Glass composition for glass fiber, glass fiber, glass fiber-reinforced resin composition, and molded article

Abstract

This glass composition for glass fiber contains: SiO2 at 51.90-62.20 mass%; Al2O3 at 14.50-20.90 mass%; CaO at 3.50-15.00 mass%; MgO at 4.50-11.40 mass%; B2O3 at 0.61-2.61 mass%; Na2O at 1.10-6.40 mass%; K2O at 0-3.00 mass%; Fe2O3 at 0.01-1.40 mass%; P2O5 at 0-2.00 mass%; Li2O at 0-0.94 mass%; and ZrO2 at 0-0.94 mass%. The combined content of Na2O and K2O is 1.10-9.40 mass%, the ratio of Na2O / B2O3 is 0.73-7.30, and the ratio of Al2O3 / B2O3 is 8.00-24.00.

Description

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

[0001] This disclosure relates to glass compositions for glass fibers, glass fibers, glass fiber reinforced resin compositions, and molded articles.

[0002] In recent years, there has been a strong demand in the industrial sector to reduce environmental impact and ensure sustainable production and consumption patterns. One initiative in the industrial sector to achieve these goals is recycling, which involves collecting products after they have been sold and used as final products and using them as raw materials to manufacture new final products. For example, Patent Document 1 describes a method for producing glass fibers from glass-containing industrial waste, industrial glass waste, etc.

[0003] One known application of glass fibers is glass fiber-reinforced resin compositions. For example, Patent Document 2 describes a flame-retardant polybutylene terephthalate resin composition containing polybutylene terephthalate resin and a fibrous inorganic compound.

[0004] Japanese Patent Publication No. 2000-511150, Japanese Patent Publication No. 2023-068401

[0005] Using discarded glass from the city results in CO2 emissions during manufacturing. ２ A reduction in emissions can be expected. However, using discarded glass from the market can lead to problems such as increased viscosity of the molten glass, a narrower working temperature range, poor spinnability, decreased elastic modulus of glass fibers, and reduced water resistance of glass fiber reinforced resin compositions.

[0006] This disclosure relates to CO2 production during glass fiber manufacturing. ２ The objective is to provide a glass composition for glass fibers that can reduce emissions, have good spinnability, form glass fibers with a high modulus of elasticity, and create a glass fiber reinforced resin composition with good 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.

[0007] The present disclosure relates to, for example, the following [1] to [5]. [1] SiO ２ has a content of 51.90 to 62.20 mass%, Al ２ O ３ has a content of 14.50 to 20.90 mass%, a CaO content of 3.50 to 15.00 mass%, an MgO content of 4.50 to 11.40 mass%, B ２ O ３ has a content of 0.61 to 2.61 mass%, Na ２ O has a content of 1.10 to 6.40 mass%, K ２ O has a content of 0 to 3.00 mass%, Fe ２ O ３ has a content of 0.01 to 1.40 mass%, P ２ O ５ has a content of 0 to 2.00 mass%, Li ２ O has a content of 0 to 0.94 mass%, ZrO ２ has a content of 0 to 0.94 mass%, the total content of Na ２ O and K ２ O is 1.10 to 9.40 mass%, the ratio of the Na ２ O ３ content to the B ２ O content (Na ２ O / B ２ O ３ ) is 0.73 to 7.30, the ratio of the Al ２ O ３ content to the B ２ O ３ content (Al ２ O ３ / B ２ O ３ ) is 8.00 to 24.00, which is a glass composition for glass fiber. [2] The ratio (Na ２ O / B ２ O ３ ) is 3.06 to 5.01, and the ratio (Al ２ O ３ / B ２ O ３[1] A glass composition for glass fibers, wherein the ratio is 8.64 to 20.51. [3] Glass fibers comprising the glass composition for glass fibers according to [1] or [2]. [4] A glass fiber reinforced resin composition comprising the glass fibers and resin according to [3]. [5] A molded article comprising the glass fiber reinforced resin composition according to [4].

[0008] According to this disclosure, CO2 during glass fiber manufacturing ２ A glass composition for glass fibers is provided that can reduce emissions, has good spinnability, can form glass fibers with a high modulus of elasticity, and can realize a glass fiber reinforced resin composition with good water resistance. Furthermore, according to this disclosure, 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 are provided.

[0009] Preferred embodiments of this disclosure are described in detail below.

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

[0011] The glass composition for glass fibers may be a glass composition that constitutes glass fibers, or it may be a glass raw material for manufacturing glass fibers. By melting and spinning the glass composition for glass fibers, glass fibers composed of the glass composition for glass fibers are obtained.

[0012] The glass composition of this embodiment has a specific composition described later, and therefore, CO2 is reduced during glass fiber production. ２ This invention achieves reduced emissions and a wider working temperature range due to the reduction in the 1000 poise temperature, resulting in excellent spinnability. Furthermore, because the glass composition of this embodiment has a specific composition described later, it is possible to form glass fibers with a high modulus of elasticity. Moreover, the glass composition of this embodiment makes it possible to realize a glass fiber reinforced resin composition with excellent strength retention after water resistance testing.

[0013] In the glass composition of this embodiment, SiO ２ The content is 51.90 to 62.20% by mass, Al ２ O３ The content of is 14.50 to 20.90 mass%, the content of CaO is 3.50 to 15.00 mass%, and the content of MgO is 4.50 to 11.40 mass%, B ２ O ３ The content is 0.61 to 2.61% by mass, and Na ２ The O content is 1.10 to 6.40% by mass, and K ２ The O content is 0 to 3.00 mass%, and Fe ２ O ３ The content is 0.01 to 1.40% by mass, P ２ O ５ The content is 0 to 2.00% by mass, Li ２ The O content is 0 to 0.94% by mass, and ZrO ２ The content is 0 to 0.94% by mass.

