Resin-reinforcing glass fiber

Abstract

Provided are resin-reinforcing glass fibers capable of coloring a resin composition containing the glass fibers without using a pigment or a dye, and capable of obtaining excellent moldability when molding a glass fiber-reinforced resin molded article by using the resin composition. Resin-reinforcing glass fibers according to the present invention are for use in reinforcing a resin having a glass transition temperature T of 260-445K and having a lightness L* in a CIE L*a*b* color system of 20-100. The total percentage content R of Na2O and K2O with respect to the total amount of the glass fibers is 3.5-20.0 mass%, and the glass transition temperature T, the lightness L*, and the total percentage content R of Na2O and K2O with respect to the total amount of the glass fibers satisfy the following formula (1).　(1): 13.67≤T×R×L* / 10000≤42.05

Description

Glass fiber for resin reinforcement

[0001] The present invention relates to a glass fiber for reinforcing resins.

[0002] Conventionally, glass fibers have been used to reinforce resins. For example, resin pellets are known that are resin compositions containing polyamide resin PA6 (manufactured by Ube Industries, Ltd., product name: UBE Nylon 1015B) and glass fibers of an E-glass composition as glass fibers for reinforcing the resin (see, for example, Patent Document 1).

[0003] In the resin pellets described in Patent Document 1, the glass fibers for resin reinforcement are used in the form of chopped strands, and the resin pellets can be made into glass fiber reinforced resin molded products by, for example, injection molding.

[0004] Patent No. 7201016

[0005] The E-glass composition is the most common glass composition, but the resin composition (resin pellets) described in Patent Document 1, which contains glass fibers of the E-glass composition as glass fibers for resin reinforcement, is not sufficiently colored. Therefore, in order to color the resin composition or a glass fiber-reinforced resin molded product molded using the resin composition, it is necessary to add a pigment or a dye to the resin composition.

[0006] However, the addition of the pigments or dyes to the resin compositions incurs additional costs, and many of the pigments and dyes used to color the resin compositions blue to green contain halogen compounds or heavy metals. Therefore, glass fiber reinforced resin molded products made from the resin compositions have the disadvantages of generating toxic gases such as dioxins when incinerated and causing environmental pollution when discarded.

[0007] Furthermore, in a resin composition containing a combination of glass fibers of a specific glass composition and a specific resin, when the resin composition is used to mold a glass fiber-reinforced resin molded product, the melt viscosity of the resin composition may be significantly reduced or, conversely, increased, making molding difficult.

[0008] The present invention aims to provide a glass fiber for resin reinforcement that can eliminate such inconveniences, can color a resin composition containing glass fiber without using a pigment or dye, and can provide excellent moldability when molding a glass fiber-reinforced resin molded product using the resin composition.

[0009] In order to achieve the above object, the glass fiber for resin reinforcement of the present invention is a glass fiber for resin reinforcement used for reinforcing a resin having a glass transition temperature T in the range of 260 to 445K and a lightness L* in the range of 20 to 100 in the CIE L*a*b* color system, and the content of Na relative to the total amount of the glass fiber is ２ O and K ２ The total content R of Na and O is in the range of 3.5 to 20.0 mass %, and the glass transition temperature T, lightness L* of the resin, and the total amount of the glass fiber ２ O and K ２ The total content R of T and O satisfies the following formula (1): 13.67≦T×R×L* / 10000≦42.05 (1)

[0010] According to the glass fiber for resin reinforcement of the present invention, when a resin having a glass transition temperature T and a lightness L* in the above range is used to form a resin composition, the glass transition temperature T, the lightness L* of the resin, and the ratio of Na to the total amount of the glass fiber are ２ O and K ２ When the total content R of the resin composition with O satisfies the formula (1), the resin composition can be colored blue to green, and excellent moldability can be obtained when the resin composition is used to mold a glass fiber reinforced resin molded product.

[0011] The phrase "capable of coloring the resin composition blue to green" means that when a glass fiber-reinforced resin molded article (hereinafter referred to as a test sample) molded using a resin composition containing the glass fiber for resin reinforcement of the present invention and a glass fiber-reinforced resin molded article (hereinafter referred to as a reference sample) molded in exactly the same manner as the test sample except that glass fiber of E-glass composition is used instead of the glass fiber for resin reinforcement of the present invention are measured for L*a*b* in the CIE L*a*b* color system using a color difference meter in accordance with JIS Z 8781-4:2013, the hue difference calculated by the following formula (A) is -0.5 or less. Hue difference = (a* of test sample) - (a* of reference sample) ... (A)

[0012] Here, the E-glass composition is a composition in which SiO is in the range of 52.0 to 56.0 mass % relative to the total amount of glass fibers. 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. ２ O ３ The glass composition includes:

[0013] Furthermore, "excellent moldability can be obtained" means that the injection pressure ratio between a test sample, which is a dumbbell test piece conforming to JIS K 7161-1:2014 and which is molded by injection molding using a resin composition containing the glass fiber for resin reinforcement of the present invention, and a reference sample molded in exactly the same manner as the test sample except that glass fiber of E-glass composition is used instead of the glass fiber for resin reinforcement of the present invention, is in the range of 0.90 to 1.10. Here, the injection pressure ratio is the ratio of the injection pressure when injection molding the test sample to the injection pressure when injection molding the reference sample (injection pressure when injection molding the test sample / injection pressure when injection molding the reference sample).

