composition of this embodiment comprises the glass fibers and resin described above.

[0094] In this disclosure, glass fiber reinforced polymer (GFRP) means a mixture containing resin and glass fibers as a reinforcing material. Glass fiber reinforced polymer has higher mechanical strength (e.g., tensile strength) than resin alone due to the inclusion of glass fibers. Because glass fiber reinforced polymer is lightweight, has excellent strength and durability, and does not cause metal corrosion problems, it is used in a very wide range of fields, including parts for automobiles, railways, ships, housing equipment, sporting goods, electronic components, and housings for electronic devices.

[0095] In the glass fiber reinforced resin composition of this embodiment, any resin commonly used by those skilled in the art can be used without particular limitation. The resin may be a thermoplastic resin or a thermosetting resin, but from the viewpoint of the recyclability of the resin itself, a thermoplastic resin is preferred.

[0096] Thermoplastic resins include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, (meth)acrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polycarbonate. Examples include polyarylene sulfide, polyethersulfone (PES), polyphenylsulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyarylether ketone, 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, etc. (Meth)acrylic means acrylic or methacrylic.

[0097] Examples of the polyethylenes mentioned above include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.

[0098] Examples of the above-mentioned polypropylenes include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0099] Examples of the above-mentioned polystyrenes 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, which has a syndiotactic structure.

[0100] Examples of the (meth)acrylic resins mentioned above include polymers obtained by homopolymerizing one of the following: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl esters, or polymers obtained by copolymerizing two or more of these.

[0101] Examples of the polyvinyl chloride mentioned above include vinyl chloride homopolymers polymerized by conventionally known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization, copolymers of vinyl chloride monomer and copolymerizable monomers, and graft copolymers obtained by graft polymerization of vinyl chloride monomer onto a polymer.

[0102] The above polyamides include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polytetramethylene sebaamide (polyamide 410), polypentamethylene adipamide (polyamide 56), polypentamethylene sebaamide (polyamide 510), polyhexamethylene sebaamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene adipamide (polyamide 106), and polyde Camethylene sebamid (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polyundecaneamide (polyamide 11), polyundecamethylene adipamide (polyamide 116), polydodecaneamide (polyamide 12), polyxylene adipamide (polyamide XD6), polyxylene sebamid (polyamide XD10), polymetaxylylene adipamide (polyamide MXD6), polyparaxylylene adipamide (polyamide PXD6), polytetramethylene terephthalamide (Po Polyamide 4T), Polypentamethylene terephthalamide (Polyamide 5T), Polyhexamethylene terephthalamide (Polyamide 6T), Polyhexamethylene isophthalamide (Polyamide 6I), Polynonamethylene terephthalamide (Polyamide 9T), Polydecamethylene terephthalamide (Polyamide 10T), Polyundecamethylene terephthalamide (Polyamide 11T), Polydodecamethylene terephthalamide (Polyamide 12T), Polytetramethylene isophthalamide (Polyamide 4I), Poly Examples include copolymers or mixtures thereof, consisting of one or more components from among bis(3-methyl-4-aminohexyl)methaneterephthalamide (polyamide PACMT), polybis(3-methyl-4-aminohexyl)methaneisophthalamide (polyamide PACMI), polybis(3-methyl-4-aminohexyl)methanendodecamido (polyamide PACM12), polybis(3-methyl-4-aminohexyl)methanetetradecamide (polyamide PACM14), etc.

[0103] Examples of the above-mentioned polyacetals include homopolymers in which oxymethylene units are the main repeating units, and copolymers that mainly consist of oxymethylene units and contain oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0104] Examples of the polyethylene terephthalate mentioned above include polymers obtained by polycondensation of terephthalic acid or its derivatives with ethylene glycol.

[0105] Examples of the polybutylene terephthalate mentioned above include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,4-butanediol.

[0106] Examples of the above-mentioned polytrimethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,3-propanediol.

[0107] Examples of the polycarbonates mentioned above include polymers obtained by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate in a molten state, or polymers obtained by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

[0108] Examples of the above-mentioned polyarylene sulfides include linear polyphenylene sulfides, cross-linked polyphenylene sulfides with high molecular weight obtained by curing reactions after polymerization, polyphenylene sulfide sulfones, polyphenylene sulfide ethers, and polyphenylene sulfide ketones.

