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

Abstract

SiO2 is 51.90-62.20% by mass, Al2O3 is 14.50-20.90% by mass, CaO is 3.50-15.00% by mass, MgO is 4.50-11.40% by mass, B2O3 is 0.61-2.61% by mass, Na2O is 1.10-6.40% by mass, K2O is 0-3.00% by mass, and Fe2O3 is 0.01-1.40% by mass. A glass composition for glass fibers, wherein the mass content is 0-2.00 mass% for P2O5, 0-0.94 mass% for Li2O, 0-0.94 mass% for ZrO2, 1.10-9.40 mass% for the total content of Na2O and K2O, the ratio (Na2O / B2O3) is 0.73-7.30, and the ratio (Al2O3 / B2O3) is 8.00-24.00.

Description

Technical Field

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

Background Art

[0002] In recent years, in the industrial world, there has been a strong demand for reducing environmental impact and ensuring sustainable production and consumption patterns. As one of the efforts in the industrial world to achieve these, recycling is cited, which involves collecting products after they have been sold and used as final products and manufacturing final products again using them as raw materials. For example, Patent Document 1 describes a method for manufacturing glass fibers from glass-containing industrial waste, industrial glass waste, etc.

[0003] As one of the uses of glass fibers, a glass fiber reinforced resin composition is 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 Documents

Patent Documents

[0004] [[ID=2​​​​​​​​​​​​​​​​​​​​ The present disclosure aims to provide a glass composition for glass fibers that can reduce CO2 emissions during glass fiber manufacturing, have good spinnability, form glass fibers with a high modulus of elasticity, and create a glass fiber reinforced resin composition with good water resistance. The present disclosure also 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 relates, for example, to the following [1] to [5]. [1] The SiO2 content is 51.90 to 62.20% by mass. The Al2O3 content is 14.50-20.90% by mass. The CaO content is 3.50 to 15.00% by mass. The MgO content is 4.50 to 11.40% by mass. The B2O3 content is 0.61 to 2.61% by mass. The Na2O content is 1.10 to 6.40% by mass. The K2O content is 0-3.00% by mass. The Fe2O3 content is 0.01 to 1.40% by mass. The P2O5 content is 0-2.00% by mass. The Li2O content is 0-0.94% by mass. The ZrO2 content is 0-0.94% by mass. The total content of Na2O and K2O is 1.10 to 9.40% by mass. The ratio of Na2O content to B2O3 content (Na2O / B2O3) is between 0.73 and 7.30. A glass composition for glass fibers, wherein the ratio of Al2O3 content to B2O3 content (Al2O3 / B2O3) is 8.00 to 24.00. [2] The ratio (Na2O / B2O3) is 3.06 to 5.01. The glass composition for glass fibers according to [1], wherein the ratio (Al2O3 / B2O3) is 8.64 to 20.51. [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 and resin described in [3]. [5] A molded article comprising the glass fiber reinforced resin composition described in [4]. [Effects of the Invention]

[0008] This disclosure provides a glass composition for glass fibers that can reduce CO2 emissions during glass fiber manufacturing, 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, this disclosure provides 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. [Modes for carrying out the invention]

[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] Since the glass composition of the present embodiment has a specific composition described below, it can reduce the CO₂ emissions during the production of glass fibers, and since the temperature at 1000 poises is reduced and the working temperature range is widened, it has excellent spinnability. Further, since the glass composition of the present embodiment has a specific composition described below, it can form glass fibers having a high elastic modulus. Furthermore, according to the glass composition of the present embodiment, a glass fiber reinforced resin composition excellent in the strength retention rate after a water resistance test can be realized.

[0013] In the glass composition of the present embodiment, the content of SiO₂ is 51.90 to 62.20% by mass, the content of Al₂O₃ is 14.50 to 20.90% by mass, the content of CaO is 3.50 to 15.00% by mass, the content of MgO is 4.50 to 11.40% by mass, the content of B₂O₃ is 0.61 to 2.61% by mass, the content of Na₂O is 1.10 to 6.40% by mass, the content of K₂O is 0 to 3.00% by mass, the content of Fe₂O₃ is 0.01 to 1.40% by mass, the content of P₂O₅ is 0 to 2.00% by mass, the content of Li₂O is 0 to 0.94% by mass, and the content of ZrO₂ is 0 to 0.94% by mass.

[0014] Also, in the glass composition of the present embodiment, the total content of Na₂O and K₂O is 1.10 to 9.40% by mass, the ratio of the content of Na₂O to the content of B₂O₃ (Na₂O / B₂O₃) is 0.73 to 7.30, and the ratio of the content of Al₂O₃ to the content of B₂O₃ (Al₂O₃ / B₂O₃) is 8.00 to 24.00.

