JP6702099B2 - Glass fiber reinforced resin composition and molded article - Google Patents

Description

  The present invention relates to a glass fiber reinforced resin composition and a molded article made of the glass fiber reinforced resin composition.

Conventionally, glass fibers have been widely used in various applications for improving the strength of resin compositions. As the glass fiber, the E glass composition (SiO _{2 in} the range of 52.0 to 56.0 mass% and Al ₂ O _{3 in} the range of 12.0 to 16.0 mass% with respect to the total amount of the glass fiber, the total) And the glass fiber (E glass fiber) having the composition containing MgO and CaO in the range of 20.0 to 25.0 mass% and the range of 5.0 to 10.0 mass% and B ₂ O ₃ is the most. It is used for general purposes. Further, as a glass fiber capable of imparting extremely high strength to the resin composition and its molded product, an S glass composition (SiO _{2 in} a range of 64.0 to 66.0 mass% with respect to the total amount of glass fiber, 24.0 to 24.0) is used. A glass fiber (S glass fiber) having a composition containing Al ₂ O _{3 in} the range of 26.0 mass% and MgO in the range of 9.0 to 11.0 mass% is known. Here, the S glass composition is 1000 poise temperature (temperature at which the viscosity of the melt of the glass composition is 1000 poise (100 Pa·s)) and liquidus temperature (when the temperature of the melt of the glass composition is lowered. The temperature at which crystal precipitation first occurs) is high, and the working temperature range (the temperature range suitable for the production of glass fibers) expressed by the difference between these two temperatures is narrow, so the production of the S glass composition is not always easy. The problem was not known.

In recent years, there has been a demand for glass fibers capable of imparting higher strength to a resin composition than E glass fibers, and more excellent in manufacturability than S glass fibers. , SiO _{2 in} the range of 57.0 to 63.0 mass %, Al ₂ O _{3 in} the range of 19.0 to 23.0 mass %, and MgO in the range of 10.0 to 15.0 mass %, Proposed glass fiber having a composition containing CaO in the range of 4.0 to 11.0 mass% and having a total content of SiO ₂ , Al ₂ O ₃ , MgO and CaO of 99.5 mass% or more. (See Patent Document 1).

  By using the glass fiber described in Patent Document 1, it is possible to impart higher tensile strength, higher flexural strength and higher flexural modulus to the resin composition and its molded product than when using E glass fiber.

International Publication No. 2011/155362

  Molded articles made of a glass fiber reinforced resin composition are increasingly used for housings of electronic devices such as smartphones and notebook computers. Since the smartphones, laptops, etc. are often carried and therefore often exposed to impacts such as dropping, molded products made of the glass fiber reinforced resin composition have tensile strength, bending strength and bending strength. In addition to the elastic modulus, high impact strength is required.

  However, the molded article made of the glass fiber reinforced resin composition containing the glass fiber described in Patent Document 1 has an impact strength equal to or less than that of the molded article made of the glass fiber reinforced resin composition containing the E glass fiber. There is an inconvenience.

  The present invention eliminates such inconveniences and can realize a molded product having high tensile strength, high bending strength, high bending elastic modulus, and high impact strength, and a glass fiber reinforced resin composition and the glass fiber reinforced resin. The object is to provide a molded article composed of the composition.

In order to achieve such an object, the glass fiber reinforced resin composition of the present invention contains a glass fiber in the range of 10 to 90% by mass and a resin in the range of 90 to 10% by mass with respect to the total amount of the glass fiber reinforced resin composition. a glass fiber reinforced resin composition containing the door, the glass fiber has a SiO ₂ in the range of 57.0 to 60.0 wt% with respect to glass fiber based on the total amount of 17.5 to 20.0 wt% Al ₂ O _{3 in} the range, MgO in the range 8.5 to 12.0 mass %, CaO in the range 10.0 to 13.0 mass %, and 0.5 to 1.5 mass %. and a B ₂ O _{3, and, SiO 2, Al 2 O 3} , the total amount of MgO and CaO is Ri der least 98.0 wt%, _B 2 for content (mass%) of _Al 2 _{O 3} O The ratio ((B ₂ O ₃ (mass %)×CaO (mass %))/Al ₂ O ₃ (mass %)) of the content rate (mass %) of _{3 and} the content rate (mass %) of CaO is It is characterized by having a composition in the range of 0.25 to 0.75 .

