Glass composition for glass fiber and glass fiber

Abstract

Provided is a glass composition that can be produced by reducing the amount of CO2 emission, imparts water resistance to a glass fiber-reinforced resin molded product, and can suppress changes in hue. The glass composition contains, relative to the total amount, 57.75-64.25 mass% of SiO2, 3.51-11.80 mass% of Al2O3, 4.01-5.80 mass% of B2O3, 9.60-20.00 mass% of CaO, 0.55-1.94 mass% of MgO, 0.30-1.55 mass% of SrO, 0.32-1.65 mass% of BaO, 0.05-0.94 mass% of Fe2O3, 0.05-0.94 mass% of TiO2, 3.05-13.80 mass% of Na2O, 0.40-2.00 mass% of K2O, 0.01-0.94 mass% of ZrO2, and 0.05-0.94 mass% of F2. The total of CaO, MgO, SrO, and BaO is 12.40-21.45 mass%, and the total of Na2O and K2O is 3.50-15.80 mass%.

Description

Glass composition for glass fiber and glass fiber

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

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

[0003] In response to this demand, a method has been proposed in which long glass fibers are produced from glass raw materials including waste glass in the market, and the long glass fibers are used to produce a glass fiber reinforced resin composition or a glass fiber reinforced resin molded product (see, for example, Patent Document 1). ２ The patent application relates to a glass fiber reinforced resin composition containing long glass fibers obtained by melting and spinning a glass raw material containing more than 50% by mass of commercial waste glass, or a glass fiber material obtained by cutting or crushing the long glass fibers, which has excellent reduction efficiency and reinforcement efficiency for glass fiber reinforced resin molded products (see Patent Document 2).

[0004] The term "commercial waste glass" refers to glass recovered from commercial waste (e.g., waste containing 30% by mass or more of glass of undefined shape relative to the total amount) without undergoing a process of heating at 500°C or higher. Commercial waste includes not only waste discarded after use in the city, but also waste that has been manufactured and completed as a product but discarded without being used or distributed in the city. The commercial waste glass does not include waste glass generated in factories, etc. during the manufacturing process of glass or products using glass. Examples of the commercial waste glass include glass cullet recovered by crushing fluorescent tubes, glass cullet recovered by crushing automobile windshields, glass cullet recovered by crushing digital device screens, and glass cullet recovered by crushing glass bottles used as containers for beverages, etc. Such commercial waste glass is made of SiO ２ , Al ２ O ３ and B ２ O ３ The basic composition is at least one of CaO, MgO, BaO and SrO, and Na ２ O and K ２The glass may be made of a glass composition further containing at least one of O.

[0005] JP-T-2000-511150 A JP-A-2024-133149 A JP-A-2016-030787 A JP-A-2023-068401 A

[0006] However, it is known that glass fiber reinforced resin molded products generally do not have sufficient water resistance (see, for example, Patent Documents 3 and 4). Glass fiber reinforced resin molded products using long glass fibers produced from glass raw materials including waste glass in the market are prone to CO ２ Although it is excellent from the viewpoint of reduction efficiency and reinforcement efficiency of glass fiber reinforced resin molded products, it has the disadvantages of not being able to obtain sufficient water resistance strength and causing color changes.

[0007] The present invention overcomes these problems and ２ The object of the present invention is to provide a glass composition for glass fiber that can be produced while realizing a reduction in emissions, imparts water resistance strength to glass fiber reinforced resin molded products, and can suppress changes in the hue of the glass fiber reinforced resin molded products.

[0008] In order to achieve this object, the glass composition for glass fiber of the present invention contains SiO in the range of 57.75 to 64.25 mass % based on the total amount of the glass composition for glass fiber. ２ and Al in the range of 3.51 to 11.80 mass% ２ O ３ and B in the range of 4.01 to 5.80 mass% ２ O ３ %, CaO in the range of 9.60 to 20.00 wt.%, MgO in the range of 0.55 to 1.94 wt.%, SrO in the range of 0.30 to 1.55 wt.%, BaO in the range of 0.32 to 1.65 wt.%, and Fe in the range of 0.05 to 0.94 wt.%. ２ O ３ and TiO in the range of 0.05 to 0.94 mass %. ２ and Na in the range of 3.05 to 13.80 mass% ２ O and K in the range of 0.40 to 2.00 mass% ２ O and ZrO in the range of 0.01 to 0.94 mass % ２and F in the range of 0.05 to 0.94 mass%. ２ The total content of CaO, MgO, SrO and BaO is in the range of 12.40 to 21.45 mass %, and the Na ２ O and K ２ The total content of O is in the range of 3.50 to 15.80 mass %.

[0009] According to the glass composition for glass fiber of the present invention, CO ２ It is possible to manufacture glass fiber reinforced resin molded products while realizing a reduction in emissions, and it is possible to impart water resistance strength to glass fiber reinforced resin molded products and suppress color changes in the glass fiber reinforced resin molded products.

[0010] The glass composition for glass fiber of the present invention is ２ The ratio of the content of SrO to the content of SrO (SrO / F ２ ) is preferably in the range of 0.50 to 12.50, and the ratio of the B to the SrO content is preferably ２ O ３ The ratio of the content of (B ２ O ３ / SrO) is preferably in the range of 2.51 to 24.40.