[0014] The glass fiber for resin reinforcement of the present invention has a glass transition temperature T of the resin, a lightness L*, and a ratio of Na to the total amount of the glass fiber. ２ O and K ２It is preferable that the total content R of T and O satisfies the following formula (2): 13.70≦T×R×L* / 10000≦29.98 (2)

[0015] According to the glass fiber for resin reinforcement of the present invention, when a resin having a glass transition temperature T and a lightness L* in the above range is used to form a resin composition, the glass transition temperature T, the lightness L* of the resin, and the ratio of Na to the total amount of the glass fiber are ２ O and K ２ When the total content R of O satisfies the formula (2), the resin composition can be colored blue to green, and better moldability can be obtained when molding a glass fiber reinforced resin molded product using the resin composition.

[0016] The phrase "better moldability can be obtained" means that the injection pressure ratio is in the range of 0.95 to 1.05.

[0017] The glass fiber for resin reinforcement of the present invention can take the form of, for example, long glass fibers.

[0018] Next, the embodiment of the present invention will be described in more detail.

[0019] The glass fiber for resin reinforcement of this embodiment is a glass fiber for resin reinforcement used to reinforce a resin having a glass transition temperature T in the range of 260 to 445K and a lightness L* in the range of 20 to 100 in the CIE L*a*b* color system, and ... glass fiber for resin reinforcement ２ O and K ２ The total content R of Na and O is in the range of 3.5 to 20.0 mass %, and the glass transition temperature T, lightness L* of the resin, and the total amount of the glass fiber ２ O and K ２ The total content R of T×R×L* / 10000 and O satisfies the following formula (1), and preferably the following formula (2): 13.67≦T×R×L* / 10000≦42.05 (1) 13.70≦T×R×L* / 10000≦29.98 (2)

[0020] If the resin reinforced by the resin-reinforcing glass fiber of this embodiment (hereinafter sometimes referred to as reinforced resin) has a glass transition temperature T of less than 260 K, when a resin composition containing the resin-reinforcing glass fiber is used to mold a glass fiber-reinforced resin molded product, the melt viscosity of the resin composition tends to be low, the shear force that the resin-reinforcing glass fiber receives from the molten resin is reduced, and the coloring state of the resin composition becomes non-uniform. On the other hand, if the reinforced resin of this embodiment has a glass transition temperature T of more than 445 K, when a resin composition containing the resin-reinforcing glass fiber is used to mold a glass fiber-reinforced resin molded product, the molding temperature tends to be high, and secondary reactions with the resin-reinforcing glass fiber are promoted.

[0021] The glass transition temperature of the reinforced resin of the present embodiment can be measured using a differential scanning calorimeter in accordance with JIS K7121:2012.

[0022] Furthermore, when the lightness L* of the reinforced resin of this embodiment is less than 20 in the CIE L*a*b* color system, the color of the resin itself is dark, making it difficult to color the resin composition containing the glass fiber for resin reinforcement blue to green.

[0023] The glass fiber for resin reinforcement of this embodiment is a glass fiber having a ratio of Na to the total amount of glass fiber. ２ O and K ２ If the total content R of Na and O is less than 3.5 mass %, when the glass fiber for resin reinforcement of this embodiment is used to form a resin composition with the reinforced resin, the resin composition cannot be colored blue to green. ２ O and K ２ If the total content R of the glass fibers and O exceeds 20.0% by mass, when the resin composition is used to mold a glass fiber-reinforced resin molded product, the reaction between the resin-reinforcing glass fibers and the reinforcing resin is promoted, resulting in a significant increase or decrease in melt viscosity and deterioration of moldability.

[0024] In a resin composition composed of the resin-reinforcing glass fiber of this embodiment and the reinforced resin, the higher the glass transition temperature T of the reinforced resin, the higher the molding temperature of the resin composition tends to be, and a secondary chemical reaction between the resin-reinforcing glass fiber and the reinforced resin tends to be promoted, resulting in a sudden change in viscosity of the resin composition during injection molding and deterioration of moldability.

[0025] In addition, the ratio of Na to the total amount of glass fibers for resin reinforcement in this embodiment ２ O and K ２ The higher the total O content R, the more likely the resin composition is to change in hue, while the reaction between the resin-reinforcing glass fiber and the reinforcing resin during molding is more likely to be accelerated, resulting in poor moldability. On the other hand, the higher the lightness L* of the reinforcing resin, the more significant the effect of the change in hue caused by adding the resin-reinforcing glass fiber of this embodiment.