  The glass fiber reinforced resin composition of the present invention contains a glass fiber having the above composition to realize a molded article having high tensile strength, high bending strength, high bending elastic modulus, and high impact strength. be able to.

  The glass fiber reinforced resin composition of the present invention contains the glass fiber reinforced resin composition when the glass fiber content is less than 10 mass% or the resin content exceeds 90 mass% with respect to the total amount of the glass fiber reinforced resin composition. Sufficient tensile strength, flexural strength, flexural modulus and impact strength cannot be obtained in a molded article made of the composition. On the other hand, the glass fiber reinforced resin composition of the present invention, when the glass fiber content is more than 90 mass% or the resin content is less than 10 mass% with respect to the total amount of the glass fiber reinforced resin composition, It becomes difficult to manufacture a molded article made of the glass fiber reinforced resin composition.

  The glass fiber reinforced resin composition of the present invention, in the case of forming a molded product by injection molding, has a range of 20 to 70 mass% from the viewpoint of achieving both the strength of the molded product and the ease of manufacturing the molded product. Glass fiber and the resin in the range of 80 to 30% by mass are preferable, and the glass fiber in the range of 25 to 60% by mass and the resin in the range of 75 to 40% by mass are more preferable. It is more preferable to contain the glass fiber in the range of 30 to 50% by mass and the resin in the range of 70 to 50% by mass.

In the glass fiber contained in the glass fiber reinforced resin composition of the present invention, when the content of SiO ₂ is less than 57.0 mass% with respect to the total amount of the glass fiber, the tensile strength of the molded article made of the glass fiber reinforced resin composition. However, the bending strength and bending elastic modulus cannot be sufficiently improved. On the other hand, in the glass fiber, when the content of SiO ₂ with respect to the total amount of the glass fiber exceeds 60.0 mass %, the 1000 poise temperature and the liquidus temperature become high, and the production of the glass fiber becomes difficult.

In the glass fiber, the content of SiO ₂ with respect to the total amount of glass fiber is preferably in the range of 58.2 to 59.8 mass %, more preferably in the range of 58.4 to 59.7 mass %. , 58.6 to 59.6% by mass, more preferably 58.8 to 59.5% by mass, particularly preferably 58.9 to 59.4% by mass. Is most preferred. When the content of SiO ₂ in the glass fiber is in such a range, high tensile strength, bending strength and bending elastic modulus of a molded article made of the glass fiber reinforced resin composition, and ease of production of glass fiber are obtained. Can be achieved at the same time.

Further, in the glass fiber contained in the glass fiber reinforced resin composition of the present invention, when the content of Al ₂ O ₃ is less than 17.5 mass% with respect to the total amount of glass fiber, a molded article made of the glass fiber reinforced resin composition. It is impossible to sufficiently improve the tensile strength, bending strength, and bending elastic modulus. On the other hand, in the glass fiber, when the content of Al ₂ O ₃ with respect to the total amount of the glass fiber exceeds 20.0 mass %, the liquidus temperature becomes high, so that the working temperature range becomes narrow and the production of the glass fiber becomes difficult, Further, the impact strength of the molded product made of the glass fiber reinforced resin composition cannot be sufficiently improved.