[0109] Examples of the above-mentioned 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, and polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene / acrylonitrile copolymer.

[0110] Examples of the polyaryl ether ketones mentioned above include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK).

[0111] Examples of the above-mentioned liquid crystal polymer (LCP) include (co)polymers consisting of one or more structural units selected from thermotropic liquid crystal polyesters such as aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, and aliphatic dicarbonyl units.

[0112] Examples of the above-mentioned fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluoroethylene propylene resin (FEP), fluoroethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0113] Examples of the ionomer (IO) resin mentioned above include polymers obtained by copolymerizing an olefin or styrene with an unsaturated carboxylic acid, in which some of the carboxyl groups are neutralized with metal ions.

[0114] Examples of the olefin / vinyl alcohol resins mentioned above include ethylene / vinyl alcohol copolymers, propylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymer saponifies, and propylene / vinyl acetate copolymer saponifies.

[0115] Examples of the above-mentioned cyclic olefin resins include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0116] Examples of the above-mentioned polylactic acid include poly-L-lactic acid, which is a homopolymer of the L-isomer; poly-D-lactic acid, which is a homopolymer of the D-isomer; or stereocomplex-type polylactic acid, which is a mixture thereof.

[0117] Examples of the cellulose resins mentioned above include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0118] Examples of the thermosetting resins mentioned above include unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic (PF) resins, urethane (PU) resins, polyisocyanates, polyisocyanurates, polyimide (PI), urea (UF) resins, silicone (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismalade triazine (BT) resins, diallyl phthalate (PDAP) resins, and the like.

[0119] The resins used in the glass fiber reinforced resin composition of this embodiment include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycarbonate, polyarylene sulfide, polyethersulfone (PES), and polyphenylsulfide. Examples include polyphenylene ether (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryl ether ketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate (PEN), ethylene / vinyl acetate (EVA) resin, ionomer (IO) resin, polybutadiene, styrene / butadiene resin, polybutylene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, polyvinyl alcohol (PVA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), and the like.The resin in the glass fiber reinforced resin composition of this embodiment may preferably be at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate, and polyphenylene sulfide, and more preferably at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate, and polyphenylene sulfide, with polybutylene terephthalate being a specific example.

[0120] The glass fiber content in the glass fiber reinforced resin composition of this embodiment may be, for example, 10.0% by mass or more, 15.0% by mass or more, 20.0% by mass or more, or 25.0% by mass or more, based on the total amount of the glass fiber reinforced resin composition, and may also be 50.0% by mass or less, 45.0% by mass or less, 40.0% by mass or less, or 35.0% by mass or less. In other words, the glass fiber content in the glass fiber reinforced resin composition of this embodiment may be, for example, 10.0 to 50.0% by mass, 10.0 to 45.0% by mass, 10.0 to 40.0% by mass, 10.0 to 35.0% by mass, 15.0 to 50.0% by mass, 15.0 to 45.0% by mass, 15.0 to 40.0% by mass, 15.0 to 35.0% by mass, 20.0 to 50.0% by mass, 20.0 to 45.0% by mass, 20.0 to 40.0% by mass, 20.0 to 35.0% by mass, 25.0 to 50.0% by mass, 25.0 to 45.0% by mass, 25.0 to 40.0% by mass, or 25.0 to 35.0% by mass, based on the total amount of the glass fiber reinforced resin composition.

[0121] In the glass fiber reinforced resin composition of this embodiment, the resin-to-glass fiber content ratio may be, on a mass basis, for example, 9.0:1.0 to 5.0:5.0, 8.5:1.5 to 5.5:4.5, 8.0:2.0 to 6.0:4.0, or 7.5:2.5 to 6.5:3.5.

[0122] The glass fiber reinforced resin composition of this embodiment can be obtained by mixing glass fibers and resin (mixing step). The mixing method in the mixing step is not particularly limited as long as it is a method that can mix glass fibers and resin, and can be carried out by a method that is normally practiced by those skilled in the art, for example, kneading, and kneading may be carried out using a twin-screw mixer, for example.