[0011] The glass fiber of the present invention is characterized by comprising the glass composition for glass fiber of the present invention.

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

[0013] The glass composition for glass fiber of this embodiment contains SiO in the range of 57.75 to 64.25 mass % based on the total amount of the glass composition for glass fiber. ２ and Al in the range of 3.51 to 11.80 mass% ２ O ３ and B in the range of 4.01 to 5.80 mass% ２ O ３ %, CaO in the range of 9.60 to 20.00 wt.%, MgO in the range of 0.55 to 1.94 wt.%, SrO in the range of 0.30 to 1.55 wt.%, BaO in the range of 0.32 to 1.65 wt.%, and Fe in the range of 0.05 to 0.94 wt.%. ２ O ３and TiO in the range of 0.05 to 0.94 mass %. ２ and Na in the range of 3.05 to 13.80 mass% ２ O and K in the range of 0.40 to 2.00 mass% ２ O and ZrO in the range of 0.01 to 0.94 mass % ２ and F in the range of 0.05 to 0.94 mass%. ２ The total content of CaO, MgO, SrO and BaO is in the range of 12.40 to 21.45 mass %, and the Na ２ O and K ２ The total content of O is in the range of 3.50 to 15.80 mass %.

[0014] In the glass composition for glass fiber of this embodiment, SiO ２ If the content of SiO is less than 57.75 mass%, the skeleton ratio of the network structure formed in the glass will be low, and sufficient mechanical properties will not be obtained. ２ If the content exceeds 64.25 mass %, the melt viscosity becomes high and the meltability decreases, making it difficult to obtain a uniform glass and to fiberize it stably and continuously for a long period of time.

[0015] SiO relative to the total amount of the glass composition for glass fiber of this embodiment ２ The content of CO ２ The range of 57.75 to 63.50 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 58.51 to 62.90 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A range of 58.55 to 61.00 mass % is more preferable because it provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0016] In addition, in the glass composition for glass fiber of this embodiment, Al ２ O ３If the content of Al is less than 3.51% by mass, the skeleton ratio of the network structure formed in the glass will be low, and sufficient mechanical properties will not be obtained, and durability when in contact with water or chemicals will decrease. In addition, the effect of suppressing crystallization will decrease, and the liquidus temperature will increase, making fiberization difficult. On the other hand, if the content of Al is less than 3.51% by mass, the skeleton ratio of the network structure formed in the glass will be low, and sufficient mechanical properties will not be obtained, and durability when in contact with water or chemicals will decrease. In addition, the effect of suppressing crystallization will decrease, and the liquidus temperature will increase, making fiberization difficult. ２ O ３ If the content exceeds 11.80 mass %, the melt viscosity becomes high and the meltability decreases, making it difficult to obtain a uniform glass and to fiberize it stably and continuously for a long period of time.

[0017] The amount of Al relative to the total amount of the glass composition for glass fiber of this embodiment ２ O ３ The content of CO ２ The range of 3.55 to 10.00 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 4.20 to 9.94 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A more preferable range is 6.35 to 9.50% by mass, since this provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0018] In addition, in the glass composition for glass fiber of this embodiment, B ２ O ３ If the content of B is less than 4.01% by mass, the melt viscosity increases, making it difficult to stably and continuously form fibers for a long period of time. ２ O ３ If the content exceeds 5.80% by mass, the generation of volatile matter and scum increases during glass melting, making it difficult to fiberize the glass stably and continuously for a long period of time.

[0019] B relative to the total amount of the glass composition for glass fiber of this embodiment ２ O ３ The content of CO ２ The range of 4.05 to 5.45 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２The range of 4.25 to 5.40 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A more preferable range is 4.70 to 5.30 mass % because this provides an excellent reduction rate in emissions, an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and little change in color of the glass fiber reinforced resin molded product.

[0020] In addition, in the glass composition for glass fiber of this embodiment, if the CaO content is less than 9.60 mass % relative to the total amount, the tensile strength and tensile modulus of the glass fiber will decrease, making it difficult to satisfy sufficient mechanical properties for composite material applications. ２ Emissions will increase, making it difficult to ensure sustainable production and consumption patterns.

[0021] The content of CaO relative to the total amount of the glass composition for glass fiber of this embodiment is ２ The range of 9.61 to 17.65 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 10.40 to 17.00 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A more preferable range is 13.10 to 16.60 mass % because this provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

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

[0023] The content of MgO relative to the total amount of the glass composition for glass fiber of this embodiment is preferably in the range of 0.60 to 0.94 mass%, more preferably in the range of 0.72 to 0.86 mass%, and ２The range of 0.73 to 0.83 mass% is more preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 0.74 to 0.82 mass % is particularly preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ The most preferred range is 0.78 to 0.82 mass % because this provides an excellent reduction rate in emissions, an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and little change in color of the glass fiber reinforced resin molded product.

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

[0025] The content of SrO relative to the total amount of the glass composition for glass fiber of this embodiment is ２ The range of 0.60 to 1.50 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 0.65 to 1.35 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A more preferable range is 0.66 to 1.05% by mass, because this provides an excellent reduction rate in emissions, an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and little change in color of the glass fiber reinforced resin molded product.