In the glass fiber, the content of Al ₂ O ₃ with respect to the total amount of glass fiber is preferably in the range of 18.0 to 19.5 mass %, and preferably in the range of 18.2 to 19.3 mass %. More preferably, it is more preferably in the range of 18.3 to 19.1% by mass, still more preferably in the range of 18.4 to 18.9% by mass. When the content of Al ₂ O _{3 in} the glass fiber is in such a range, high tensile strength, bending strength, bending elastic modulus and impact strength of a molded article made of the glass fiber reinforced resin composition, and glass It is possible to achieve both ease of fiber production.

  Further, in the glass fiber contained in the glass fiber reinforced resin composition of the present invention, when the content of MgO with respect to the total amount of glass fiber is less than 8.5% by mass, the tensile strength of a molded article made of the glass fiber reinforced resin composition However, the bending strength and bending elastic modulus cannot be sufficiently improved. On the other hand, in the above-mentioned glass fiber, when the content of MgO with respect to the total amount of glass fiber exceeds 12.0 mass %, the liquidus temperature becomes high, so that the working temperature range becomes narrow and the production of glass fiber becomes difficult.

  In the glass fiber, the content of MgO with respect to the total amount of glass fiber is preferably in the range of 8.8 to 11.5 mass%, more preferably in the range of 9.0 to 11.0 mass%, The range of 9.2 to 10.5 mass% is more preferable, the range of 9.3 to 10.2 mass% is particularly preferable, and the range of 9.4 to 9.9 mass% is preferable. Is most preferred. In the glass fiber, when the content of MgO is in such a range, high tensile strength, bending strength, bending elastic modulus, and impact strength of the molded article made of the glass fiber reinforced resin composition and the glass fiber It is possible to achieve both ease of manufacture and compatibility.

  Further, in the glass fiber contained in the glass fiber reinforced resin composition of the present invention, if the content of CaO is less than 10.0 mass% with respect to the total amount of the glass fiber, the liquidus temperature becomes high and the working temperature range becomes narrow. It becomes difficult to produce glass fibers, and the impact strength of a molded article made of the glass fiber reinforced resin composition cannot be sufficiently improved. On the other hand, in the glass fiber, when the content of CaO with respect to the total amount of the glass fiber exceeds 13.0 mass %, the tensile strength, bending strength and bending elastic modulus of the molded article made of the glass fiber reinforced resin composition are sufficiently improved. I can't let you do it.

  In the glass fiber, the content of CaO with respect to the total amount of glass fiber is preferably in the range of 10.3 to 12.5% by mass, more preferably in the range of 10.5 to 12.3% by mass, The range of 10.7 to 12.1% by mass is further preferable, the range of 10.9 to 11.9% by mass is particularly preferable, and the range of 11.1 to 11.8% by mass is set. Is most preferred. In the glass fiber, when the CaO content is in such a range, the high tensile strength, bending strength, bending elastic modulus, and impact strength of the molded article made of the glass fiber reinforced resin composition and the glass fiber It is possible to achieve both ease of manufacture and compatibility.

Moreover, in the glass fiber contained in the glass fiber reinforced resin composition of the present invention, when the content of B ₂ O ₃ is less than 0.5% by mass relative to the total amount of glass fiber, the glass fiber content of Cutting is likely to occur, and manufacturing efficiency is reduced. on the other hand. In the glass fiber. When the content of B ₂ O ₃ with respect to the total amount of glass fibers is more than 1.5% by mass, the tensile strength, bending strength and bending elastic modulus of the molded product made of the glass fiber reinforced resin composition cannot be sufficiently improved. .

In the glass fiber, the content of B ₂ O ₃ relative to the total amount of glass fiber is preferably in the range of 0.5 to 1.2% by mass, and in the range of 0.5 to 1.0% by mass. More preferable. When the content of B ₂ O _{3 in} the glass fiber is in such a range, the molded product made of the glass fiber reinforced resin composition has high tensile strength, bending strength, bending elastic modulus, and excellent glass fiber. It is possible to achieve both production efficiency.