[0123] The glass fiber reinforced resin composition of this embodiment may further contain various additives in addition to glass fibers and resin. Examples of various additives include flame retardants, colorants, mold release agents, antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, plasticizers, fillers, and modifiers. These additives may be incorporated into the glass fiber reinforced resin composition by, for example, mixing them with the glass fibers and resin in a mixing process.

[0124] Examples of flame retardants include phosphorus-based flame retardants such as non-halogenated phosphate esters, halogenated phosphate esters, non-halogenated condensed phosphate esters, halogenated condensed phosphate esters, polyphosphates, and red phosphorus; brominated flame retardants such as TBA (tetrabromobisphenol A), DBDPO (decabromodiphenyl ether), OCTA (octabromodiphenyl oxide), and TBP (tribromophenol); and inorganic flame retardants such as aluminum hydroxide, antimony trioxide, tin oxide, tin hydroxide, molybdenum oxide, antimony pentoxide, and magnesium hydroxide.

[0125] Examples of coloring agents include titanium dioxide, zinc oxide, zinc sulfide, and carbon black.

[0126] Examples of release agents include magnesium stearate, talc stearate, metal soap, polyethylene wax, ethylenebisstearamide, EDA (ethylenediamine), EBA (ethylenebisstearamide), lithium stearate, and higher fatty acid metal salts.

[0127] Examples of antioxidants include phenolic antioxidants, amine antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

[0128] Examples of UV absorbers include salicylate-based UV absorbers, benzophenone-based UV absorbers, benzotriador-based UV absorbers, cyanoacrylate-based UV absorbers, nickel chelate-based UV absorbers, and hindered amine-based UV absorbers.

[0129] Examples of antistatic agents include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0130] Examples of nucleating agents include talc, dibenzylidenesorbitol, and β-crystal nucleating agents.

[0131] Examples of plasticizers include phthalate-based plasticizers (DOP (dioctyl phthalate), DBP (dibutyl phthalate), DHP (diheptyl phthalate), DIDP (diisodecyl phthalate), DINP (diisononyl phthalate)), fatty acid-based plasticizers, phosphate-based plasticizers (TCP (tricresyl phosphate), TMP (trimethyl phosphate), TEP (triethyl phosphate), etc.), adipic acid-based plasticizers (DOA (dioctyl adipate), DINA (diisononyl adipate), DIDA (diisodecyl adipate)), polyester-based plasticizers, epoxy-based plasticizers, and the like.

[0132] Examples of fillers include talc, mica, glass flakes, glass beads, and calcium carbonate.

[0133] Examples of modifiers include polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene copolymer, acrylonitrile-styrene-acrylic rubber copolymer, acrylonitrile-ethylene propylene rubber-styrene copolymer, methyl methacrylate-acrylic rubber copolymer, methyl methacrylate-acrylic rubber-styrene copolymer, methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate-(acrylic-silicone IPN rubber) copolymer, natural rubber, etc.

[0134] The glass fiber reinforced resin composition of this embodiment contains the aforementioned glass fibers. Therefore, the glass fiber reinforced resin composition of this embodiment exhibits sufficient suppression of hue change and has excellent tensile strength and water resistance.

[0135] The tensile strength of the glass fiber reinforced resin composition of this embodiment may be, for example, 120 MPa or more, or 125 MPa or more. The tensile strength of the glass fiber reinforced resin composition is measured by the method described in the example.

[0136] In the glass fiber reinforced resin composition of this embodiment, the tensile strength after a water resistance test, in which the material is held under saturated water vapor at 2 atmospheres and 121°C for 24 hours, may be, for example, greater than 35 MPa, greater than 40 MPa, greater than 45 MPa, or greater than 50 MPa. The tensile strength after the water resistance test is measured by the method described in the examples.

[0137] In the glass fiber reinforced resin composition of this embodiment, the strength retention rate after the water resistance test may be 30.0% or more, 35.0% or more, or 40.0% or more. The strength retention rate after the water resistance test represents the ratio of the tensile strength after the water resistance test to the tensile strength of the glass fiber reinforced resin composition described above.

[0138] (molded product) The molded article of this embodiment contains the glass fiber reinforced resin composition described above. The molded article of this embodiment may be a molded article made of the glass fiber reinforced resin composition, or it may be a molded article formed from the glass fiber reinforced resin composition.