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

[0016] Hereinafter, the composition of the glass composition will be described in detail.

[0017] The SiO2 content may be 51.90% by mass or more on a total basis of the glass composition, and from the viewpoint of obtaining better mechanical properties by achieving 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. Alternatively, the SiO2 content may be 62.20% by mass or less on a total basis of the glass composition, and from the viewpoint of achieving a lower 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] The Al2O3 content may be 14.50% by mass or more on a total basis of the glass composition, which results in a higher skeletal ratio of the network structure formed in the glass, leading to better mechanical properties, improved durability when in contact with water and chemicals, and further suppression of crystallization, resulting in a lower liquidus temperature. This 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. Alternatively, the Al2O3 content may be 20.90% by mass or less on a total basis of the glass composition, which results in a lower melt viscosity, easier formation of a uniform glass, and easier stably and continuously fiber formation over a long period of time. This 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.

[0019] The CaO content may be 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. Alternatively, the CaO content may be 15.00% by mass or less on a total basis of the glass composition, and 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, from the viewpoint of further suppressing CO2 emissions and being more effective in ensuring sustainable production and consumption patterns.

[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] The B2O3 content 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. Alternatively, the B2O3 content is 2.61% by mass or less on a total basis of the glass composition, and 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, from the viewpoint of further suppressing the generation of volatile substances and scum when glass melts.

[0022] The Na2O 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. Alternatively, the Na2O content is 6.40% by mass or less on a total basis of the glass composition, and 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, from the viewpoint of further increasing the skeletal ratio of the network structure formed in the glass, obtaining better mechanical properties for use as a glass fiber reinforced resin composition, further improving durability when in contact with water and chemicals, and further suppressing erosion of the furnace material during manufacturing.

[0023] The K2O content may be 0% by mass on a total basis of the glass composition, or 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, 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 K2O content may be 3.00% by mass or less on a total basis of the glass composition, or 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, from the viewpoint of further increasing the skeletal ratio of the network structure formed in the glass, obtaining better mechanical properties for use as a glass fiber reinforced resin composition, further improving durability when in contact with water and chemicals, and further suppressing erosion of the furnace material during manufacturing.

[0024] The Fe2O3 content is 0.01% by mass or more on a total basis of the glass composition, and 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, from the viewpoint of further improving meltability and facilitating stable and continuous fiber formation over a long period of time. In addition, the Fe2O3 content is 1.40% by mass or less on a total basis of the glass composition, and 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, from the viewpoint of further suppressing glass discoloration.

[0025] The P2O5 content is 2.00% by mass or less on a total basis 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. The P2O5 content may also be 0% by mass.

[0026] The Li2O content is 0.94% by mass or less on a total basis of the glass composition, but 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, from the viewpoint of increasing the skeletal ratio of the network structure formed in the glass, obtaining better mechanical properties for use as a glass fiber reinforced resin composition, further improving durability when in contact with water and chemicals, and further suppressing erosion of the furnace material during manufacturing. The Li2O content may also be 0% by mass.

[0027] The ZrO2 content is 0.94% by mass or less on a total basis of the glass composition. From the viewpoint of further reducing the melt viscosity and improving meltability, which makes it easier to obtain a uniform glass and to stably and continuously fiberize over a long period of time, it 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. The ZrO2 content may also be 0% by mass.

[0028] Examples of components that the glass composition may contain include TiO2, ZnO, Y2O3, ThO2, CuO, AgO, MnO, F2, SrO, and BaO.

[0029] The TiO2 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 TiO2 content may also be 0% by mass.

[0030] The Cr2O3 content may be, for example, less than 1.00% by mass of the total 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 Cr2O3 content may also be 0% by mass.

[0031] The ZnO content may be, for example, less than 1.00% by mass of the total 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] The Y2O3 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 Y2O3 content may also be 0% by mass.

[0033] The ThO2 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 ThO2 content may also be 0% by mass.

[0034] The CuO 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 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] The F2 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 F2 content may also be 0% by mass.

[0038] The Cl2 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 Cl2 content may also be 0% by mass.

[0039] The SrO content may be, for example, less than 1.00% by mass of the total 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, MoO3, WO3, SnO2, CeO2, La2O3, Bi2O3, Gd2O3, Pr2O3, Sc2O3, and Yb2O 3、 Alternatively, if Sb2O3 is included, its content may be independently in the range of, for example, less than 0.40% by mass, less than 0.20% by mass, less than 0.10% by mass, less than 0.05% by mass, or less than 0.01% by mass.