Further, in the glass fiber contained in the glass fiber reinforced resin composition of the present invention, when the total amount of SiO ₂ , Al ₂ O ₃ , MgO and CaO is less than 98.0% by mass relative to the total amount of glass fiber, The content of the impurity component becomes relatively large. As a result, the working temperature range is narrowed to make it difficult to produce glass fiber, or the molded article made of the glass fiber reinforced resin composition is sufficiently improved in tensile strength, bending strength, bending elastic modulus, and impact strength. I can't.

In the glass fiber, the total amount of _{SiO 2, Al 2 O 3,} MgO and CaO to glass fibers the total amount is preferably less than 98.0 wt% 99.5 wt%, 98.5 wt% 99 It is more preferably less than 0.0% by mass. In the glass fiber, by setting the total amount of SiO ₂ , Al ₂ O ₃ , MgO and CaO in such a range, the molded article made of the glass fiber reinforced resin composition has high tensile strength, bending strength and bending elastic modulus. , And impact strength, and the ease of manufacturing glass fibers can be made compatible.

Further, in the glass fiber contained in the glass fiber reinforced resin composition of the present invention, the ratio (CaO (mass %)/Al ₂ O) of the CaO content (mass %) to the Al ₂ O ₃ content (mass %). ₃ (mass %)) is in the range of 0.50 to 0.72, and the content (mass %) of B ₂ O _{3 and} the content (mass %) of Ca _{2 with} respect to the content (mass %) of Al ₂ O ₃ (mass %). The ratio ((B ₂ O ₃ (mass %)×CaO (mass %))/Al ₂ O ₃ (mass %)) of the product with (mass %) is preferably in the range of 0.22 to 1.00. , CaO (mass %)/Al ₂ O ₃ (mass %) is in the range of 0.55 to 0.67, and (B ₂ O ₃ (mass %)×CaO (mass %))/Al ₂ O ₃ (mass %) is more preferably in the range of 0.25 to 0.75, CaO (mass %)/Al ₂ O ₃ (mass %) is in the range of 0.57 to 0.65, and , (B ₂ O ₃ (mass %)×CaO (mass %))/Al ₂ O ₃ (mass %) are more preferably in the range of 0.27 to 0.65. By doing so, the high tensile strength, bending strength, bending elastic modulus, and impact strength of the molded article made of the glass fiber reinforced resin composition can be made compatible with the excellent glass fiber production efficiency.

Further, the glass fiber contained in the glass fiber reinforced resin composition of the present invention may contain Na ₂ O and K ₂ O in addition to the above components. Na ₂ O and K ₂ O are usually added in order to reduce the viscosity of the glass and make it easier to melt, but since the strength and chemical resistance of the glass fiber are reduced, Na ₂ O and K ₂ O relative to the total amount of glass fiber are added. The total amount of is preferably in the range of 0.05 to 1.0 mass %.

Further, the glass fiber contained in the glass fiber reinforced resin composition of the present invention may contain Fe ₂ O ₃ . Fe ₂ O ₃ usually exists as an impurity in the glass raw material, but since it influences the absorption of radiant heat in the molten glass and the coloring of the glass fiber, the content of Fe ₂ O ₃ relative to the total amount of glass fiber is 0.05. It is preferable to set it in the range of 1.0 mass%.

Further, the glass fibers contained in the glass fiber-reinforced resin composition of the present _invention, Na 2 O, if it contains _{K 2} O and _Fe 2 _{O 3, Na} 2 O with respect to glass fibers the total amount, _{K 2} O and _Fe 2 _{O 3} The total amount of is preferably in the range of 0.1 to 2.0% by mass, more preferably in the range of 0.1 to 0.5% by mass.

  In addition, in the glass fiber contained in the glass fiber reinforced resin composition of the present invention, the content ratio of each component described above is measured for the light element B by using an ICP emission spectroscopic analyzer, and other elements are wavelengths. It can be performed using a dispersion type fluorescent X-ray analyzer.