[0026] Therefore, it is believed that T×R×L* indicates the balance between the moldability and color of the resin composition.

[0027] Here, when the glass fiber for resin reinforcement of this embodiment is used to form a resin composition with a resin having a glass transition temperature T and a lightness L* in the above range, the value of T×R×L* / 10000 is in the range of 13.67 to 42.05 (the glass transition temperature T and lightness L* of the resin, the ratio of Na to the total amount of the glass fiber, ２ O and K ２ When the total content R of the resin composition containing O satisfies the formula (1), the resin composition can be colored blue to green, and excellent moldability can be obtained when the resin composition is used to mold a glass fiber reinforced resin molded product.

[0028] If the glass fiber for resin reinforcement of this embodiment has a T×R×L* / 10,000 value of less than 13.67, when the glass fiber and the reinforcing resin form a resin composition, the resin composition cannot be colored blue to green, or when the resin composition is used to mold a glass fiber-reinforced resin molded product, the melt viscosity changes significantly, resulting in poor moldability.On the other hand, if the glass fiber for resin reinforcement of this embodiment has a T×R×L* / 10,000 value of more than 42.05, when the resin composition is used to mold a glass fiber-reinforced resin molded product, the melt viscosity changes significantly, resulting in poor moldability.

[0029] In addition, when the glass fiber for resin reinforcement of this embodiment is used to form a resin composition with a resin having a glass transition temperature T and a lightness L* in the above range, the value of T×R×L* / 10000 is in the range of 13.70 to 29.98 (the glass transition temperature T and lightness L* of the resin, the ratio of Na to the total amount of the glass fiber, ２ O and K ２ By making the total content R of the resin composition containing O satisfy the formula (2), the resin composition can be colored blue to green, and better moldability can be obtained when the resin composition is used to mold a glass fiber reinforced resin molded product.

[0030] The phrase "capable of coloring the resin composition blue to green" means that when a glass fiber-reinforced resin molded article (hereinafter referred to as a test sample) molded using a resin composition containing the resin-reinforcing glass fiber of this embodiment and a glass fiber-reinforced resin molded article (hereinafter referred to as a reference sample) molded in exactly the same manner as the test sample except that glass fiber of E-glass composition is used instead of the resin-reinforcing glass fiber of this embodiment are measured for L*a*b* in the CIE L*a*b* color system using a color difference meter in accordance with JIS Z 8781-4:2013, the hue difference calculated by the following formula (A) is -0.5 or less. Hue difference = (a* of test sample) - (a* of reference sample) ... (A)

[0031] The E-glass composition is a composition in which SiO is in the range of 52.0 to 56.0 mass % relative to the total amount of glass fibers. ２ and Al in the range of 12.0 to 16.0 mass% ２ O ３and a total of 20.0 to 25.0 mass% of MgO and CaO, and 5.0 to 10.0 mass% of B. ２ O ３ The glass composition includes:

[0032] In the CIE L*a*b* color system, lightness L* represents the brightness of a color; the smaller the L*, the darker the color; and the larger the L*, the brighter the color. The chrominance coordinates a* and b* represent hue and saturation; the larger the a*, the redder the color; and the smaller the a*, the greener the color. When a* is small, particularly when b* is large, the color becomes yellow-green, and when b* is small, the color becomes blue. The smaller the a* value, the bluer or greener the color.

[0033] Furthermore, "excellent moldability can be obtained" means that the injection pressure ratio between a test sample, which is a dumbbell test piece conforming to JIS K 7161-1:2014 and which is molded by injection molding using a resin composition containing the resin-reinforcing glass fiber of this embodiment, and a reference sample molded in exactly the same manner as the test sample except that glass fiber of E-glass composition is used instead of the resin-reinforcing glass fiber of this embodiment, is in the range of 0.90 to 1.10, and "even better moldability can be obtained" means that the injection pressure ratio is in the range of 0.90 to 1.05. Here, the injection pressure ratio is the ratio of the injection pressure when injection molding the test sample to the injection pressure when injection molding the reference sample (injection pressure when injection molding the test sample / injection pressure when injection molding the reference sample).