[0139] The molded article of this embodiment can be obtained, for example, by molding a glass fiber reinforced resin composition (molding process).

[0140] The molding method in the molding process is not particularly limited and may be any known molding method such as injection compression molding, two-color molding, hollow molding, foam molding (including supercritical fluid foam molding), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, stamping molding, infusion, hand lay-up, spray-up, resin transfer molding, sheet molding compound, bulk molding compound, pultrusion, or filament winding. As a specific example of the molding process, a molded product can be obtained by injection molding using pellets of a glass fiber reinforced resin composition.

[0141] While preferred embodiments of this disclosure have been described above, this disclosure is not limited to the embodiments described above.

[0142] While preferred embodiments of this disclosure have been described above, this disclosure is not limited to the embodiments described above. [Examples]

[0143] Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples.

[0144] In the following Examples and Comparative Examples, the glass composition was measured as follows. First, glass fiber or recycled glass cullet is placed in a platinum crucible and held for 6 hours in an electric furnace at a temperature within the range of 1200 to 1650°C, at which the glass fiber or recycled glass cullet can be completely melted into molten glass without any residue, and the molten glass can flow out of the platinum crucible when the platinum crucible containing the molten glass is tilted upward by 60° from the horizontal direction relative to the opening plane; the molten glass is melted while being stirred, thereby obtaining homogeneous molten glass. Next, the obtained molten glass is poured onto a carbon plate to prepare glass cullet, which is then pulverized and powdered to obtain glass powder. For Li, which is a light element, the obtained glass powder is thermally decomposed with an acid, and then quantitatively analyzed using an ICP optical emission spectrometer. For other elements, after the glass powder is formed into a disk shape with a press machine, quantitative analysis is performed using a wavelength dispersive X-ray fluorescence spectrometer. The results of these quantitative analyses are converted to oxide equivalents, the content of each component and the total amount are calculated, and the glass composition is obtained from these numerical values.

[0145] <Preparation of Recycled Glass 1> Sheet glass for building materials collected as municipal waste was washed and pulverized to obtain cullet of recycled glass 1. The composition of the obtained recycled glass 1 is shown in Table 1.

[0146] <Preparation of Recycled Glass 2> Glass for solar panels collected as municipal waste was washed and pulverized to obtain glass cullet of recycled glass 2. The composition of the obtained recycled glass 2 is shown in Table 1.

[0147] <Preparation of E-Glass Batch> As glass raw materials, ore-derived glass raw materials were mixed so as to have the E-glass composition shown in Table 1, whereby an E-glass raw material batch was obtained.

[0148]

Table 1

[0149] <Example 1> A mixture of 50 parts by mass of recycled glass 1 and 50 parts by mass of glass raw material batch E was placed in a platinum crucible. The platinum crucible was held in an electric furnace at a temperature in the range of 1400 to 1550°C for 4 hours, and the glass raw material was melted while stirring to obtain homogeneous molten glass. The obtained molten glass was poured onto a carbon plate and cooled to obtain the glass composition as a solid glass cullet. The composition of the obtained glass composition is shown in Table 2.

[0150] <Example 2> A glass composition was obtained in the same manner as in Example 1, except that the amount of recycled glass 1 was changed to 40 parts by mass and the amount of glass raw material batch E was changed to 60 parts by mass. The composition of the obtained glass composition is shown in Table 2.

[0151] <Example 3> A glass composition was obtained in the same manner as in Example 1, except that the amount of recycled glass 1 was changed to 75 parts by mass and the amount of glass raw material batch E was changed to 25 parts by mass. The composition of the obtained glass composition is shown in Table 2.

[0152] <Example 4> A glass composition was obtained in the same manner as in Example 1, except that the amount of recycled glass 1 was changed to 85 parts by mass and the amount of glass raw material batch E was changed to 15 parts by mass. The composition of the obtained glass composition is shown in Table 2.

[0153] <Example 5> A glass composition was obtained in the same manner as in Example 1, except that 50 parts by mass of recycled glass 2 was used instead of recycled glass 1. The composition of the obtained glass composition is shown in Table 3.