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

[0027] The content of BaO relative to the total amount of the glass composition for glass fiber of this embodiment is ２The range of 0.60 to 1.60 mass % is preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 0.65 to 1.40 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A more preferable range is 0.70 to 1.10% by mass, since this provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0028] In addition, in the glass composition for glass fiber of this embodiment, Fe ２ O ３ If the content of Fe is less than 0.05% by mass, the melting property is reduced, making it difficult to continuously and stably form fibers for a long period of time, and the cost of removing impurities is increased, which becomes a factor that puts pressure on the production cost. ２ O ３ If the content exceeds 0.94% by mass, coloring of the glass increases, and problems tend to occur when the glass is applied to a composite material.

[0029] Fe relative to the total amount of the glass composition for glass fiber of this embodiment ２ O ３ The content is preferably in the range of 0.10 to 0.44 mass%, more preferably in the range of 0.15 to 0.30 mass%.

[0030] In addition, in the glass composition for glass fiber of this embodiment, TiO ２ If the content of TiO is less than 0.05 mass%, the cost of removing impurities increases, which becomes a factor that puts pressure on the production cost. ２ If the content exceeds 0.94% by mass, the high-temperature viscosity of the glass increases, the melting property tends to deteriorate, and the glass tends to be easily colored, which tends to cause problems when applied to a composite material.

[0031] TiO relative to the total amount of the glass composition for glass fiber of this embodiment ２ The content of CO is preferably in the range of 0.10 to 0.44 mass%, more preferably in the range of 0.22 to 0.36 mass%, ２The range of 0.23 to 0.33 mass % is more preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 0.24 to 0.32 mass % is particularly preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ The most preferred range is 0.28 to 0.32 mass % because this provides an excellent reduction rate in emissions, an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and little change in color of the glass fiber reinforced resin molded product.

[0032] In addition, in the glass composition for glass fiber of this embodiment, Na ２ If the O content is less than 3.05 mass %, the melt viscosity increases and the meltability decreases, making it difficult to obtain a uniform glass and to perform continuous fiberization stably for a long period of time. ２ If the O content exceeds 13.80% by mass, the skeleton ratio of the network structure formed in the glass will be low, which will result in reduced mechanical properties and durability when in contact with water or chemicals, and will also increase corrosion of the furnace materials, shortening the life of the melting furnace.

[0033] The amount of Na relative to the total amount of the glass composition for glass fiber of this embodiment ２ The content of O is ２ The range is preferably 5.20 to 13.00 mass %, more preferably 5.60 to 12.00 mass %, because this provides an excellent reduction rate in CO emissions. ２ A more preferable range is 6.00 to 9.50% by mass, since this provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0034] In addition, in the glass composition for glass fiber of this embodiment, K ２ If the O content is less than 0.40 mass %, the melt viscosity increases and the meltability decreases, making it difficult to obtain a uniform glass and to stably and continuously fiberize the glass for a long period of time. ２If the O content exceeds 2.00% by mass, the skeleton ratio of the network structure formed in the glass will be low, which will result in reduced mechanical properties and durability when in contact with water or chemicals, and will also increase corrosion of the furnace materials, shortening the life of the melting furnace.

[0035] K relative to the total amount of the glass composition for glass fiber of this embodiment ２ The content of O is ２ The range of 0.75 to 1.90 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 0.80 to 1.75 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A more preferable range is 0.85 to 1.35% by mass, since this provides an excellent reduction rate in emissions, an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and little change in color of the glass fiber reinforced resin molded product.

[0036] In addition, in the glass composition for glass fiber of the present embodiment, ZrO ２ If the content of ZrO is less than 0.01 mass%, the cost of removing impurities will increase, which will put pressure on the production cost. ２ If the content exceeds 0.94 mass %, the melt viscosity increases and the meltability decreases, making it difficult to obtain a uniform glass and to fiberize it stably and continuously for a long period of time.

[0037] ZrO relative to the total amount of the glass composition for glass fiber of this embodiment ２ The content of CO is preferably in the range of 0.05 to 0.44 mass%, more preferably in the range of 0.06 to 0.28 mass%, ２ The range of 0.10 to 0.26 mass % is more preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 0.11 to 0.24 mass % is particularly preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２The most preferred range is 0.12 to 0.19% by mass, as this provides an excellent reduction rate in emissions, an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and little change in color of the glass fiber reinforced resin molded product.

[0038] In addition, in the glass composition for glass fiber of this embodiment, F ２ If the amount of F is less than 0.05% by mass, the amount of bubbles increases, making it difficult to stably form fibers for a long period of time. ２ If the content exceeds 0.94 mass %, the viscosity of the molten glass decreases significantly, making it difficult to fiberize the glass stably for a long period of time.

[0039] F relative to the total amount of the glass composition for glass fiber of this embodiment ２ The content of CO is preferably in the range of 0.06 to 0.66 mass %. ２ The range of 0.10 to 0.54 mass % is more preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 0.16 to 0.50 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ The most preferred range is 0.30 to 0.49 mass % because this provides an excellent reduction rate in emissions, an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and little change in color of the glass fiber reinforced resin molded product.