  As the measuring method, first, a glass fiber reinforced resin composition or a molded article made of a glass fiber reinforced resin composition is heated, for example, in a muffle furnace at 300 to 650° C. for about 0.5 to 24 hours, Decomposes organic matter. Next, the remaining glass fibers are put into a platinum crucible and held in an electric furnace at a temperature of 1550° C. for 6 hours to be melted with stirring to obtain a homogeneous molten glass. Next, the obtained molten glass is cast onto a carbon plate to prepare a glass cullet, which is then crushed and powdered. Regarding B, which is a light element, the glass powder is subjected to alkali melting decomposition and then quantitatively analyzed using an ICP emission spectroscopic analyzer. Other elements are quantitatively analyzed using a wavelength dispersive X-ray fluorescence analyzer after glass powder is molded into a disk shape by a press. The quantitative analysis results are converted into oxides to calculate the content and total amount of each component, and the content rate of each component described above can be obtained from these numerical values.

  In the present invention, the glass fiber contained in the glass fiber reinforced resin composition has a ratio of the major axis to the minor axis of the cross-sectional shape (major axis/minor axis) in the range of 2.0 to 10.0, and the cross sectional area is a perfect circle. It is preferable to have a flat cross section in which the fiber diameter (hereinafter, also referred to as the converted fiber diameter) when converted to is in the range of 3.0 to 35.0 μm. When the glass fiber contained in the glass fiber reinforced resin composition has such a cross section, as compared with the case where the glass fiber has a circular cross section, when E glass fiber is used under the same conditions except for the composition, the glass fiber is reinforced. The improvement rate of tensile strength, bending strength, bending elastic modulus, and impact strength based on the tensile strength, bending strength, bending elastic modulus, and impact strength of the molded product made of the resin composition becomes extremely high.

  In the glass fiber, the ratio of the major axis to the minor axis of the cross-sectional shape (major axis/minor axis) is high tensile strength, bending strength, bending elastic modulus, and impact strength of the molded article made of the glass fiber reinforced resin composition, and glass. From the viewpoint of compatibility with the fiber easiness of manufacture, the range is preferably 2.2 to 6.0, and more preferably 3.2 to 4.5. When the glass fiber is formed by bundling a plurality of glass filaments, the cross-sectional shape of the glass fiber means the cross-sectional shape of the glass filament forming the glass fiber.

  In the glass fiber, the reduced fiber diameter is high tensile strength, bending strength, bending elastic modulus, and impact strength of a molded article made of the glass fiber reinforced resin composition, and the glass fiber or the glass fiber reinforced resin composition is produced. From the viewpoint of compatibility with the ease of production at the time of performing, it is preferably in the range of 6.0 to 20 μm, and more preferably 6.5 to 16.0 μm. When the glass fiber is formed by bundling a plurality of glass filaments, the fiber diameter of the glass fiber means the fiber diameter of the glass filament forming the glass fiber.

  Further, in the glass fiber, as the shape of the flat cross section, cocoon shape, elliptical shape or oval shape (semicircle at both ends of a rectangle) because of excellent fluidity when producing a molded product from the glass fiber reinforced resin composition. A shape with a shape like or a shape similar thereto is preferable, and an ellipse is more preferable.

  In the present invention, the glass fiber contained in the glass fiber reinforced resin composition is preferably coated with urethane resin, epoxy resin, or a mixture of these resins. By coating the glass fiber with these, the adhesiveness between the glass fiber and the resin is increased, and the high tensile strength, bending strength, bending elastic modulus, and impact strength of the molded article made of the glass fiber reinforced resin composition are Will be realized. If the glass fiber is coated with a urethane resin, an epoxy resin, or a mixture of these resins, the glass fiber is coated with a component other than these resins in addition to these resins. Good.