[0154] <Example 6> A glass composition was obtained in the same manner as in Example 5, except that the amount of recycled glass 2 was changed to 40 parts by mass and the amount of glass raw material batch E was changed to 60 parts by mass. The composition of the obtained glass composition is shown in Table 3.

[0155] <Example 7> A glass composition was obtained in the same manner as in Example 5, except that the amount of recycled glass 2 was changed to 75 parts by mass and the amount of glass raw material batch E was changed to 25 parts by mass. The composition of the obtained glass composition is shown in Table 3.

[0156] <Example 8> A glass composition was obtained in the same manner as in Example 5, except that the amount of recycled glass 2 was changed to 25 parts by mass and the amount of glass raw material batch E was changed to 75 parts by mass. The composition of the obtained glass composition is shown in Table 3.

[0157] <Comparative Example 1> A glass composition was obtained in the same manner as in Example 5, except that the amount of recycled glass 2 was changed to 15 parts by mass and the amount of glass raw material batch E was changed to 85 parts by mass. The composition of the obtained glass composition is shown in Table 4.

[0158] <Comparative Example 2> A glass composition was obtained in the same manner as in Example 5, except that the amount of recycled glass 2 was changed to 98 parts by mass and the amount of glass raw material batch E was changed to 2 parts by mass. The composition of the obtained glass composition is shown in Table 4.

[0159] <Comparative Example 3> A glass composition was obtained in the same manner as in Example 5, except that the amount of recycled glass 2 was changed to 22 parts by mass and the amount of glass raw material batch E was changed to 78 parts by mass. The composition of the obtained glass composition is shown in Table 4.

[0160] <Comparative Example 4> A glass composition was obtained in the same manner as in Example 1, except that 35 parts by mass of recycled glass 1, 60 parts by mass of recycled glass 2, and 5 parts by mass of a batch of glass raw materials E were mixed. The composition of the obtained glass composition is shown in Table 4.

[0161] <Comparative Example 5> A glass composition was obtained in the same manner as in Example 1, except that 24 parts by mass of recycled glass 1, 74 parts by mass of E glass raw material batch, and 2 parts by mass of boron oxide were mixed. The composition of the obtained glass composition is shown in Table 4.

[0162] Using the glass compositions obtained in Examples 1-8 and Comparative Examples 1-5, the following procedures were performed: measurement of 1000 poise temperature, measurement of liquidus temperature, preparation of monofilaments, measurement of tensile strength of monofilaments, measurement of elastic modulus of monofilaments, preparation of glass fibers, preparation of glass fiber-reinforced resin compositions, measurement of tensile strength of glass fiber-reinforced resin compositions, and water resistance testing of glass fiber-reinforced resin compositions. In addition, the CO2 emission reduction rate, hue change evaluation, and acid resistance evaluation were performed using the following methods. The results are shown in Tables 2, 3, and 4.

[0163] (Measurement of 1000 poise temperature) The glass composition was melted in a platinum crucible, and the viscosity of the molten glass was continuously measured while varying the melting temperature using a high-temperature electric furnace equipped with a rotational viscometer (manufactured by Motoyama Co., Ltd.). The temperature at which the rotational viscosity reached 1000 poise was determined as the 1000 poise temperature.

[0164] (Measurement of liquid phase temperature) The bulk glass composition was crushed to obtain glass particles with a particle size of 0.5 to 1.5 mm. 40 g of the glass particles were placed in a platinum boat measuring 180 × 20 × 15 mm and heated for more than 8 hours in a tubular electric furnace with a temperature gradient of 900°C to 1300°C. After removal from the tubular electric furnace, the material was observed with a polarizing microscope to identify the location where crystals derived from devitrified glass began to precipitate. The temperature inside the tubular electric furnace was measured using a B thermocouple, and the temperature at the location where precipitation began was defined as the liquidus temperature.

[0165] (Monofilament fabrication) The glass composition was placed in a platinum container equipped with a nozzle tip at the bottom, and heated to 1000°C to 1200°C to melt the glass composition and obtain molten glass. Next, the molten glass was drawn out from the nozzle tip of the platinum container and wound onto a winding device. Then, monofilaments were taken one by one from between the nozzle tip and the winding device.