[0042] In the glass composition of this embodiment, the total content of Na2O and K2O is 1.10 to 9.40% by mass. Na2O is mainly derived from waste glass in the city, and by adjusting the composition of the glass composition so that the total content of Na2O and K2O falls within the above range, the above-mentioned excellent effects can be obtained while making full use of waste glass in the city.

[0043] The total content of Na2O and K2O is 1.10% by mass or more on a total basis of the glass composition, and 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, from the viewpoint of further improving the reduction rate of CO2 emissions. The total content of Na2O and K2O is 9.40% by mass or less on a total basis 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] When the content of Na2O, the content of K2O, and the total content of Na2O and K2O are specified, the content of Na2O and K2O are selected from the specified numerical ranges that satisfy the requirement for the total content of Na2O and K2O.

[0045] In the glass composition of this embodiment, the ratio of the Na2O content to the B2O3 content (Na2O / B2O3) is 0.73 to 7.30. Na2O is mainly derived from waste glass in the market, and by adjusting the composition of the glass composition so that the ratio (Na2O / B2O3) falls within the above range, the above-mentioned excellent effects can be obtained while making full use of waste glass in the market.

[0046] The ratio (Na2O / B2O3) is 0.73 or higher, and may be 1.60 or higher, 2.10 or higher, 3.06 or higher, 3.60 or higher, or 4.10 or higher, from the viewpoint of further improving the reduction rate of CO2 emissions and ensuring sufficient melting properties. Alternatively, the ratio (Na2O / B2O3) is 7.30 or lower, and may be 6.30 or lower, 5.30 or lower, 5.01 or lower, or 4.70 or lower, from the viewpoint of further improving the strength retention rate of the glass fiber reinforced resin composition after the water resistance test.

[0047] When the content of Na2O and the content and ratio (Na2O / B2O3) of B2O3 are specified, the content of Na2O and B2O3 are selected from the specified numerical range that satisfies the requirement for the ratio (Na2O / B2O3).

[0048] In the glass composition of this embodiment, the ratio of Al2O3 content to B2O3 content (Al2O3 / B2O3) is 8.00 to 24.00. Having the ratio (Al2O3 / B2O3) within this range enables the formation of glass fibers with a high modulus of elasticity. Furthermore, the lower liquidus temperature widens the difference between the liquidus temperature and the 1000 poise temperature, expanding the working temperature range and improving spinnability.

[0049] The ratio (Al2O3 / B2O3) is 8.00 or higher, and 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, from the viewpoint of further improving the elastic modulus of the glass fiber. Alternatively, the ratio (Al2O3 / B2O3) is 24.00 or lower, and may be 21.00 or lower, 20.51 or lower, or 19.90 or lower, from the viewpoint of lowering the liquidus temperature and further improving spinnability.

[0050] When the content of Al2O3 and the content and ratio (Al2O3 / B2O3) of B2O3 are specified, the content of Al2O3 and B2O3 are selected from the specified numerical range that satisfies the requirement for the ratio (Al2O3 / B2O3).

[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 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.

[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, 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.

[0056] 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%.

[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 may be glass fibers composed of a glass composition having, for example, an SiO2 content of 40.00 to 60.00 mass%, an Al2O3 content of 8.00 to 20.00 mass%, a CaO content in the range of 15.00 to 30.00 mass%, and a total content of Na2O and K2O of 0.00 to 5.00 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. When the proportion of waste glass is high, the energy required to vitrify the glass raw materials can be suppressed, and a composition with a higher CO2 emission reduction rate tends to be obtained. In addition, the proportion of waste glass in the glass raw materials may be, for example, 80% by mass or less, 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. A higher proportion of waste glass tends to result in a composition that further improves the reduction rate of CO2 emissions. In addition, the proportion of waste glass in the glass raw materials may be, for example, 80% by mass or less, 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. A lower proportion of waste glass tends to further improve the water resistance and hue of the glass fiber reinforced resin composition.

[0061] 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.

[0062] 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%.

[0063] 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%.

[0064] 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.

[0065] 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%.

[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 range of 1 to 30,000 nozzle tips of 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. 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 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.

[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 more than 8 hours. After being removed from the tubular electric furnace, the boat 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 fiber) The glass fibers of this embodiment are composed of 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 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, 30.0 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 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.

[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 Henschil 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 one 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 one 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, it is possible to reduce CO2 emissions during manufacturing and to form a glass fiber reinforced resin composition with 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. Glass fiber reinforced polymer compositions are lightweight, have excellent strength and durability, and do not cause metal corrosion problems, so they are 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.