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

[0041] The total content of CaO, MgO, SrO and BaO relative to the total amount of the glass composition for glass fiber of this embodiment is ２ The range of 13.00 to 19.60 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２The range of 13.95 to 19.00 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A range of 16.10 to 18.80 mass % is more preferable because it provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0042] In addition, in the glass composition for glass fiber of the present embodiment, the Na ２ O and K ２ If the total content of O is less than 3.50% by mass, the melt viscosity increases, making it difficult to stably and continuously form fibers. ２ O and K ２ If the total content of O exceeds 15.80 mass %, corrosion of the melting furnace material increases, shortening the life of the melting furnace.

[0043] The amount of the Na relative to the total amount of the glass composition for glass fiber of this embodiment ２ O and K ２ The total content of O is CO ２ The range of 7.01 to 15.00 mass% is preferable because it is excellent in the reduction rate of CO emissions. ２ The range of 7.05 to 13.75 mass % is more preferable because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A more preferable range is 7.10 to 10.80% by mass, since this provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0044] The glass composition for glass fiber of this embodiment is preferably a glass composition for long glass fiber. The long glass fiber is a glass fiber that is formed into a state having a length of at least 1,000 m or more in a production process described below, and is composed of a single glass filament or a bundle of multiple glass filaments.

[0045] In the glass composition for glass fiber of this embodiment, the F ２The ratio of the content of SrO to the content of SrO (SrO / F ２ ) is preferably in the range of 0.50 to 12.50. ２ The ratio of the content of SrO to the content of SrO (SrO / F ２ ) is CO ２ More preferably, the range is 1.10 to 12.10 because this provides an excellent reduction rate in CO emissions. ２ It is more preferable that the range is 1.20 to 9.20 because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A range of 1.30 to 4.20 is particularly preferable because it provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0046] In addition, in the glass composition for glass fiber of this embodiment, the ratio of the B content to the SrO content is ２ O ３ The ratio of the content of (B ２ O ３ It is preferable that the ratio of B to the content of SrO is in the range of 2.51 to 24.40. ２ O ３ The ratio of the content of (B ２ O ３ / SrO) is CO ２ More preferably, the range is 2.70 to 10.50 because this provides an excellent reduction rate in CO emissions. ２ It is more preferable that the range is 3.15 to 9.50 because it is excellent in the reduction rate of CO emissions and the water resistance strength retention rate of the glass fiber reinforced resin molded product. ２ A range of 4.65 to 8.90 is particularly preferable because it provides an excellent reduction rate in emissions and an excellent water resistance strength retention rate of the glass fiber reinforced resin molded product, and also results in little change in the color of the glass fiber reinforced resin molded product.

[0047] where CO ２"Excellent emission reduction rate" means that the value corresponding to the emission intensity on a physical volume basis for "other non-metallic minerals" shown in No. 32, column code 62909 of the "Emission Intensity Unit Database for Calculating Organizational Greenhouse Gas Emissions Throughout the Supply Chain (Ver. 2.5)" is in the range of 0 to 0.0070.

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

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

[0050] In addition, the glass composition for glass fiber of this embodiment contains ZnO, Cr, ２ O ３ , Nb ２ O ５ , W.O. ３ , Bi ２ O ３ , Li ２ It may contain O and PbO.

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

[0052] In addition, the glass composition for glass fiber of the present embodiment is２ O ３ When the glass composition for glass fiber contains ２ O ３ The content is, for example, in the range of 0.10 mass % or less, preferably in the range of 0.01 to 0.09 mass %, and more preferably in the range of 0.01 to 0.05 mass %.

[0053] In addition, the glass composition for glass fiber of this embodiment contains the above-mentioned Nb ２ O ５ When the glass composition for glass fiber contains Nb, the amount of Nb is ２ O ５ The content is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0054] In addition, the glass composition for glass fiber of the present embodiment is ３ When the glass composition for glass fiber contains ３ The content is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0055] In addition, the glass composition for glass fiber of the present embodiment is ２ O ３ When the glass composition for glass fiber contains ２ O ３ The content is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

[0056] In addition, the glass composition for glass fiber of the present embodiment is ２When O is contained, the amount of Li relative to the total amount of the glass composition for glass fiber is ２ The O content is, for example, in the range of less than 1.00 mass%, preferably in the range of 0.40 mass% or less, more preferably in the range of 0.10 mass% or less, even more preferably in the range of 0.05 mass% or less, and particularly preferably in the range of 0.01 mass% or less.

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

[0058] In the glass composition for glass fiber of this embodiment, the content of each of the above-mentioned components can be measured using an ICP optical emission spectrometer for the light element Li, and using a wavelength dispersive X-ray fluorescence analyzer for the other elements.

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

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

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

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

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

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

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

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

[0067] In one aspect, the glass fiber of this embodiment is produced as follows. First, based on the components contained in the waste glass and the content of each component, the amount of volatilization of each component during the melting process, and the components contained in the ore serving as the glass raw material and the content of each component, and the amount of volatilization of each component during the melting process, a glass raw material (glass batch) is obtained by blending the waste glass and the ore serving as the glass raw material to obtain the composition of the glass composition for glass fiber of this embodiment. The glass batch is supplied to a melting furnace and melted at a temperature in the range of 1,350 to 1,550° C., for example. Next, the molten glass batch (molten glass) is drawn out from 1 to 20,000 nozzle tips of a bushing controlled at a predetermined temperature and quenched to form glass filaments.