  In the glass fiber, the urethane resin, the epoxy resin, or the mixture of these resins is a glass fiber at a ratio of 0.1 to 1.0% by mass based on the mass of the glass fiber not covered with the urethane resin, the epoxy resin, or the resin. Is preferably coated. By coating the glass fiber with a urethane resin, an epoxy resin, or a mixture of these resins within this range, the adhesiveness between the glass fiber and the resin can be reliably enhanced.

  The molded article of the present invention comprises the glass fiber reinforced resin composition of the present invention described above. More specifically, the molded article of the present invention is produced by using the glass fiber reinforced resin composition of the present invention by injection molding, injection compression molding, two-color molding, blow molding, foam molding (also for supercritical fluids). Including, insert molding, in-mold coating molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminated molding method, press molding method, blow molding method, stamping molding method, infusion method, handlay It is obtained by molding by a known molding method such as an up method, a spray up method, a resin transfer molding method, a sheet molding compound method, a bulk molding compound method, a pultrusion method, or a filament winding method.

  Next, embodiments of the present invention will be described in more detail.

The glass fiber reinforced resin composition of the present embodiment contains a glass fiber in the range of 10 to 90 mass% and a resin in the range of 10 to 90 mass% with respect to the total amount of the glass fiber reinforced resin composition. The fibers are SiO _{2 in} the range of 57.0 to 60.0% by mass, Al ₂ O _{3 in} the range of 17.5 to 20.0% by mass, and 8.5 to 12.0% by mass with respect to the total amount of the glass fibers. and% of the MgO, CaO in the range of 10.0 to 13.0 wt%, and a _B 2 _{O 3} in the range of 0.5 to 1.5 wt%, _and, SiO 2, _Al 2 O _3, the total amount of MgO and CaO is Ri der 98.0 mass% or more, content of _B 2 _{O 3} with respect to the content of _Al 2 _{O 3} (wt%) (wt%) and the CaO content (wt% )) ((B ₂ O ₃ (mass %)×CaO (mass %))/Al ₂ O ₃ (mass %)) is in the range of 0.25 to 0.75 .

  When the glass fiber has a composition within the above range, high tensile strength, high bending strength, high bending elastic modulus, and high impact strength of a molded article made of the glass fiber reinforced resin composition are realized.

  The glass fiber is manufactured by the following method. First, a glass raw material (glass batch) prepared to have the above-described composition is supplied to a melting furnace and melted at a temperature in the range of 1450 to 1550°C, for example. Next, the melted molten glass is discharged from a nozzle tip of a bushing whose temperature is controlled to a predetermined temperature, and is wound at a high speed to be cooled while being stretched and solidified to form glass fibers. Here, usually, the glass fiber is formed in a state in which a plurality of glass filaments drawn out from one nozzle tip are bundled. Also, the glass fibers usually have a circular cross section.

  For example, in the case of manufacturing glass fibers having an irregular cross section such as a flat shape, the nozzle tip has a nozzle plate on the bottom surface of the bushing with a ratio of major axis to minor axis (major axis/minor axis) of 2.0 to 10. An opening (orifice hole) having a major axis of 1.0 to 10.0 mm and a minor axis of 0.5 to 2.0 mm in the range of 0, and a notch for quenching the molten glass that has passed through the opening. It is possible to use a device provided with a cooling means such as a portion or a protrusion.

  The glass fiber has a weight in the range of 100 to 10000 tex (g/km) by being bundled with a plurality of glass filaments.

  In the process of forming the glass fiber, the surface thereof is coated with an organic material for the purpose of improving the filament converging property and the adhesiveness between the glass fiber and the resin. As such an organic substance, a urethane resin, an epoxy resin, or a mixture of these resins can be preferably used, and in addition to these resins, a resin composition containing a silane coupling agent, a film forming agent, a lubricant, etc. A thing can be used. Such a resin composition coats the glass fibers at a rate of 0.1 to 2.0 mass% based on the mass of the glass fibers not coated with the resin composition. Incidentally, the coating of the glass fiber with an organic material, for example, in the manufacturing process of the glass fiber, a resin solution or a resin composition solution is applied to the glass fiber using a known method such as a roller-type applicator, and then the resin solution or the resin. It can be performed by drying the glass fiber provided with the composition solution.