[0166] (Measurement of tensile strength of monofilament) A monofilament was bonded to a predetermined cardboard base 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 create a test specimen. Under a temperature of 23°C, the obtained test specimens were set in the grips of a tensile testing machine (manufactured by A&D Co., Ltd., product name: Single Column Tensile Testing Machine STB-1225S), the edges of the cardboard base were cut off, and a tensile test was performed at a crosshead speed of 5 mm / min, measuring the maximum load value at fracture. Test specimens that experienced fiber breakage or shedding during measurement were excluded. The tensile strength (GPa) of the monofilament at a tensile speed of 5 mm / min at 23°C was calculated by dividing the obtained maximum load value by the fiber cross-sectional area. The same measurement was performed on 30 monofilaments, and the two highest and two lowest values ​​were excluded from the obtained values. The numerical average of the remaining values ​​was calculated. This numerical average was used as the measured value of the monofilament's tensile strength. The fiber cross-sectional area of ​​the monofilament was determined using the following method. First, the fiber diameter of 10 monofilaments was measured by observing them with a scanning electron microscope (Hitachi High-Tech Corporation, product name: S-3400N). Next, the two largest and two smallest measurements were excluded from the obtained measurements, and the numerical average of the remaining measurements was calculated. This numerical average was taken as the average fiber diameter, and assuming a circular cross-sectional shape, the fiber cross-sectional area of ​​the monofilament was determined.

[0167] (Measurement of the elastic modulus of monofilament) A test specimen was prepared by bonding a monofilament to a predetermined cardboard base with a rectangular hole in the center, measuring 50 mm on the long side and 10 mm on the short side, such that the fiber length within the hole was 50 mm. This test specimen was set in the grips of a tensile testing machine (manufactured by A&D Co., Ltd., product name: Single Column Tensile Testing Machine STB-1225S), the edges of the cardboard base were trimmed, and a tensile test was performed at a crosshead speed of 5 mm / min. The modulus of elasticity (GPa) was calculated from the stress gradient for strains of 0.05 to 0.025%. Test specimens in which the thread came loose during measurement were excluded. Of the obtained values, the two highest and two lowest values ​​were excluded, and the numerical average of the remaining calculated values ​​was obtained. This numerical average was taken as the measured value of the monofilament modulus of elasticity.

[0168] (Production of glass fibers) The glass composition was placed in a platinum container equipped with 200 nozzle tips at the bottom, and heated to 1000°C to 1200°C to melt the glass composition and obtain molten glass. Next, the molten glass was drawn out from the nozzle tips of the platinum container and wound onto a winding device. Spinning was performed by rotating the winding device and winding the molten glass at a rotational speed of 1000 rpm. Additionally, using an applicator placed 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 monofilament at a ratio of 1.0 mass% relative to the monofilament, thereby obtaining glass long fibers with 200 bundled monofilaments and a number-average fiber diameter of 15 μm. The obtained glass long fibers were cut to 3 mm to obtain chopped strands.

[0169] (Preparation of glass fiber reinforced resin composition (molded product)) The chopped strands obtained above and polybutylene terephthalate resin (manufactured by Polyplastics Co., Ltd., product name: Duranex 2000) were mixed in a twin-screw mixer (manufactured by Shibaura Machine Co., Ltd., product name: TEM-26SS) at a screw rotation speed of 100 rpm to produce pellets (glass fiber reinforced resin composition pellets) with a glass content of 30.0% by mass. Using the obtained pellets, injection molding was performed 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 that are dumbbell test pieces in accordance with Japanese Industrial Standard (JIS) K 7161-1:2014.

[0170] (Measurement of tensile strength of glass fiber reinforced resin composition (molded product)) The molded product (dumbbell test piece) obtained as described above was subjected to a static tensile test in accordance with Japanese Industrial Standards (JIS) K7161-1, 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) was measured.

[0171] (Water resistance test of glass fiber reinforced resin composition (molded product)) The molded product (dumbbell test piece) obtained above was held in a saturated water vapor environment at 2 atmospheres and 121°C for 24 hours to obtain a test piece after the water resistance test. Next, a static tensile test was performed on the test piece after the water resistance test 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, in accordance with Japanese Industrial Standard (JIS) K7161-1, 2:2014, and the tensile strength (MPa) was measured. The tensile strength before and after the water resistance test was compared to determine the strength retention rate (%) after the water resistance test.