[0014] Furthermore, in the glass composition of this embodiment, Na ２ O and K ２ The total content of O is 1.10 to 9.40% by mass, and B ２ O ３ Na content ２ Ratio of O content (Na ２ O / B ２ O ３ ) is 0.73 to 7.30, B ２ O ３ Al content ２ O ３ Ratio of content (Al ２ O ３ / B ２ O ３ The range is 8.00 to 24.00.

[0015] Note that "the content of A is 0% by mass" means that A is not present, or the content of A is below the detection limit.

[0016] The composition of the glass composition is described in detail below.

[0017] SiO ２The content of SiO is 51.90% by mass or more on a total basis of the glass composition, and from the viewpoint of obtaining better mechanical properties by having a higher skeletal ratio of the network structure formed in the glass, it may be 52.50% by mass or more, 54.00% by mass or more, 54.60% by mass or more, 55.10% by mass or more, or 55.30% by mass or more. ２ The content of is 62.20% by mass or less on a total basis of the glass composition, and 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, it may be 60.40% by mass or less, 58.90% by mass or less, 57.90% by mass or less, 56.90% by mass or less, or 55.90% by mass or less.

[0018] Al ２ O ３ The content of Al may be 14.50% by mass or more on a total basis of the glass composition, and may be 15.10% by mass or more, 16.10% by mass or more, 17.10% by mass or more, or 17.50% by mass or more, from the viewpoint of obtaining better mechanical properties by having a higher skeletal ratio of the network structure formed in the glass, from the viewpoint of further improving durability when in contact with water or chemicals, and from the viewpoint of further suppressing crystallization and further lowering the liquidus temperature. ２ O ３ The content of is 20.90% by mass or less on a total basis of the glass composition, and may be 20.40% by mass or less, 19.90% by mass or less, 19.40% by mass or less, or 18.70% by mass or less, 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.

[0019] The CaO content is 3.50% by mass or more on a total basis of the glass composition, and may be 5.10% by mass or more, 6.10% by mass or more, 7.10% by mass or more, or 8.10% by mass or more, from the viewpoint of further improving the tensile strength and tensile modulus of the glass fibers and making it easier to obtain better mechanical properties for use in glass fiber reinforced resin compositions. In addition, the CaO content is 15.00% by mass or less on a total basis of the glass composition, CO ２From the perspective of further reducing emissions and being more effective in ensuring sustainable production and consumption patterns, the amount may be 14.40% by mass or less, 13.90% by mass or less, 12.90% by mass or less, 11.90% by mass or less, or 9.90% by mass or less.

[0020] The MgO content is 4.50% by mass or more on a total basis of the glass composition, and may be 5.60% by mass or more, 6.60% by mass or more, 7.60% by mass or more, 8.60% by mass or more, or 9.10% by mass or more, from the viewpoint of further reducing the melt viscosity and making it easier to stably and continuously fiberize over a long period of time. Alternatively, the MgO content is 11.40% by mass or less on a total basis of the glass composition, and may be 10.40% by mass or less, 9.80% by mass or less, or 9.40% by mass or less, from the viewpoint of further suppressing the formation of crystals with other components.

[0021] B ２ O ３ The content of is 0.61% by mass or more on a total basis of the glass composition, and may be 0.70% by mass or more, 0.80% by mass or more, 0.90% by mass or more, or 0.94% by mass or more, from the viewpoint of further reducing the melt viscosity and making it easier to stably and continuously fiberize over a long period of time. Also, B ２ O ３ The content of is 2.61% by mass or less on a total basis of the glass composition, and from the viewpoint of further suppressing the generation of volatile substances and scum when glass melts, it may be 2.30% by mass or less, 2.00% by mass or less, 1.90% by mass or less, 1.50% by mass or less, 1.40% by mass or less, 1.20% by mass or less, or 0.99% by mass or less.

[0022] Na ２ The O content is 1.10% by mass or more on a total basis of the glass composition, and may be 2.10% by mass or more, 3.10% by mass or more, 3.60% by mass or more, or 4.10% by mass or more, from the viewpoint of further reducing the melt viscosity and making it easier to stably and continuously fiberize over a long period of time. ２The content of O is 6.40% by mass or less based on the total amount of the glass composition. From the viewpoint of increasing the skeleton ratio of the network structure formed in the glass, obtaining better mechanical properties for use in glass fiber reinforced resin compositions, further improving durability when in contact with water or chemicals, and further suppressing erosion of furnace materials during production, it may be 5.90% by mass or less, 5.40% by mass or less, 4.90% by mass or less, or 4.40% by mass or less.

[0023] K ２ The content of O may be 0% by mass based on the total amount of the glass composition. From the viewpoint of further lowering the melt viscosity and facilitating stable continuous fiberization over a long period of time, it may be 0.01% by mass or more, 0.10% by mass or more, 0.20% by mass or more, or 0.25% by mass or more. Further, K ２ The content of O is 3.00% by mass or less based on the total amount of the glass composition. From the viewpoint of increasing the skeleton ratio of the network structure formed in the glass, obtaining better mechanical properties for use in glass fiber reinforced resin compositions, further improving durability when in contact with water or chemicals, and further suppressing erosion of furnace materials during production, it may be 1.90% by mass or less, 1.00% by mass or less, 0.70% by mass or less, 0.50% by mass or less, 0.40% by mass or less, or 0.35% by mass or less.