[0068] Next, a sizing agent or binder is applied to the formed glass filaments using an applicator, which is a coating device, and 1 to 20,000 glass filaments are bundled using a bundling shoe, and then wound at high speed onto a tube using a winding machine, thereby obtaining glass fibers.

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

[0070] Here, the glass single fiber (glass filament) discharged from one nozzle tip or hole and cooled and solidified preferably has a perfectly circular cross-sectional shape and a diameter (filament diameter) of 3.0 to 30.0 μm. On the other hand, when the nozzle tip has a non-circular shape and has a protrusion or notch for quenching the molten glass, it is possible to obtain a glass filament having a non-circular cross-sectional shape, such as an ellipse or oval, by controlling the temperature conditions. When the glass filament has an elliptical or oval cross-sectional shape, it is preferable that the converted fiber diameter, which is the fiber diameter when the cross-sectional area is converted to a perfect circle, is 3.0 to 30.0 μm.

[0071] The filament diameter of the glass filament can be calculated, for example, as follows. First, glass fibers are embedded in a resin such as an epoxy resin and the resin is cured. The cured resin is then cut and its cross section is polished. Next, the cross section of the cured resin is observed using an electron microscope, and for 50 or more glass filaments exposed in the cross section, if the cross section of the glass filament is a perfect circle or a nearly perfect circle, the diameter of the glass filament is measured. If the cross section of the glass filament is other than a perfect circle or a nearly perfect circle, the cross section of the glass filament is calculated, and the equivalent fiber diameter is calculated based on the cross section. Next, the filament diameter of the glass filament is calculated by averaging the measured or calculated diameters or equivalent fiber diameters. Alternatively, the filament diameter of the glass filament can also be measured by image processing of an image obtained from the electron microscope using an automatic analyzer.

[0072] On the other hand, when the glass fiber of this embodiment is contained in a glass fiber reinforced resin molded product, the filament diameter of the glass filament can be measured, for example, as follows. First, the glass fiber reinforced resin molded product is heated at 625°C for 30 minutes to burn off the thermoplastic resin and extract the glass fiber. Next, the filament diameter of the glass filament is measured in the same manner as the method for measuring the filament diameter of the glass filament in the glass fiber described above.

[0073] The surface of the glass fiber of this embodiment may be coated with an organic substance for the purposes of improving the bundling of the glass filaments, improving the adhesion between the glass fiber and the resin, and improving the uniform dispersion of the glass fiber in a mixture of the glass fiber and the resin or inorganic material. Examples of such organic substances include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene, particularly carboxylic acid-modified polypropylene, (poly)carboxylic acid, particularly a copolymer of maleic acid and an unsaturated monomer or a copolymer of acrylic acid and an unsaturated monomer. The glass fiber of this embodiment may also be coated with a resin composition containing, in addition to these resins, a silane coupling agent, a lubricant, a surfactant, and the like. The glass fiber of this embodiment may also be coated with a treatment composition containing a silane coupling agent, a surfactant, and the like, without including the above-mentioned resin. Such a resin composition or treatment composition coats the glass fiber in a proportion of 0.03 to 2.0 mass % based on the mass of the glass fiber of this embodiment in a state where it is not coated with the resin composition or treatment composition. Here, the coating ratio based on the mass of the glass fiber and the coating ratio based on the mass of a glass monofilament (sometimes referred to as a monofilament), which usually consists of a plurality of fibers, are substantially the same. Coating of glass fiber with an organic substance can be carried out, for example, in the glass fiber manufacturing process by applying a resin solution or a resin composition solution to the glass fiber using a known method such as a roller applicator, and then drying the glass fiber to which the resin solution or resin composition solution has been applied. Alternatively, coating of glass fiber with an organic substance can be carried out by immersing the glass fiber of this embodiment in the form of a woven fabric in a treatment composition solution, and then drying the glass fiber to which the treatment composition has been applied.

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

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

[0076] Examples of the silane coupling agent include aminosilane, ureidosilane, chlorosilane, epoxysilane, mercaptosilane, vinylsilane, (meth)acrylicsilane, phenylsilane, styrylsilane, and isocyanatesilane. In this embodiment, the silane coupling agent may be used alone or in combination of two or more.

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

[0078] Examples of ureidosilane include γ-ureidopropyltriethoxysilane.

[0079] Examples of chlorosilanes include γ-chloropropyltrimethoxysilane.

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

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

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

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

[0084] Examples of phenylsilane include phenyltrimethoxysilane.

[0085] The styrylsilane may include p-styryltrimethoxysilane.

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

[0087] Examples of lubricants include modified silicone oils, animal oils and their hydrogenated products, vegetable oils and their hydrogenated products, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimines, polyalkylpolyamine alkylamide derivatives, fatty acid amides, and quaternary ammonium salts. In this embodiment, the lubricants may be used alone or in combination of two or more.

[0088] Examples of animal oils include beef tallow.

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

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

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

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

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

[0094] Examples of fatty acid amides include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid.

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

[0096] Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, the surfactants may be used alone or in combination of two or more.