[0034] The glass fiber for resin reinforcement of this embodiment has, for example, SiO in the range of 48.0 to 72.0 mass % relative to the total amount of glass fiber. ２ and Al in the range of 0.5 to 23.0 mass%. ２ O ３ and B in the range of 9.8 mass% or less ２ O ３ and a total of 8.0 to 25.0 mass% of CaO, MgO, SrO, and BaO, and 13.0 mass% or less of ZrO. ２ and P in the range of 9.8 mass% or less. ２ O ５and a total of 3.5 to 20.0 mass% of Na ２ O and K ２ O, and preferably, SiO in the range of 48.0 to 72.0 mass% based on the total amount of glass fibers. ２ and Al in the range of 0.5 to 15.0 mass%. ２ O ３ and B in the range of 9.8 mass% or less ２ O ３ and a total of 8.0 to 25.0 mass% of CaO, MgO, SrO, and BaO, and 13.0 mass% or less of ZrO. ２ and P in the range of 9.8 mass% or less. ２ O ５ and a total of 3.5 to 20.0 mass% of Na ２ O and K ２ O.

[0035] In the glass fiber for resin reinforcement of this embodiment, SiO ２ The content is preferably in the range of 52.0 to 69.0 mass %, more preferably in the range of 58.1 to 62.4 mass %.

[0036] In addition, in the glass fiber for resin reinforcement of this embodiment, Al relative to the total amount of glass fiber ２ O ３ The content is preferably in the range of 1.1 to 11.9 mass %, more preferably in the range of 4.8 to 9.7 mass %.

[0037] In addition, in the glass fiber for resin reinforcement of this embodiment, B ２ O ３ The content is preferably in the range of 9.9 mass % or less, more preferably in the range of 6.9 mass % or less, and even more preferably in the range of 3.0 to 5.5 mass %.

[0038] In addition, in the glass fiber for resin reinforcement of this embodiment, the total content of CaO, MgO, SrO, and BaO relative to the total amount of the glass fiber is preferably in the range of 11.3 to 22.5 mass%, more preferably in the range of 14.6 to 19.4 mass%.

[0039] In addition, in the glass fiber for resin reinforcement of this embodiment, ZrO ２ The content of is preferably in the range of 6.4 mass% or less, more preferably in the range of 4.0 mass% or less, and even more preferably in the range of less than 1.0 mass%.

[0040] In addition, in the glass fiber for resin reinforcement of this embodiment, P ２ O ５ The content of is preferably in the range of 2.8 mass % or less, more preferably in the range of 0.9 mass % or less, and even more preferably in the range of less than 0.05 mass %.

[0041] In addition, in the glass fiber for resin reinforcement of this embodiment, the amount of Na relative to the total amount of glass fiber ２ O and K ２ The total O content R is preferably in the range of 5.1 to 18.5 mass %, more preferably in the range of 6.6 to 12.9 mass %, and even more preferably in the range of 7.1 to 11.2 mass %.

[0042] In addition, the glass fiber for resin reinforcement of this embodiment contains TiO as a trace component. ２ may be contained, but TiO relative to the total amount of glass fibers ２ The content of is preferably in the range of less than 3.0 mass%, more preferably in the range of less than 2.0 mass%, and even more preferably in the range of less than 1.0 mass%.

[0043] In addition, the glass fiber for resin reinforcement of this embodiment contains Fe as a trace component. ２ O ３ may be contained, but Fe relative to the total amount of glass fibers ２ O ３ The content of is preferably in the range of less than 3.0 mass%, more preferably in the range of less than 2.0 mass%, and even more preferably in the range of less than 1.0 mass%.

[0044] The glass fiber for resin reinforcement of this embodiment contains CuO, Ag as trace components. ２ O may be contained, but CuO, Ag, ２The O content is preferably less than 1.0 mass%, more preferably less than 0.4 mass%, even more preferably less than 0.2 mass%, particularly preferably less than 0.1 mass%, particularly preferably less than 0.05 mass%, and most preferably less than 0.01 mass%.

[0045] Furthermore, the glass fiber for resin reinforcement of this embodiment may contain, as impurities derived from raw materials, oxides of Li, Mn, Co, Ni, Zn, Cr, Mo, W, Sr, Sn, Ba, Ce, Y, La, Bi, Gd, Pr, Sc, Yb, or Sb in a total amount of less than 3.0 mass%, preferably less than 2.0 mass%, and more preferably less than 1.0 mass%, based on the total amount of the glass fiber. In particular, the glass fiber for resin reinforcement of this embodiment may contain, as impurities, oxides of Li, Mn, Co, Ni, Zn, Cr, Mo, W, Sr, Sn, Ba, Ce, Y, La, Bi, Gd, Pr, Sc, Yb, or Sb in a total amount of less than 3.0 mass%, preferably less than 2.0 mass%, and more preferably less than 1.0 mass%. ２ O, MnO ２ , CoO, NiO, ZnO, Cr ２ O ３ , MoO ３ , W.O. ３ , SrO, SnO ２ , BaO, CeO ２ , Y ２ O ３ , La ２ O ３ , Bi ２ O ３ , Gd ２ O ３ , Pr ２ O ３ , Sc ２ O ３ , Yb ２ O ３ or Sb ２ O ３ When the impurities are contained, the contents of the impurities are each independently preferably in the range of less than 2.0 mass%, more preferably in the range of less than 1.0 mass%, even more preferably in the range of less than 0.4 mass%, particularly preferably in the range of less than 0.1 mass%, particularly preferably in the range of less than 0.05 mass%, and most preferably in the range of less than 0.01 mass%.