[0172] (Calculation of CO2 emission reduction rate) For each glass composition, we calculated a value corresponding to the volume-based emission intensity for No. 32, column code 62909 "Other Nonmetallic Minerals" in the "Input-Output Table-Based Emission Intensity" listed in the "Emission Intensity Database for Calculating Greenhouse Gas Emissions, etc., of Organizations Through the Supply Chain (Ver. 2.5)". We evaluated the values ​​corresponding to this emission intensity as follows: those in the range of 0 to 0.0070 were rated "A", those in the range of 0.0070 to 0.0085 were rated "B", and those rated 0.0085 or higher were rated "C".

[0173] (Evaluation of hue change) For the glass fiber reinforced molded products prepared as described above, the L*a*b* values ​​were evaluated using a spectrophotometer SE6000 manufactured by Nippon Denshoku Industries Ltd., and the coordinates in the L*a*b* color space were determined. Next, the color difference ΔE was calculated when compared with a glass fiber reinforced resin molded product made using glass fibers from non-recycled raw materials, and the cases 0 < ΔE ≤ 3 were evaluated as "A", 3 < ΔE ≤ 7 as "B", and 7 < ΔE as "C".

[0174] (Evaluation of acid resistance) A glass composition was placed in a platinum container equipped with a nozzle tip at the bottom, and heated to 1000°C to 1200°C to melt the glass composition and obtain molten glass. Next, the molten glass was drawn out from the nozzle tip of the platinum container and wound onto a winding device. The glass fibers wound onto the winding device were collected, and the obtained glass fibers were immersed in 10% sulfuric acid heated to 80°C for 2 hours, and the weight loss rate was measured. A weight loss rate of 2.5% or less was evaluated as "A", a weight loss rate between 2.5% and 10% was evaluated as "B", and a weight loss rate greater than 10% was evaluated as "C".

[0175] In Tables 2 to 4, B / (S+A+C) represents the value of the formula B / (S+A+C) when S (mass%) is the SiO2 content, A (mass%) is the Al2O3 content, C (mass%) is the CaO content, and B (mass%) is the B2O3 content.

[0176] [Table 2]

[0177] Table 3

[0178] Table 4

Claims

1. A glass composition for glass fibers, SiO ２ The content is 56.10 to 70.10% by mass, Al ２ O ３ The content is 2.10 to 12.20% by mass, The CaO content is 8.10 to 20.50% by mass. The MgO content is 0.50 to 5.00% by mass. B ２ O ３ The content is 0.60 to 7.20% by mass, Na ２ The O content is within the range where the total content of Na₂O and K₂O is between 4.10 and 12.85% by mass. F ２ The content is 0.01 to 1.00% by mass, Fe ２ O ３ the content of which is 0.01 to 1.00 mass%, K ２ The O content is 0 to 0.80% by mass. Li ２ The O content is 0 to 0.40% by mass. TiO ２ The content is 0.01 to 0.90% by mass, The ZnO content is 0 to 0.40% by mass. ZrO ２ The content is 0 to 0.40% by mass, P ２ O ５ The content is less than 0.10% by mass, B ２ O ３ Na content ２ Ratio of O content (Na ２ O / B ２ O ３ ) ranges from 0.81 to 8.10, Al ２ O ３ Na content ２ Ratio of O content (Na ２ O / Al ２ O ３ ) is between 0.30 and 4.00, Al ２ O ３ The ratio of MgO content to Al content (MgO / Al ２ O ３ ) is 0.16 to 1.44, SiO ２ The content of S (mass%), Al ２ O ３ The content of is A (mass%), the content of CaO is C (mass%), B ２ O ３ A glass composition for glass fibers that satisfies the following formula (1), where B (mass%) is the content of [substance]. 0.010≦B / (S+A+C)≦0.070...(1)

2. The ratio (Na ２ O / Al ２ O ３ The glass composition for glass fibers according to claim 1, wherein the ratio is 0.53 to 1.

38.

3. Glass fiber comprising the glass composition for glass fiber according to claim 1 or 2.

4. A glass fiber reinforced resin composition comprising the glass fibers described in claim 3 and a resin.

5. A molded article comprising the glass fiber reinforced resin composition described in claim 4.

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