[0097] Examples of nonionic surfactants include ethylene oxide propylene oxide alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene block copolymers, alkyl polyoxyethylene-polyoxypropylene block copolymer ethers, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid monoesters, polyoxyethylene fatty acid diesters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid ester ethylene oxide adducts, polyoxyethylene castor oil ethers, hydrogenated castor oil ethylene oxide adducts, alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, glycerol fatty acid esters, polyglycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyhydric alcohol alkyl ethers, fatty acid alkanolamides, acetylene glycol, acetylene alcohol, ethylene oxide adducts of acetylene glycol, and ethylene oxide adducts of acetylene alcohol.

[0098] Examples of cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (acetates, hydrochlorides, etc.), ethylene oxide adducts of higher alkylamines, condensates of higher fatty acids and polyalkylenepolyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridinium salts.

[0099] Examples of anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfonates, α-olefin sulfonates, reaction products of fatty acid halides and N-methyltaurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphate salts of higher alcohol ethylene oxide adducts.

[0100] Examples of amphoteric surfactants include amino acid type amphoteric surfactants such as alkali metal salts of alkylaminopropionic acid, betaine type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline type amphoteric surfactants.

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

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

[0103] For example, when the glass fiber of this embodiment is a chopped strand, the number of glass filaments constituting the glass fiber of this embodiment is, for example, 10 to 20,000, preferably 50 to 10,000, and more preferably 1,000 to 8,000. The length of the chopped strand, which is the glass fiber of this embodiment, is, for example, 1.0 to 100.0 mm, preferably 1.2 to 51.0 mm, more preferably 1.5 to 30.0 mm, even more preferably 2.0 to 15.0 mm, and particularly preferably 2.3 to 7.8 mm. Here, the chopped strand can be obtained by cutting the glass fiber produced by the above-mentioned method to the predetermined length using a known device such as a long fiber cutting device that cuts the glass fiber by feeding it between a cutter roller having cutters (cutting blades) attached radially at equal intervals and a rubber roller that rotates in contact with the cutter roller and has rubber on its outer circumferential surface.

[0104] When the glass fiber of this embodiment is a roving, the number of glass filaments constituting the glass fiber of this embodiment is, for example, 200 to 30,000. The roving, which is the glass fiber of this embodiment, has a mass per unit length of 0.5 to 10,000 tex (g / 1,000 m).

[0105] When the glass fiber of this embodiment is a glass woven fabric, the glass woven fabric can be obtained by weaving the glass fiber of this embodiment as warp and weft using a known loom. Examples of the loom include a jet loom such as an air jet or water jet loom, a shuttle loom, and a rapier loom. Examples of the weaving method used with the loom include plain weave, satin weave, sash weave, and twill weave, with plain weave being preferred from the viewpoint of production efficiency.

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

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

[0108] The glass fiber fabric preferably comprises warp yarns having a weave density of 40 to 150 yarns / 25 mm and weft yarns having a weave density of 40 to 150 yarns / 25 mm. The weave density of the warp yarns can be determined by counting the number of warp yarns within a 25 mm range in the warp direction using a fabric speculum in accordance with Japanese Industrial Standards (JIS) R 3420. The weave density of the weft yarns can be determined by counting the number of weft yarns within a 25 mm range in the weft direction using a fabric speculum in accordance with Japanese Industrial Standards (JIS) R 3420.

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

[0110] The deoiling treatment may involve placing the glass fiber fabric in a heating furnace at an atmospheric temperature of 350° C. to 400° C. for 40 to 80 hours to thermally decompose organic matter adhering to the glass fibers.

[0111] The surface treatment may include a treatment in which a glass fiber fabric is immersed in a solution containing the silane coupling agent or the silane coupling agent and the surfactant, excess water is squeezed out, and the fabric is then heated and dried at a temperature in the range of 80 to 180°C for 1 to 30 minutes.

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

[0113] The glass fiber fabric has a density of 5.0 to 220 g / m ２and a thickness in the range of 4.0 to 200.0 μm.

[0114] The glass fiber fabric may also have a surface treatment layer containing the silane coupling agent, or the silane coupling agent and the surfactant. When the glass fiber fabric of this embodiment includes the surface treatment layer, the surface treatment layer may have a mass of, for example, 0.03 to 1.50 mass% relative to the total mass of the glass fiber fabric including the surface treatment layer.

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

[0116] Specifically, the glass fiber reinforced resin molded product is a glass fiber reinforced resin molded product containing a resin (thermoplastic resin or thermosetting resin), glass fiber, and other additives, and contains 10 to 90 mass % of glass fiber based on the total amount of the glass fiber reinforced resin molded product. Also, the glass fiber reinforced resin molded product contains 90 to 10 mass % of resin based on the total amount of the glass fiber reinforced resin molded product, and contains other additives in the range of 0 to 40 mass %.

[0117] Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycarbonate, polyarylene sulfide, polyethersulfone (PES), polyphenylsulfone (PPS), and the like. U), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryletherketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate (PEN), ethylene / vinyl acetate (EVA) resin, ionomer (IO) resin, polybutadiene, styrene / butadiene resin, polybutylene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, polyvinyl alcohol (PVA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), and the like.

[0118] Specific examples of polyethylene include high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.