[0024] Fe ２ O ３ The content of is 0.01% by mass or more based on the total amount of the glass composition. From the viewpoint of further improving meltability and facilitating stable continuous fiberization over a long period of time, it may be 0.05% by mass or more, 0.09% by mass or more, 0.11% by mass or more, 0.13% by mass or more, or 0.14% by mass or more. Further, Fe ２ O ３ The content of is 1.40% by mass or less based on the total amount of the glass composition. From the viewpoint of further suppressing coloration of the glass, it may be 1.10% by mass or less, 0.80% by mass or less, 0.50% by mass or less, 0.30% by mass or less, or 0.20% by mass or less.

[0025] P ２ O ５The content of P is 2.00% by mass or less based on the total mass of the glass composition, and may be 1.90% by mass or less, 1.40% by mass or less, 1.00% by mass or less, 0.90% by mass or less, 0.50% by mass or less, 0.30% by mass or less, or 0.10% by mass or less. P ２ O ５ The content thereof may be 0% by mass.

[0026] Li ２ The content of O is 0.94% by mass or less based on the total mass of the glass composition. From the viewpoints of increasing the framework ratio of the network structure formed in glass, obtaining better mechanical properties for use in glass fiber-reinforced resin compositions, further improving durability when in contact with water or chemicals, and further suppressing erosion of furnace materials during production, the content may be 0.70% by mass or less, 0.50% by mass or less, 0.30% by mass or less, or 0.10% by mass or less. Li ２ The content of O may be 0% by mass.

[0027] ZrO ２ The content of is 0.94% by mass or less based on the total mass of the glass composition. From the viewpoints that lower melt viscosity and improved meltability facilitate obtaining uniform glass and enable stable continuous fiberization for a long time, the content may be 0.70% by mass or less, 0.50% by mass or less, 0.30% by mass or less, or 0.10% by mass or less. ZrO ２ The content of may be 0% by mass.

[0028] Examples of components that may be contained in the glass composition include TiO ２ , ZnO, Y ２ O ３ , ThO ２ , CuO, AgO, MnO, F ２ , SrO, BaO, etc., can also be mentioned.

[0029] TiO ２ The content of, based on the total mass of the glass composition, may be, for example, less than 1.00% by mass, and may also be less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass. TiO ２ The content of may be 0% by mass.

[0030] Cr ２ O ３ The content may be, for example, less than 1.00% by mass, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass, based on the total amount of the glass composition. Cr ２ O ３ The content may be 0% by mass.

[0031] The ZnO content may be, for example, less than 1.00% by mass on a total basis of the glass composition, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass. The ZnO content may also be 0% by mass.

[0032] Y ２ O ３ The content may be, for example, less than 1.00% by mass, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass, based on the total amount of the glass composition. ２ O ３ The content may be 0% by mass.

[0033] ThO ２ The content may be, for example, less than 1.00% by mass, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass, based on the total amount of the glass composition. ２ The content may be 0% by mass.

[0034] The CuO content may be, for example, less than 1.00% by mass, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass, based on the total amount of the glass composition. The CuO content may also be 0% by mass.

[0035] The AgO content may be, for example, less than 1.00% by mass on a total basis of the glass composition, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass. The AgO content may also be 0% by mass.

[0036] The MnO content may be, for example, less than 1.00% by mass on a total basis of the glass composition, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass. The MnO content may also be 0% by mass.

[0037] F ２ The content of may be, for example, less than 1.00% by mass, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass, based on the total amount of the glass composition. ２ The content may be 0% by mass.

[0038] Cl ２ The content may be, for example, less than 1.00% by mass, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass, based on the total amount of the glass composition. ２ The content may be 0% by mass.

[0039] The SrO content may be, for example, less than 1.00% by mass on a total basis of the glass composition, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass. The SrO content may also be 0% by mass.

[0040] The BaO content may be, for example, less than 1.00% by mass on a total basis of the glass composition, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass. The BaO content may also be 0% by mass.

[0041] The glass composition may further contain other components not listed above. Examples of other components include oxides of Co, Ni, Mo, W, Ce, La, Bi, Gd, Pr, Sc, Sn, Yb, or Sb. The total content of other components may be, for example, less than 3.00% by mass, less than 2.00% by mass, less than 1.00% by mass, less than 0.50% by mass, less than 0.30% by mass, less than 0.10% by mass, or less than 0.05% by mass, based on the total amount of the glass composition. In particular, the glass composition for glass fibers of this embodiment may contain impurities such as CoO, NiO, and MoO. ３ WO３ , SnO ２ , CEO ２ La ２ O ３ , Bi ２ O ３ , Gd ２ O ３ , Pr ２ O ３ , Sc ２ O ３ Yb ２ O ３、 or Sb ２ O ３ If these are included, their respective content percentages may be, for example, in the range of less than 0.40% by mass, less than 0.20% by mass, less than 0.10% by mass, less than 0.05% by mass, and less than 0.01% by mass.

[0042] In the glass composition of this embodiment, Na ２ O and K ２ The total O content is 1.10 to 9.40% by mass. ２ O is a component mainly derived from discarded glass in the city, and Na ２ O and K ２ By adjusting the composition of the glass composition so that the total O content falls within the above range, the above-mentioned excellent effects can be obtained while making full use of discarded glass from the market.