[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 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.

[0102] 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.

[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 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.

[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), 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.

[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 polyethylene terephthalate 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 polyaryl ether ketones mentioned above 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 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 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, 9.0:1.0~2.5:7.5, 8.5:1.5~5.0:5.0, 8.0:2.0~5.5:4.5, 7.5:2.5~6.0:4.0, or 7.5:2.5~6.5:3.5.

[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, etc.

[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 can reduce CO2 emissions during manufacturing and achieve 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 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.

[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. [Examples]

[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 was maintained so that the glass fibers or waste glass cullet would melt completely into molten glass without any unmelted residue, and so that the molten glass could flow out of the platinum crucible when it was tilted 60° upward from a direction horizontal 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 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 discarded glass from the city> Plate glass used for building materials, collected as urban waste, was washed and crushed to obtain cullet of urban waste glass 1. The composition of the obtained urban waste glass 1 is shown in Table 1.

[0153] <Preparation of recovered glass fibers> A glass fiber reinforced resin composition collected as municipal waste 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] [Table 1]

[0155] <Example 1> First, 30 parts by mass of waste glass and 70 parts by mass of mineral-derived glass raw materials were mixed and the mineral-derived glass raw materials were 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 materials 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 materials 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] [Table 2]

[0159] [Table 3]

[0160] [Table 4]

[0161] Using the glass compositions obtained in Examples 1-8 and Comparative Examples 1-4, 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 5-7.

[0162] <Evaluation of glass compositions> (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 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.

[0163] (1-2) 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 boat 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 Type B thermocouple, and the temperature at the location 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) Fabrication of monofilament The glass composition was placed in a platinum container equipped with a 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 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] (2-3) Measurement of elastic modulus A monofilament was bonded to a predetermined cardboard base with a rectangular hole measuring 50 mm in length and 10 mm in width, so that the fiber length within the hole was 50 mm, to create a test specimen. This 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 0.25%. 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 monofilament's modulus of elasticity.

[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. 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 and evaluation of glass fiber reinforced resin compositions> (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 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 110°C and an injection temperature of 300°C to produce molded articles 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 as described above were subjected to static tensile testing 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 their tensile strength (MPa) was measured.

[0171] (3-3) Water resistance test of glass fiber reinforced resin composition (molded product) The dumbbell test specimens obtained above were held in a saturated water vapor environment at 2 atmospheres and 121°C for 24 hours to obtain specimens after the water resistance test. Next, the specimens after the water resistance test 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. In Comparative Example 4, the specimens after the water resistance test did not maintain their 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) Evaluation of CO2 emission reduction 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".

[0174] [Table 5]

[0175] [Table 6]

[0176] [Table 7]

Claims

1. SiO ２ The content is 51.90 to 62.20% by mass, Al ２ O ３ The content is 14.50 to 20.90% by mass, The CaO content is 3.50 to 13.10% by mass. The MgO content is 4.50 to 11.40% by mass. B ２ O ３ The content is 0.61 to 2.61% by mass. Na ２ The O content is 1.10 to 6.40% by mass. K ２ The O content is 0 to 3.00% by mass. Fe ２ O ３ The content of which 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. ZrO ２ The content is 0 to 0.94% by mass, Na ２ O and K ２ The total O content is 1.10 to 9.40% by mass. B ２ O ３ Na content ２ Ratio of O content (Na ２ O / B ２ O ３ ) ranges from 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 A glass composition for glass fibers, wherein the ratio is 8.00 to 24.

00.

2. The ratio (Na ２ O / B ２ O ３ ) ranged from 3.06 to 5.01, 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. The SiO₂ content is 51.90 to 62.20% by mass, The Al₂O₃ content is 14.50 to 20.90% by mass. The CaO content is 3.50 to 15.00% by mass. The MgO content is 4.50 to 11.40% by mass. The B2O3 content is 0.61 to 2.61% by mass. The Na₂O content is 1.10 to 6.40% by mass. The K₂O content is 0 to 3.00% by mass. The Fe₂O₃ content is 0.01 to 1.40% by mass. The P2O5 content is 0 to 2.00% by mass. The Li₂O content is 0 to 0.94% by mass. The ZrO₂ content is 0 to 0.94% by mass. The total content of Na₂O and K₂O is 1.10 to 9.40% by mass. The ratio of Na₂O content to B₂O₃ content (Na₂O / B₂O₃) is between 3.06 and 5.

01. A glass composition for glass fibers, wherein the ratio of Al₂O₃ content to B₂O₃ content (Al₂O₃ / B₂O₃) is 8.64 to 20.

51.

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

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

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

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