[0046] In the glass fiber for resin reinforcement 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.

[0047] The measurement method is as follows: first, a glass batch prepared by mixing glass raw materials or glass fiber is placed in a platinum crucible, and then melted in an electric furnace at a predetermined temperature for 6 hours while stirring, to obtain a homogeneous molten glass. The predetermined temperature is a temperature in the range of 1350 to 1550°C for the glass batch, and a temperature in the range of 1300 to 1450°C for the glass fiber.

[0048] Here, if organic matter is attached to the surface of the glass fiber, or if the glass fiber is contained mainly as a reinforcing material in an organic material such as a resin, the organic matter is removed before use, for example, by heating for about 0.5 to 24 hours in a muffle furnace at 300 to 650° C. Next, the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then crushed and powdered to produce glass powder.

[0049] The light element Li is quantitatively analyzed using an ICP optical emission spectrometer after the glass powder is thermally decomposed with acid. The 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 spectrometer can be performed by preparing a calibration curve sample 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. The results of these quantitative analyses are 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.

[0050] The glass fiber for resin reinforcement of this embodiment can be produced, for example, as follows.

[0051] First, based on the components and content of each component contained in the multiple types of ores or materials refined from ores (sometimes referred to as ore-derived refined materials) that serve as glass raw materials, and the amount of volatilization of each component during the melting process, multiple types of ores or materials refined from ores that serve as glass raw materials are mixed to obtain a glass raw material (glass batch) so as to obtain a glass composition for the resin-reinforcing glass fiber of this embodiment.

[0052] In the production of the glass fiber for resin reinforcement of this embodiment, the glass raw material may contain, in addition to the multiple types of ores or ore-derived refined materials, glass fibers (recovered glass fibers) recovered from glass fiber-reinforced resin moldings containing glass fibers, or commercially available waste glass.

[0053] 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 a process of heating at a temperature of 500°C or higher. The commercial waste includes not only waste discarded after use in the community, but also waste that has been manufactured and completed as a product but discarded without being used or distributed in the community. The commercial waste glass does not include waste glass generated in factories, etc. during the manufacturing process of glass or products using glass.

[0054] Examples of the waste glass in the market include glass cullet recovered by crushing fluorescent tubes, glass cullet recovered by crushing automobile windshields, glass cullet recovered by crushing screens of digital devices, glass cullet recovered by crushing glass bottles used as containers for beverages, etc., glass cullet recovered by crushing glass such as window glass used in buildings, etc., glass cullet recovered by crushing glass constituting solar panels, glass wool insulation recovered when buildings are demolished or home appliances are disposed of, and mixtures thereof. Such waste glass in the market includes glass cullet recovered by crushing 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 K２ The glass may be made of a glass composition further containing at least one of O.

[0055] The glass fibers can be recovered from the glass fiber reinforced resin molded product by, for example, heating the glass fiber reinforced resin molded product at 450 to 800 ° C. for 0.5 to 8 hours to incinerate the thermoplastic resin contained in the glass fiber reinforced resin molded product, or by dissolving the resin contained in the glass fiber reinforced thermoplastic resin molded product in a solvent such as benzyl alcohol.

[0056] Next, the glass raw material (glass batch) is supplied to a melting furnace and melted at a temperature in the range of, for example, 1000 to 1550° C. 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.

[0057] 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, while being wound at high speed around a tube using a winder, to obtain a glass fiber. Note that the process of melting a glass batch, fiberizing it to obtain glass filaments, and then bundling a plurality of these glass filaments to obtain a glass fiber is called spinning.

[0058] The glass fiber for resin reinforcement of this embodiment may be surface-coated with an organic substance, so long as the effect of coloring the resin composition blue to green when it is combined with the reinforcing resin to form a resin composition is not impaired. This coating may be used to improve the bundling of the glass filaments, improve the adhesion between the glass fiber and the resin, and improve the uniform dispersion of the glass fiber in the resin composition, which is a mixture of the glass fiber and the resin. Examples of such organic substances include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene, particularly carboxylic acid-modified polypropylene, and (poly)carboxylic acid, particularly a copolymer of maleic acid and an unsaturated monomer (hereinafter referred to as a surface-treated resin).