[0043] Na ２ O and K ２ The total O content is 1.10% by mass or more on a total basis of the glass composition, and CO ２ From the perspective of further improving the emission reduction rate, the amount may be 1.60% by mass or more, 2.10% by mass or more, 2.60% by mass or more, 3.10% by mass or more, 3.60% by mass or more, or 4.10% by mass or more. ２ O and K ２ The total O content is 9.40% by mass or less based on the total amount of the glass composition, and may be 8.40% by mass or less, 7.40% by mass or less, 6.40% by mass or less, 5.40% by mass or less, or 4.90% by mass or less, from the viewpoint of further improving the strength retention rate of the glass fiber reinforced resin composition after the water resistance test.

[0044] Note that Na ２ O content and K２ O content and Na ２ O and K ２ When the total content of O and Na are specified, ２ O content and K ２ The O content is within the specified numerical range, Na ２ O and K ２ The numerical range is selected from a range that satisfies the requirement for the total content of O.

[0045] In the glass composition of this embodiment, B ２ O ３ Na content ２ Ratio of O content (Na ２ O / B ２ O ３ ) is 0.73 to 7.30. Na ２ O is a component mainly derived from discarded glass in the city, and the ratio (Na ２ O / B ２ O ３ By adjusting the composition of the glass composition so that the above range is achieved, the above-mentioned excellent effects can be obtained while making full use of discarded glass from the city.

[0046] Ratio (Na ２ O / B ２ O ３ ) is 0.73 or higher, CO ２ From the viewpoint of further improving the emission reduction rate and ensuring sufficient melting properties, the ratio may be 1.60 or higher, 2.10 or higher, 3.06 or higher, 3.60 or higher, or 4.10 or higher. Also, the ratio (Na ２ O / B ２ O ３ ) is 7.30 or less, and from the viewpoint of further improving the strength retention rate of the glass fiber reinforced resin composition after the water resistance test, it may be 6.30 or less, 5.30 or less, 5.01 or less, or 4.70 or less.

[0047] Note that Na ２ O content and B ２ O ３ Content and ratio (Na ２ O / B ２ O ３ When ) and are defined respectively, Na ２ O content and B２ O ３ The content is within the specified numerical range, as a ratio (Na ２ O / B ２ O ３ It is selected from a range of numbers that can satisfy the requirements of ).

[0048] In the glass composition of this embodiment, B ２ O ３ Al content ２ O ３ Ratio of content (Al ２ O ３ / B ２ O ３ The ratio is 8.00 to 24.00. ２ O ３ / B ２ O ３ When the above range is maintained, it becomes possible to form glass fibers with a high modulus of elasticity, and the liquidus temperature is lowered, widening the difference between the liquidus temperature and the 1000 poise temperature, thus expanding the working temperature range and improving spinnability.

[0049] Ratio (Al ２ O ３ / B ２ O ３ The ratio (Al) is 8.00 or higher, and from the viewpoint of further improving the elastic modulus of the glass fiber, it may be 8.64 or higher, 9.60 or higher, 10.60 or higher, 11.60 or higher, 13.60 or higher, 14.60 or higher, 16.60 or higher, 17.60 or higher, or 18.10 or higher. ２ O ３ / B ２ O ３ The temperature is 24.00 or less, and from the viewpoint of lowering the liquidus temperature and further improving spinnability, it may be 21.00 or less, 20.51 or less, or 19.90 or less.

[0050] Al ２ O ３ Content and B ２ O ３ Content and ratio (Al ２ O ３ / B ２ O ３ When ) and are respectively defined, Al ２ O３ Content and B ２ O ３ The content is within the specified numerical range, as a ratio (Al ２ O ３ / B ２ O ３ It is selected from a range of numbers that can satisfy the requirements of ).

[0051] 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.

[0052] 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 discarded glass from the city and recycled glass fibers.

[0053] "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 use in the city, but also waste discarded after being manufactured and completed as a product without being used or distributed to the city. "Waste glass in the city" does not include waste glass generated in factories, etc., during the manufacturing process of glass or glass products. 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 is SiO2. ２ Al ２ O ３ and B ２ O ３The basic composition is CaO and MgO, at least one of BaO and SrO, and Na ２ O and K ２ It may be a glass made of a glass composition further comprising at least one of O.

[0054] 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.

[0055] Heating waste materials in the city to over 500°C can increase carbon dioxide emissions. Therefore, if waste glass collected from the city that does not undergo heating to over 500°C is used as a raw material for glass, the amount of carbon dioxide (CO2) emitted during the manufacturing of the glass composition may increase. ２ This can reduce the amount of waste generated and lessen the environmental burden.

[0056] For example, discarded glass in the city is SiO ２ The content is 65.00 to 72.50% by mass, Al ２ O ３ The content is 1.50 to 3.50% by mass, B ２ O ３ The content of is 0 to 3.00% by mass, the total content of CaO and MgO is 10.00 to 15.00% by mass, the total content of BaO and SrO is 0 to 3.40% by mass, and Na ２ O and K ２ The composition may have a total O content of 10.00 to 17.30% by mass.

[0057] Recovered glass fibers refer to glass fibers recovered from public waste containing glass fibers (for example, public waste containing 30% or more glass fibers by mass of the total amount) through a process of heating the public waste to 500°C or higher.

[0058] The recovered glass fibers are, for example, SiO ２ The content is 40.00 to 60.00% by mass, Al ２ O ３ The content of is 8.00 to 20.00 mass%, the CaO content is in the range of 15.00 to 30.00 mass%, and Na ２ O and K ２ The glass fiber may be made from a glass composition having a total oxygen content of 0.00 to 5.00% by mass.