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

[0120] Examples of polystyrene include general-purpose polystyrene (GPPS), which is an atactic polystyrene having an atactic structure, high impact polystyrene (HIPS), which is GPPS with a rubber component added, and syndiotactic polystyrene having a syndiotactic structure.

[0121] Examples of methacrylic resins include a homopolymer of one of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and a fatty acid vinyl ester, or a copolymer of two or more of them.

[0122] Examples of polyvinyl chloride include vinyl chloride homopolymers polymerized by conventional methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization; copolymers of vinyl chloride monomers with copolymerizable monomers; and graft copolymers obtained by graft-polymerizing vinyl chloride monomers onto polymers.

[0123] Examples of polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), and polydecamethylene adipamide (nylon 410). Polyethylene sebacamide (Nylon 1010), polydecamethylene dodecamide (Nylon 1012), polyundecane amide (Nylon 11), polyundecamethylene adipamide (Nylon 116), polydodecanamide (Nylon 12), polyxylene adipamide (Nylon XD6), polyxylene sebacamide (Nylon XD10), polymeta-xylylene adipamide (Nylon MXD6), polypara-xylylene adipamide (Nylon PXD6), polytetramethylene terephthalamide (Nylon 4T), polypentamethylene terephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), polytetramethylene isophthalamide (nylon 4I), polybis( Examples of the copolymer include one or a copolymer of two or more of the following components: polybis(3-methyl-4-aminohexyl)methane terephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methane isophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methaneandodecamide (nylon PACM12), polybis(3-methyl-4-aminohexyl)methane tetradecamide (nylon PACM14), and the like, as well as mixtures thereof.

[0124] Examples of polyacetals include homopolymers having oxymethylene units as the main repeating units, and copolymers that are mainly composed of oxymethylene units and contain oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

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

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

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

[0128] Examples of polycarbonates include polymers obtainable by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate in a molten state, and polymers obtainable by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

[0129] Examples of polyarylene sulfide include linear polyphenylene sulfide, crosslinked polyphenylene sulfide which has been polymerized and then subjected to a curing reaction to increase the molecular weight, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.

[0130] Examples of polyphenylene ethers include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl-1,4-phenylene ether), poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), and the like.

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

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

[0133] Examples of the liquid crystal polymer (LCP) include a (co)polymer, which is a thermotropic liquid crystal polyester, comprising one or more structural units selected from an aromatic hydroxycarbonyl unit, an aromatic dihydroxy unit, an aromatic dicarbonyl unit, an aliphatic dihydroxy unit, an aliphatic dicarbonyl unit, and the like.

[0134] Examples of fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0135] Examples of ionomer (IO) resins include copolymers of olefin or styrene with unsaturated carboxylic acid, in which a portion of the carboxyl groups is neutralized with metal ions.

[0136] Examples of the olefin / vinyl alcohol resin include an ethylene / vinyl alcohol copolymer, a propylene / vinyl alcohol copolymer, a saponified ethylene / vinyl acetate copolymer, and a saponified propylene / vinyl acetate copolymer.

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

[0138] Examples of polylactic acid include poly-L-lactic acid, which is a homopolymer of the L-form, poly-D-lactic acid, which is a homopolymer of the D-form, and stereocomplex polylactic acid, which is a mixture thereof.

[0139] Examples of the cellulose resin include methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0140] Examples of the thermosetting resin include unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenolic resin (PF), urethane resin (PU), polyisocyanate, polyisocyanurate, modified polyimide (PI) resin, urea (UF) resin, silicone (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleimide triazine (BT) resin, and diallyl phthalate resin (PDAP).

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

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

[0143] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexidienebisphenol type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, and the like. Examples of epoxy resins include epoxy resins, novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure, biphenyl-type epoxy resins, aralkyl-type epoxy resins such as xylylene-type epoxy resins and phenylaralkyl-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins, difunctional to tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalenearalkyl-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, and fluorene-type epoxy resins.

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

[0145] Examples of the phenolic resin include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol A-type novolac resin; resole-type phenolic resins such as methylol-type resole resin and dimethylene ether-type resole resin; and aryl alkylene-type phenolic resins, and examples thereof include one or a combination of two or more of these.

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

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

[0148] Examples of the other additives include reinforcing fibers other than glass fibers, such as carbon fibers and metal fibers; fillers other than glass fibers, such as glass powder, talc, and mica; flame retardants, ultraviolet absorbers, heat stabilizers, hydrolysis resistance improvers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, and pigments.

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

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

[0033] Examples of the 2-hydroxy-4-octyloxyphenyl-1,3,5-triazine include 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-triazine, and 2-(alkylidene)malonic acid esters.

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

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

[0153] The glass fiber reinforced resin molded article may be a prepreg obtained by impregnating the glass fiber fabric of the present embodiment with the resin by a method known per se and semi-curing the impregnated resin.

[0154] The glass fiber reinforced resin molded article can be molded by a known molding method to obtain various glass fiber reinforced resin molded articles. Examples of known molding methods include injection molding, injection compression molding, two-color molding, blow molding, foam molding including supercritical fluids, insert molding, in-mold coating molding, autoclave molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, blow molding, stamping molding, infusion molding, hand layup, spray-up, low-pressure RIM molding, resin transfer molding, sheet molding compounding, bulk molding compounding, pultrusion, and filament winding. Glass fiber reinforced resin molded articles can also be obtained by curing the prepreg.