[0059] Furthermore, the glass fiber for resin reinforcement of this embodiment may be coated with a surface-treated resin composition containing, in addition to the surface-treated resin, a silane coupling agent, a lubricant, a surfactant, etc., as long as the effect of coloring the resin composition blue to green is not impaired when the glass fiber for resin reinforcement of this embodiment is formed with the reinforcing resin. Alternatively, the glass fiber for resin reinforcement of this embodiment may be coated with a treatment composition containing a silane coupling agent, a surfactant, etc., without containing the surface-treated resin. Such a surface-treated resin composition or treatment composition coats the glass fiber at a ratio of 0.03 to 2.0 mass%, based on the mass of the glass fiber for resin reinforcement of this embodiment in a state not coated with the surface-treated resin composition or treatment composition. Coating of the glass fiber with an organic substance can be performed, for example, during the glass fiber manufacturing process, by applying a surface-treatment resin solution or a surface-treatment 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 surface-treatment resin solution or surface-treatment resin composition solution has been applied.

[0060] 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.

[0061] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0062] Examples of ureidosilane include γ-ureidopropyltriethoxysilane.

[0063] Examples of chlorosilanes include γ-chloropropyltrimethoxysilane.

[0064] Examples of epoxy silanes include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0065] Examples of mercaptosilane include γ-mercaptotrimethoxysilane and γ-mercaptopropyltrimethoxysilane.

[0066] Examples of vinylsilanes include vinyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, and N-benzyl-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0067] Examples of the (meth)acrylic silane include γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

[0068] Examples of phenylsilane include phenyltrimethoxysilane.

[0069] The styrylsilane may include p-styryltrimethoxysilane.

[0070] Examples of isocyanate silanes include γ-isocyanate propyl triethoxy silane.

[0071] 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.

[0072] Examples of animal oils include beef tallow.

[0073] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, etc.

[0074] Examples of animal waxes include beeswax and lanolin.

[0075] Examples of vegetable waxes include candelilla wax and carnauba wax.

[0076] Examples of mineral waxes include paraffin wax and montan wax.

[0077] Examples of the condensation products of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.

[0078] 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.

[0079] Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] The glass fiber for resin reinforcement of this embodiment can be in the form of a long glass fiber, such as a roving, a yarn, a strand, a chopped strand, a cut fiber, or a chopped strand mat.

[0086] The roving, yarn or strand is in a form in which the number of glass filaments constituting the glass fiber is in the range of 10 to 30,000 and is not cut.

[0087] The chopped strands are glass fibers (glass strands) in which the number of glass filaments constituting the glass fiber is preferably in the range of 1 to 30,000, more preferably in the range of 50 to 10,000, and even more preferably in the range of 1,000 to 8,000, and the glass fiber is cut to a length preferably in the range of 1.0 to 100.0 mm, more preferably in the range of 1.2 to 51.0 mm, still more preferably in the range of 1.5 to 30.0 mm, particularly preferably in the range of 2.0 to 15.0 mm, and most preferably in the range of 2.3 to 7.8 mm.

[0088] The cut fibers are glass fibers having a number of glass filaments in the range of 1 to 30,000, which are pulverized to lengths in the range of 1 to 900 μm by a known method such as a ball mill or a Henschel mixer.

[0089] The chopped strand mat is formed by cutting the glass fibers into lengths ranging from 40 to 150 mm, dispersing them in random directions on a plane, and molding them into a mat shape using a resin binder.

[0090] The reinforced resin reinforced with the resin-reinforcing glass fiber of this embodiment may be a thermoplastic resin or a thermosetting resin as long as it has a glass transition temperature T and lightness L* within the above-mentioned ranges. However, when a glass fiber-reinforced resin molded product is formed using a resin composition containing the resin-reinforcing glass fiber of this embodiment, a high shear force acts from the molten resin on the resin-reinforcing glass fiber, which promotes dispersion of the resin-reinforcing glass fiber in the molten resin and ensures that the molten resin as the resin composition has a uniform colored state. From this viewpoint, however, a thermoplastic resin is preferred.

[0091] Examples of thermoplastic resins that can be used for the reinforced resin of this embodiment include polyamide, polybutylene terephthalate, polypropylene, linear polyarylene sulfide, liquid crystal polymer, polystyrene, cycloolefin polymer, acrylonitrile-butadiene-styrene resin, modified polyphenylene ether, polyvinyl chloride, perfluoroalkoxyalkane resin, polylactic acid, and polyglycolic acid.

[0092] Examples of the polyamide 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 106). Methylene 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 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.

[0093] Examples of the polybutylene terephthalate include a polymer obtainable by polycondensing terephthalic acid or a derivative thereof with 1,4-butanediol.

[0094] Examples of the polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0095] Examples of the liquid crystal polymer include (co)polymers, which are thermotropic liquid crystal polyesters, each of which comprises 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.

[0096] Examples of the 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.

[0097] Examples of the modified polyphenylene ether include a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / butadiene copolymer, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / maleic anhydride copolymer, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a polyamide, a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene / butadiene / acrylonitrile copolymer, the polyphenylene ether having a functional group such as an amino group, an epoxy group, a carboxy group, or a styryl group introduced into the polymer chain terminal, and the polyphenylene ether having a functional group such as an amino group, an epoxy group, a carboxy group, a styryl group, or a methacryl group introduced into a polymer chain side chain.