[0059] The proportion of waste glass in the glass raw materials is not particularly limited and may be changed as appropriate to satisfy the composition of the glass composition described above. The proportion of waste glass in the glass raw materials may be, for example, 1% by mass or more, 5% by mass or more, 7% by mass or more, 9% by mass or more, 12% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more. A higher proportion of waste glass can reduce the energy required to vitrify the glass raw materials, and CO2 ２ Compositions with a higher reduction in emissions tend to be obtained. Furthermore, the proportion of waste glass in the glass raw materials may be, for example, 80% by mass or less, and may also be 70% by mass or less, 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less. When the proportion of waste glass is low, the water resistance and hue of the glass fiber reinforced resin composition tend to be further improved.

[0060] The proportion of waste glass in the glass raw materials is not particularly limited and may be changed as appropriate to satisfy the composition of the glass composition described above. The proportion of waste glass in the glass raw materials may be, for example, 1% by mass or more, 5% by mass or more, 7% by mass or more, 9% by mass or more, 12% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more. If the proportion of waste glass is high, CO ２ Compositions that further improve the reduction rate of emissions tend to be obtained. In addition, the proportion of waste glass in the glass raw materials may be, for example, 80% by mass or less, and may be 70% by mass or less, 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less. When the proportion of waste glass is low, the water resistance and hue of the glass fiber reinforced resin composition tend to improve further.

[0061] The glass raw materials may include glass raw materials other than waste glass. As glass raw materials other than waste glass, for example, known glass raw materials designed for the manufacture of glass fibers can be used. 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.

[0062] E glass is SiO ２ The content is 52.0 to 56.0% by mass, Al ２ O ３ The content of is 12.0 to 16.0% by mass, and the total content of MgO and CaO is 20.0 to 25.0% by mass, B ２ O ３ The glass may have a composition in which the content of is 5.0 to 10.0% by mass.

[0063] High-strength, high-modulus glass is made of SiO ２ The content is 60.0 to 70.0% by mass, Al ２ O ３ The content of is 20.0 to 30.0% by mass, the content of MgO is 5.0 to 15.0% by mass, Fe ２ O ３ The content is 0 to 1.5% by mass, Na ２ O, K ２ O and Li ２ The glass may have a composition in which the total oxygen content is 0 to 0.2% by mass.

[0064] High modulus of elasticity, easily manufactured glass, is SiO ２ The content is 57.0 to 60.0% by mass, Al ２ O ３ The content of is 17.5 to 20.0 mass%, the content of MgO is 8.5 to 12.0 mass%, the content of CaO is 10.0 to 13.0 mass%, B ２ O ３ The content of is 0.5 to 1.5% by mass, and SiO ２ Al ２ O ３ The glass may have a composition in which the total content of MgO and CaO is 98.0% by mass or more.

[0065] Low dielectric constant low dielectric loss tangent glass is SiO２ The content is 48.0 to 62.0% by mass, B ２ O ３ The content is 17.0 to 26.0% by mass, Al ２ O ３ The content of is 9.0 to 18.0% by mass, the content of CaO is 0.1 to 9.0% by mass, the content of MgO is 0 to 6.0% by mass, Na ２ O, K ２ O and Li ２ Total O content is 0.05 to 0.5 mass%, TiO ２ The content of is 0-5.0% by mass, the content of SrO is 0-6.0% by mass, F ２ and Cl ２ The total content is 0-3.0% by mass, P ２ O ５ The glass may have a composition in which the content of is 0 to 6.0% by mass.

[0066] Other glass raw materials besides waste glass can include silica sand, feldspar, clay, limestone, silica powder, dolomite, talc, alumina, soda ash, or mixtures thereof.

[0067] As glass raw materials, multiple glass raw materials may be used in appropriate combinations to satisfy the composition of the glass composition described above.

[0068] 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.

[0069] 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 number of nozzle tips ranging from 1 to 30,000 in a platinum bushing controlled to a predetermined temperature, and then rapidly cooling it.

[0070] 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 that has a non-circular shape and has 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. Examples of flattened cross-sectional shapes include oval (a shape in which the short side of a rectangle is replaced by a semicircle with the same diameter as the short side), ellipse, and rectangle. When the glass filament has a flattened cross-sectional shape, the major axis of the glass filament may be, for example, 15.0 to 50.0 μm, the minor axis of the glass filament may be, for example, 3.0 to 14.0 μm, and the ratio of the major axis to the minor axis (major axis / minor axis) may be, for example, 1.8 to 8.0.

[0071] 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.

[0072] 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 types. 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.

[0073] Examples of urethane resins include polyether-based urethane resins and polyester-based urethane resins.

[0074] 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.

[0075] 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.

[0076] 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, 1350°C or lower, and from the viewpoint of superior meltability, it may be 1295°C or lower, 1280°C or lower, 1270°C or lower, or 1260°C or lower. The lower limit of the 1000 poise temperature is not particularly limited, but may be, for example, 1180°C or higher, 1220°C or higher, or 1240°C or higher.

[0077] 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 using a rotational viscometer while changing the melting temperature. The temperature at which the rotational viscosity reaches 1000 poise is defined as the 1000 poise temperature.

[0078] The liquidus temperature of the glass composition in this embodiment may be, for example, 1220°C or lower, and from the viewpoint of further suppressing crystal precipitation during spinning, it may be 1200°C or lower, or 1180°C or lower. The lower limit of the liquidus temperature is not particularly limited, but may be, for example, 1100°C or higher, 1120°C or higher, or 1140°C or higher.