[0155] Examples of uses of such molded articles include electronic components such as printed wiring boards and connectors, housings for electronic devices, interior and exterior vehicle components, housings for electronic devices such as antennas and radars, and separators for fuel cells.

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

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

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

[0159] [Examples 1 to 5, Comparative Examples 1 and 2] A glass raw material A derived from commercially available waste glass and having the composition shown in Table 1 as Comparative Example 1, and a glass raw material B containing 52.0 to 56.0 mass % of SiO ２ and Al in the range of 12.0 to 16.0 mass% ２ O ３ and a total of 20.0 to 25.0 mass% of MgO and CaO, and 5.0 to 10.0 mass% of B. ２O ３ and an ore-derived glass raw material B containing the above in a predetermined ratio, thereby obtaining glass raw materials that can obtain glass compositions for glass fiber having the compositions of Examples 1 to 5 and Comparative Example 2 when producing glass fibers from the glass raw materials.

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

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

[0162] Next, the glass cullet was melted in a platinum crucible using a high-temperature electric furnace equipped with a rotational viscometer (manufactured by Motoyama Corporation), and the viscosity of the molten glass was continuously measured using a rotational viscometer while changing the melting temperature. The 1000 poise temperature was determined by measuring the temperature corresponding to the rotational viscosity of 1000 poise.

[0163] [Method for measuring liquidus temperature] 40 g of glass particles having a particle size of 0.5 to 1.5 mm obtained by crushing glass cullet obtained in the same manner as in the method for measuring 1000 poise temperature was placed in a platinum boat of 180 × 20 × 15 mm, and heated for 8 hours or more in a tubular electric furnace with a temperature gradient of 900 to 1300 ° C., and then removed from the tubular electric furnace and observed with a polarizing microscope to identify the position where crystals derived from the devitrified glass began to precipitate. Next, the temperature inside the tubular electric furnace was measured using a B thermocouple, and the temperature at the position where precipitation began was taken as the liquidus temperature.

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

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

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

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

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

[0169] [Method for measuring the elastic modulus of the monofilament] A sample for measurement was selected in the same manner as in the method for measuring the tensile strength of the monofilament.

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

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

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

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

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

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

[0176] [Method for Measuring Tensile Strength of Glass Fiber Reinforced Resin Molded Article After PCT Treatment] A glass fiber reinforced resin molded article was prepared in the same manner as in the method for measuring the tensile strength of the glass fiber reinforced resin molded article described above.

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

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

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

[0180] [Method for Measuring the Flexural Modulus of a Glass Fiber Reinforced Resin Molded Article] A glass fiber reinforced resin molded article was prepared in the same manner as in the method for measuring the tensile strength of a glass fiber reinforced resin molded article.

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

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

[0183] [CO ２ Method for Evaluating Emission Reduction Rate] For the glass compositions for glass fiber of Examples 1 to 5 and Comparative Examples 1 and 2, a numerical value equivalent to the emission intensity on a physical volume basis for "other non-metallic minerals" shown in No. 32, column code 62909 in the "Emission Intensity Unit Based on Input-Output Table" described in the "Emission Intensity Unit Database for Calculating Greenhouse Gas Emissions, etc. of Organizations Throughout the Supply Chain (Ver. 2.5)" was calculated from the usage ratio of other non-metallic minerals in the raw materials. Then, numerical values ​​equivalent to the emission intensity in the range of 0 to 0.0070 were evaluated as "A," values ​​in the range of 0.0070 to 0.0085 as "B," and values ​​of 0.0085 or more as "C."

[0184] [Method for Evaluating Change in Color of Glass Fiber Reinforced Resin Molded Article] A glass fiber reinforced resin molded article was prepared in the same manner as in the above-mentioned method for measuring the tensile strength of a glass fiber reinforced resin molded article.

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

[0186]

[0187] From Table 1, according to the glass compositions for glass fiber of Examples 1 to 5, CO ２On the other hand, it is clear from Table 1 that the glass composition for glass fiber of Comparative Example 1, which is glass composition A for glass fiber derived from commercial waste glass, can be produced with reduced CO emissions, and can impart water resistance to glass fiber reinforced resin molded articles and suppress color change. ２ Although it is possible to manufacture glass fiber reinforced resin molded products with reduced emissions, it is clear that the change in color of the glass fiber reinforced resin molded products cannot be sufficiently suppressed. ２ The content of O is less than the range of the present invention, and K ２ The glass fiber composition of Comparative Example 2, in which the O content exceeds the range of the present invention, can suppress the color change of the glass fiber reinforced resin molded product, but the CO ２ It is clear that production cannot be achieved with reduced emissions.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0206]

[0207] From Table 2, it can be seen that, according to the glass compositions for glass fiber of Examples 6 to 11, even when the sizing agent used in producing the glass fiber, the sizing agent attachment rate (application rate to monofilament), and the resin used in producing the glass fiber reinforced resin molded product were changed, the glass compositions for glass fiber of Examples 1 to 5 could be used with CO ２ It is clear that the present invention can reduce emissions during production, impart water resistance to glass fiber reinforced resin molded products, and suppress color change.

Claims

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

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

50.

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

40.

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

Images