[0098] Examples of the polyvinyl chloride include a vinyl chloride homopolymer polymerized by a conventionally known method such as emulsion polymerization, suspension polymerization, microsuspension polymerization, or bulk polymerization; a copolymer of a vinyl chloride monomer with a copolymerizable monomer; and a graft copolymer obtained by graft-polymerizing a vinyl chloride monomer onto a polymer.

[0099] Examples of the 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.

[0100] The reinforcing resin is preferably polyamide, polybutylene terephthalate, linear polyarylene sulfide, or polypropylene, more preferably polyamide or polybutylene terephthalate, and even more preferably polybutylene terephthalate, from the viewpoints that there is little secondary reaction with the glass fiber for resin reinforcement of this embodiment and that the colorability of a resin composition containing the glass fiber for resin reinforcement is good.

[0101] The glass fiber for resin reinforcement of this embodiment can be kneaded with the reinforcing resin using, for example, a known twin-screw kneader to form a resin composition. The resin composition is, for example, resin pellets having a glass content in the range of 5.0 to 60.0 mass %, and various glass fiber-reinforced resin molded products can be obtained using the resin pellets by known molding methods.

[0102] The resin composition may contain reinforcing fibers other than glass fibers (e.g., carbon fibers, metal fibers), fillers other than glass fibers (e.g., glass powder, talc, mica), flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, slip agents, antibacterial agents, and the like.

[0103] Examples of the known molding methods include injection molding, injection compression molding, two-color molding, blow molding, foam molding including supercritical fluid, insert molding, in-mold coating molding, autoclave molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, blow molding, stamping molding, infusion, hand layup, spray-up, low-pressure RIM molding, resin transfer molding, sheet molding compound method, bulk molding compound method, pultrusion method, and filament winding method.

[0104] The glass fiber reinforced resin molded product is colored in the same manner as the resin pellets, since the resin pellets used as the resin composition in the molding method are colored.

[0105] Next, examples of the present invention and comparative examples will be described.

[0106] Examples 1 to 6 and Comparative Examples 1 to 4 First, glass batches were obtained by mixing glass raw materials so that the glass compositions after melting and solidifying would be the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 shown in Table 1. Next, the obtained glass batches were poured into a platinum vessel equipped with 200 nozzle tips at the bottom, and this platinum vessel was heated to a temperature in the range of 1000 to 1300°C to melt the glass, thereby obtaining molten glass. Next, the obtained molten glass was drawn out from the nozzle tips of the platinum vessel to form glass filaments (monofilaments).

[0107] Next, a sizing agent containing aminosilane and urethane resin was applied to the glass filaments using an applicator, which is a coating device, and 200 glass filaments were bundled using a bundling shoe, and then wound around a tube at a rotation speed of 1000 rpm using a winder, thereby obtaining glass strands as the glass fibers of Examples 1 to 6 and Comparative Examples 1 to 4.

[0108] The sizing agent was applied at a ratio of 0.8 mass % to the glass filaments. The glass strands had a number average fiber diameter of 15 μm and substantially the same composition as the glass batch. The strands were then cut into lengths of 3 mm to obtain chopped strands.

[0109] Next, the chopped strands and the resin shown in Table 1 were kneaded 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 having a glass content of 30.0% by mass. In Table 1, PA6 is polyamide 6 (manufactured by Toray Industries, Inc., trade name: Amilan CM1017), PA610 is polyamide 610 (manufactured by Toray Industries, Inc., trade name: Amilan CM2001), linear PPS is linear polyphenylene sulfide (manufactured by Kureha Corporation, trade name: Fortron KPS W-214A), PBT is polybutylene terephthalate (manufactured by Toray Industries, Inc., trade name: Toraycon 1401x06), PA66 is polyamide 66 (manufactured by Toray Industries, Inc., trade name: Amilan CM3001-N), cross-linked PPS is cross-linked polyphenylene sulfide (manufactured by Toray Industries, Inc., trade name: Torelina L-2631), and PEEK is polyether ether ketone (manufactured by Syensqo, trade name: Ketaspire KT-880NT), and PC is polycarbonate (manufactured by Teijin Limited, trade name: Panlite L-1250Y).

[0110] Table 1 shows the glass transition temperature T, lightness L* in the CIE L*a*b* color system, T×R×L* / 10000 value, and glass content of the resin used in each resin pellet in Examples 1 to 6 and Comparative Examples 1 to 4.

[0111] Next, the color difference and injection pressure ratio were evaluated as follows using each of the resin pellets of Examples 1 to 6 and Comparative Examples 1 to 4. The results are shown in Table 1.