[0079] 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 mm. 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 8 hours or more. After removing the boat from the tubular electric furnace, it 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.

[0080] 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, 70°C or higher, and from the viewpoint of enabling more stable spinning of glass fibers, it may be 75°C or higher, 80°C or higher, or 85°C or higher. Furthermore, there is no particular upper limit to the working temperature range of the glass composition of this embodiment, but it may be, for example, 150°C or lower, or 120°C or lower.

[0081] (Glass Fibers) The glass fibers in this embodiment are made from the glass composition described above.

[0082] 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 materials obtained by further processing the glass long fibers in various ways. Examples of glass fiber materials include yarn, woven fabrics, knitted fabrics, nonwoven fabrics (including chopped strand mats and multiaxial nonwoven fabrics), chopped strands, roving, powder, and various other forms.

[0083] 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.

[0084] 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 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 be 80.0 μm or less, 70.0 μm or less, 50.0 μm or less, 30.0 μm or less, 20.0 μm or less, or 16.0 μm or less.

[0085] 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.

[0086] If the glass fiber is a roving, the number of glass monofilaments that make it up (the number of bundled fibers) may be, for example, 10 to 30,000.

[0087] If the glass fiber in this embodiment 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, if the glass fiber in this embodiment 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. If the glass fiber in this embodiment is a chopped strand, its 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. Also, 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.

[0088] 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 Henschl mixer.

[0089] The glass fibers in this embodiment may be coated with a sizing agent. Examples of sizing agents include those described above.

[0090] 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.

[0091] 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, 2.8 GPa or more, 2.9 GPa or more, 3.1 GPa or more, or 3.2 GPa or more. Furthermore, the upper limit of the above tensile strength is not particularly limited, but may be, for example, 4.5 GPa or less, 4.0 GPa or less, or 3.8 GPa or less.

[0092] In the glass fiber of this embodiment, the elastic modulus of the glass monofilament constituting the glass fiber may be, for example, 70 GPa or more, 72 GPa or more, 74 GPa or more, or 75 GPa or more. Furthermore, the upper limit of the elastic modulus is not particularly limited, but may be, for example, 90 GPa or less, 85 GPa or less, 82 GPa or less, or 79 GPa or less.

[0093] In this specification, the tensile strength and modulus of the glass monofilament are those measured by the method described in the Examples.

[0094] 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.

[0095] 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.

[0096] The glass fibers of this embodiment can be suitably used, for example, in applications such as glass fiber reinforced resin compositions.

[0097] The glass fibers of this embodiment are composed of the glass composition described above. Therefore, by using the glass fibers of this embodiment, CO2 emissions during manufacturing are reduced. ２ This method enables the formation of a glass fiber reinforced resin composition that reduces emissions and has good water resistance.

[0098] (Glass fiber reinforced resin composition) The glass fiber reinforced resin composition of this embodiment comprises the glass fibers and resin described above.

[0099] In this disclosure, glass fiber reinforced polymer (GFRP) means a mixture containing a resin and glass fibers as a reinforcing material. Glass fiber reinforced polymer compositions have higher mechanical strength (e.g., tensile strength) than resin alone due to the inclusion of glass fibers. Because glass fiber reinforced polymer compositions are lightweight, possess excellent strength and durability, and do not pose metal corrosion problems, they are used in a very wide range of fields, including parts for automobiles, railways, and ships, housing equipment, sporting goods, electronic components, and electronic equipment casings.

[0100] 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.

[0101] 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 of materials include polyaryl ethersulfide, polyethersulfone (PES), polyphenylsulfone (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, etc. (Meth)acrylic means acrylic or methacrylic.

[0102] Examples of the above-mentioned polyethylenes include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.

[0103] Examples of the above-mentioned polypropylenes include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0104] Examples of the above-mentioned polystyrenes include general-purpose polystyrene (GPPS), which is atactic polystyrene having an atactic structure; high-impact polystyrene (HIPS), which is GPPS with a rubber component added; and syndiotactic polystyrene having a syndiotactic structure.

[0105] 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.

[0106] 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.

[0107] 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), polyundecanamide (polyamide 11), polyundecamethylene adipamide (polyamide 116), polydodecanamide (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 PACCM12), polybis(3-methyl-4-aminohexyl)methanetetradecamide (polyamide PACCM14), etc.

[0108] 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.

[0109] Examples of the polyethylene terephthalate mentioned above include polymers obtained by polycondensation of terephthalic acid or its derivatives with ethylene glycol.

[0110] Examples of the polybutylene terephthalate mentioned above include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,4-butanediol.

[0111] Examples of the above-mentioned polytrimethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,3-propanediol.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] Examples of the above-mentioned polyaryl ether ketones include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK).

[0116] 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.

[0117] 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).

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] Examples of the cellulose resins mentioned above include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0123] 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, bismaleimidotriazine (BT) resins, diallyl phthalate (PDAP) resins, and the like.

[0124] 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, (meth)acrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycarbonate, polyarylene sulfide, polyethersulfone (PES), and polyphenyls. Examples include sulfone (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), etc. 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 a specific example may be polybutylene terephthalate.

[0125] 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 75.0% by mass or less, 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.

[0126] In the glass fiber reinforced resin composition of this embodiment, the content ratio of resin to glass fiber may be, on a mass basis, for example, 9.0:1.0 to 2.5:7.5, 8.5:1.5 to 5.0:5.0, 8.0:2.0 to 5.5:4.5, 7.5:2.5 to 6.0:4.0, or 7.5:2.5 to 6.5:3.5.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] Examples of coloring agents include titanium dioxide, zinc oxide, zinc sulfide, and carbon black.

[0131] Examples of release agents include magnesium stearate, stearic acid, talc, metal soap, polyethylene wax, ethylenebisstearamide, EDA (ethylenediamine), EBA (ethylenebisstearamide), lithium stearate, and higher fatty acid metal salts.

[0132] Examples of antioxidants include phenolic antioxidants, amine antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

[0133] Examples of UV absorbers include salicylate-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, cyanoacrylate-based UV absorbers, nickel chelate-based UV absorbers, and hindered amine-based UV absorbers.

[0134] Examples of antistatic agents include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0135] Examples of nucleating agents include talc, dibenzylidenesorbitol, and β-crystal nucleating agents.

[0136] 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.

[0137] Examples of fillers include talc, mica, glass flakes, glass beads, and calcium carbonate.

[0138] 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, and the like.

[0139] The glass fiber reinforced resin composition of this embodiment contains the glass fibers described above. Therefore, the glass fiber reinforced resin composition of this embodiment is CO2-free during manufacturing. ２ It can achieve reduced emissions while also providing good water resistance.

[0140] The tensile strength of the glass fiber reinforced resin composition of this embodiment may be, for example, 100 MPa or more, 110 MPa or more, or 113 MPa or more. Furthermore, there is no particular upper limit to the tensile strength of the glass fiber reinforced resin composition of this embodiment, but it may be, for example, 150 MPa or less, or 130 MPa or less.

[0141] The tensile strength of the glass fiber reinforced resin composition is measured by the method described in the examples.

[0142] 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, 40 MPa or more, 50 MPa or more, or 55 MPa or more.

[0143] The tensile strength after the water resistance test is measured by the method described in the examples.

[0144] In the glass fiber reinforced resin composition of this embodiment, the strength retention rate after the water resistance test may be, for example, 40% or more, 45% or more, or 50% or more.

[0145] 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.

[0146] (Molded article) 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 a molded article formed from the glass fiber reinforced resin composition.

[0147] The molded article of this embodiment can be obtained, for example, by molding a glass fiber reinforced resin composition (molding process).

[0148] 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.

[0149] While preferred embodiments of this disclosure have been described above, this disclosure is not limited to the embodiments described above.

[0150] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0151] In the following examples and comparative examples, the glass composition was measured as follows. First, glass fibers or waste glass cullet were placed in a platinum crucible and melted in an electric furnace at a temperature in the range of 1200 to 1650°C for 6 hours while stirring. This temperature ensured that the glass fibers or waste glass cullet were completely melted into molten glass, and that the molten glass could flow out of the platinum crucible when it was tilted 60° upward from a horizontal direction to the opening. Homogeneous molten glass was obtained by melting the glass fibers or waste glass cullet in an electric furnace at this temperature. Next, the obtained molten glass was poured onto a carbon plate to produce glass cullet, which was then crushed and powdered to obtain glass powder. For the light element Li, the obtained glass powder was heated and decomposed with acid, and then quantitatively analyzed using an ICP emission spectrometer. For the other elements, the glass powder was formed into a disc shape using a press, and then quantitatively analyzed using a wavelength-dispersive X-ray fluorescence spectrometer. These quantitative analysis results were converted to oxides to calculate the content and total amount of each component, and the glass composition was determined from these values.

[0152] <Preparation of waste glass from the city> Plate glass used for building materials, collected as waste from the city, was washed and crushed to obtain cullet of waste glass 1. The composition of the obtained waste glass 1 is shown in Table 1.

[0153] <Preparation of Recovered Glass Fibers> Recovered glass fiber reinforced resin composition, collected as waste from the city, was heated at 625°C to remove organic matter and obtain recovered glass fibers. The composition of the obtained recovered glass fibers is shown in Table 1.

[0154]

[0155] <Example 1> First, 30 parts by mass of waste glass and 70 parts by mass of mineral-derived glass raw material were mixed and the mineral-derived glass raw material was prepared so that the glass composition of the molten glass obtained when melted would be as shown in Table 2. Next, 30 parts by mass of waste glass and 70 parts by mass of mineral-derived glass raw material were mixed and 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 homogeneous molten glass was obtained by melting the glass raw material while stirring. The obtained molten glass was poured onto a carbon plate and cooled to obtain the glass composition as a block of glass cullet.

[0156] <Examples 2-8> Glass compositions were obtained in the same manner as in Example 1, except that the mixing ratio of waste glass and mineral-derived glass raw materials (for Examples 6 and 7, the mixing ratio of waste glass, recovered glass fibers, and mineral-derived glass raw materials) and the composition of the molten glass were changed as shown in Table 2 or Table 3. The mineral-derived glass raw materials were prepared for each example so that the composition of the molten glass was as shown in Table 2 or Table 3.

[0157] <Comparative Examples 1-4> Glass compositions were obtained in the same manner as in Example 1, except that the mixing ratio of waste glass and mineral-derived glass raw materials, and the composition of the molten glass were changed as shown in Table 4. The mineral-derived glass raw materials were prepared for each comparative example so that the composition of the molten glass was as shown in Table 4.

[0158]

[0159]

[0160]

[0161] Using the glass compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4, the glass compositions were evaluated, glass fibers were prepared and evaluated, and glass fiber reinforced resin compositions were prepared and evaluated using the following methods. The results are shown in Tables 5 to 7.

[0162] <Evaluation of Glass Composition> (1-1) 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 changing the melting temperature using a high-temperature electric furnace 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.