[0112] [Hue Difference] Using each of the resin pellets of Examples 1 to 6 and Comparative Examples 1 to 4, injection molding was performed using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., product name: NEX80) at the mold temperature, injection temperature, and injection rate shown in Table 1 to prepare glass fiber reinforced resin molded products, which were dumbbell test pieces in accordance with JIS K 7161-1: 2014, as test samples. In addition, a glass fiber reinforced resin molded product was prepared in exactly the same manner as the test samples, except that glass fiber having an E-glass composition was used instead of the glass fiber for resin reinforcement in each of Examples 1 to 6 and Comparative Examples 1 to 4, and was used as a reference sample.

[0113] Next, for each of Examples 1 to 6 and Comparative Examples 1 to 4, the L*a*b* color values ​​of the test sample and the reference sample in the CIE L*a*b* color system were measured using a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name: Spectrophotometer SE6000) in accordance with JIS Z 8781-4:2013, and the hue difference was calculated using the following formula (A): Hue difference = (a* of test sample) - (a* of reference sample) (A)

[0114] [Injection Pressure Ratio] Test samples and reference samples were prepared in exactly the same manner as in the case of evaluating hue difference, and for each of Examples 1 to 6 and Comparative Examples 1 to 4, the ratio of the injection pressure used for injection molding the test sample to the injection pressure used for injection molding the reference sample (injection pressure used for injection molding the test sample / injection pressure used for injection molding the reference sample) was defined as the injection pressure ratio.

[0115]

[0116] From Table 1, the ratio of Na to the total amount of glass fiber ２ O and K ２ The total content R of Na and O is in the range of 3.5 to 20.0 mass %, and the glass transition temperature T of the resin, the lightness L*, and the ratio of Na to the total amount of glass fibers are ２ O and K ２According to the glass fibers for resin reinforcement of Examples 1 to 6, in which the total content R with O satisfies the formula (1), when used to reinforce a resin having a glass transition temperature T in the range of 260 to 445 K and a lightness L* in the CIE L*a*b* color system in the range of 20 to 100, it is clear that the hue difference is −0.5 or less and the resin can be colored green to blue.

[0117] Furthermore, from Table 1, it is clear that according to the glass fibers for resin reinforcement of Examples 1 to 6, the injection pressure ratio is in the range of 0.90 to 1.10, and excellent moldability can be obtained when molding a glass fiber reinforced resin molded product using the glass fibers for resin reinforcement.

[0118] On the other hand, from Table 1, the glass transition temperature T of the resin, the lightness L*, the ratio of Na to the total amount of glass fiber ２ O and K ２ In the case of the glass fibers for resin reinforcement of Comparative Examples 1, 2, and 4, in which the total content R with O is less than 13.67, which is the lower limit of formula (1), the hue difference exceeds −0.5, and when a resin composition is formed with the reinforced resin, the resin composition cannot be colored blue to green, or the injection pressure ratio is less than 0.90, and when a glass fiber-reinforced resin molded product is molded using the resin composition, the melt viscosity is significantly reduced, and moldability is clearly deteriorated.

[0119] As for the glass fiber for resin reinforcement of Comparative Example 4, as described above, when the resin composition is used to mold a glass fiber reinforced resin molded product, the melt viscosity is significantly reduced and moldability is deteriorated, so that a glass fiber reinforced resin molded product cannot be obtained, and therefore the hue difference is not measured.

[0120] In addition, from Table 1, the glass transition temperature T of the resin, the lightness L*, and the ratio of Na to the total amount of glass fiber ２ O and K ２ In the case of the glass fiber for resin reinforcement of Comparative Example 3, in which the total content R with O exceeds 42.05, which is the upper limit of formula (1), the injection pressure ratio exceeds 1.10, and it is clear that when the resin composition is used to mold a glass fiber-reinforced resin molded product, the melt viscosity increases significantly and moldability deteriorates.

Claims

1. A glass fiber for reinforcing resins, which has a glass transition temperature T in the range of 260 to 445K and a lightness L* in the range of 20 to 100 in the CIE L*a*b* color system, and is used to reinforce the resins, ２ O and K ２ The total content R of Na and O is in the range of 3.5 to 20.0 mass %, and the glass transition temperature T, lightness L*, and the total amount of the glass fiber of the resin are ２ O and K ２ A glass fiber for resin reinforcement, characterized in that the total content R of glass fiber and O satisfies the following formula (1): 13.67≦T×R×L* / 10000≦42.05 (1) 2. The glass fiber for resin reinforcement according to claim 1, wherein the glass transition temperature T, lightness L*, and Na ２ O and K ２ A glass fiber for resin reinforcement, characterized in that the total content R of glass fiber and O satisfies the following formula (2): 13.70≦T×R×L* / 10000≦29.98 (2) 3. The glass fiber for reinforcing resins according to claim 1, characterized in that it is in the form of long glass fibers.

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