[0163] (1-2) Measurement of liquidus temperature The block-like glass composition was crushed to obtain glass particles with a particle size of 0.5 to 1.5 mm. 40 g of 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 being removed from the tubular electric furnace, the material was observed with a polarizing microscope to identify the position where crystals derived from devitrified glass began to precipitate. The temperature inside the tubular electric furnace was measured using a Type B thermocouple, and the temperature at the position where precipitation began was defined as the liquidus temperature.

[0164] (1-3) Calculation of the working temperature range The difference between the 1000 poise temperature and the liquid phase temperature was calculated as the working temperature range.

[0165] <Preparation and Evaluation of Glass Fibers> (2-1) Preparation of Monofilaments The glass composition was placed in a platinum container equipped with one nozzle tip at the bottom, and heated to 1100°C to 1400°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] (2-2) Measurement of tensile strength A monofilament was bonded to a predetermined cardboard base with a rectangular hole measuring 25 mm on the long side and 10 mm on the short side in the center, so that the fiber length within the hole was 25 mm, to create a test specimen. At a temperature of 23°C, the obtained test specimen was set in the grips of a tensile testing machine (manufactured by A&D Co., Ltd., product name: Single Column Type Tensile Testing Machine STB-1225S), the ends of the cardboard base were cut off, and a tensile test was performed at a crosshead speed of 5 mm / min, and the maximum load value at the time of fracture was measured. Test specimens in which threads came loose or broke 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 ​​obtained were excluded, and the numerical average of the remaining values ​​was calculated. This numerical average was taken as the measured value of the tensile strength of the monofilament. 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] (2-3) Measurement of Elastic Modulus A monofilament was bonded to a predetermined cardboard base with a rectangular hole measuring 50 mm on the long side and 10 mm on the short side in the center, so that the fiber length within the hole was 50 mm, to create a test specimen. 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 cut off, and a tensile test was performed at a crosshead speed of 5 mm / min. The elastic modulus (GPa) was calculated from the stress gradient for strains of 0.05 to 0.25%. 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 elastic modulus of the monofilament.

[0168] (2-4) Preparation of glass fiber bundles The glass composition was placed in a platinum container equipped with 200 nozzle tips at the bottom, and heated to 1100°C to 1400°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. The winding device was rotated, and spinning was performed by winding the molten glass at a rotation speed of 1000 rpm. Additionally, using an applicator provided between the nozzle tips and the winding device, a sizing agent containing aminosilane, urethane resin, and bisphenol A type epoxy resin was applied to the 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 and Evaluation of Glass Fiber Reinforced Resin Composition> (3-1) Preparation of Glass Fiber Reinforced Resin Composition (Molded Product) The chopped strands obtained above and polycarbonate resin (manufactured by Teijin Limited, product name: Panlite L-1250Y) were kneaded in a twin-screw kneader (manufactured by Shibaura Machinery 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 in an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., product name: NEX80) at a mold temperature of 110°C and an injection temperature of 300°C to produce molded products of the glass fiber reinforced resin composition, which are dumbbell test pieces in accordance with Japanese Industrial Standard (JIS) K 7161-1:2014.

[0170] (3-2) Measurement of the tensile strength of glass fiber reinforced resin composition (molded product) The dumbbell test specimens obtained above were subjected to a static tensile test in accordance with Japanese Industrial Standard (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] (3-3) Water resistance test of glass fiber reinforced resin composition (molded product) The 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. In Comparative Example 4, the test piece after the water resistance test did not maintain its shape, and therefore the tensile strength could not be measured.

[0172] (3-4) The tensile strength before the water resistance test (tensile strength measured in (3-2) above) and the tensile strength after the water resistance test (tensile strength obtained in (3-3) above) were compared to determine the retention rate (%) of the tensile strength after the water resistance test.

[0173] (3-5) CO ２ For each glass composition, we evaluated its emission reduction by determining the equivalent 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 Supply Chains (Ver. 2.5)". We evaluated the composition based on the value of this emission intensity, with those in the range of 0 to 0.0070 being rated "A", those in the range of 0.0070 to 0.0085 being rated "B", and those 0.0085 or higher being rated "C".

[0174]

[0175]

[0176]

Claims

1. SiO ２ has a content of 51.90 to 62.20% by mass, Al ２ O ３ has a content of 14.50 to 20.90% by mass, CaO has a content of 3.50 to 15.00% by mass, MgO has a content of 4.50 to 11.40% by mass, B ２ O ３ has a content of 0.61 to 2.61% by mass, Na ２ O has a content of 1.10 to 6.40% by mass, K ２ O has a content of 0 to 3.00% by mass, Fe ２ O ３ has a content of 0.01 to 1.40% by mass, P ２ O ５ has a content of 0 to 2.00% by mass, Li ２ O has a content of 0 to 0.94% by mass, ZrO ２ has a content of 0 to 0.94% by mass, the total content of Na ２ O and K ２ O is 1.10 to 9.40% by mass, the ratio of the content of Na ２ O ３ to the content of B ２ O (Na ２ O / B ２ O ３ ) is 0.73 to 7.30, the ratio of the content of Al ２ O ３ to the content of B ２ O ３ (Al ２ O ３ / B ２ O ３ ) is 8.00 to 24.00, which is a glass composition for glass fiber.

2. The ratio (Na ２ O / B ２ O ３ ) is 3.06 to 5.01, and the ratio (Al ２ O ３ / B ２ O ３ The glass composition for glass fibers according to claim 1, wherein the ratio is 8.64 to 20.

51.

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 and resin described in claim 3.

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

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