  As the resin, a thermoplastic resin or a thermosetting resin can be used, but since many applications require high tensile strength, flexural strength, flexural modulus, and impact strength, the thermoplastic resin is used. Is preferred.

  Examples of the thermoplastic resin include polyethylene resin, polypropylene resin, polystyrene resin, acrylonitrile/butadiene/styrene (ABS) resin, methacrylic resin, vinyl chloride resin, polyamide resin, polyacetal resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate ( PBT) resin, polycarbonate resin, polyphenylene sulfide (PPS) resin, polyether ether ketone (PEEK) resin, liquid crystal polymer (LCP) resin, fluororesin, polyetherimide (PEI) resin, polyarylate (PAR) resin, polysulfone ( Examples thereof include PSF) resin, polyether sulfone (PES) resin, polyamide imide (PAI) resin and the like. Among these, a polyamide resin, a polybutylene terephthalate resin, or a polycarbonate resin is preferable, and a polyamide resin is more preferable, because many applications require high tensile strength, bending strength, bending elastic modulus, and impact strength.

  Examples of the thermosetting resin include unsaturated polyester resin, vinyl ester resin, epoxy resin, melamine resin, phenol resin, urethane resin, polyisocyanate resin, polyisocyanurate resin, and polyimide resin.

  The thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more kinds.

  The glass fiber reinforced resin composition of the present invention may contain components other than the glass fiber and the resin as long as the object of the present invention is not impaired. Examples of such components include glass fibers other than the glass fibers (for example, E glass fiber, S glass fiber), reinforcing fibers other than glass fiber (for example, carbon fiber, metal fiber), fillers other than glass fiber (for example, , Glass powder, talc, mica), flame retardant, UV absorber, heat stabilizer, antioxidant, antistatic agent, fluidity improver, antiblocking agent, lubricant, nucleating agent, antibacterial agent, pigment, etc. be able to. Moreover, the glass fiber reinforced resin composition of this invention can contain these components in the range of 0-40 mass% in total with respect to the total amount of the glass fiber reinforced resin composition.

  The glass fiber reinforced resin composition of the present invention is obtained, for example, by kneading a glass fiber (chopped strand), which is formed by bundling a plurality of glass filaments and cut into a length of 1 to 25 mm, with a resin. be able to. The obtained glass fiber reinforced resin composition can be processed into a pellet shape by extruding it from a nozzle and cutting it into a predetermined length (for example, 1 to 50 mm). Alternatively, the glass fiber reinforced resin composition of the present invention is formed by bundling a plurality of glass filaments and continuously impregnating the glass fibers (roving) with a molten thermoplastic resin. It can be obtained by holding the thermoplastic resin around the roving by cooling. The obtained glass fiber reinforced resin composition can be processed into a pellet shape by cutting into a predetermined length (for example, 1 to 50 mm). In the latter example, the fiber length of the glass fiber in the glass fiber reinforced resin composition is substantially equal to the length of the pellet (predetermined cut length).

  A molded product made of the glass fiber reinforced resin composition of the present invention can be obtained, for example, by processing the pellets obtained as described above into a molded product by the above-mentioned known molding method.

  In the molded article comprising the glass fiber reinforced resin composition of the present invention, when the glass fiber has the above-mentioned flat cross section, the number average fiber length of the glass fiber in the molded article is, for example, in the range of 250 to 400 μm, and 265 It is preferably in the range of ˜350 μm. In the glass fiber reinforced resin composition, the glass fibers have an average fiber length in the above range, so that a molded article made of the glass fiber reinforced resin composition has high tensile strength, bending strength, bending elastic modulus, and impact. Strength is realized.

  Here, when the number average fiber length of the glass fibers in the molded article made of the glass fiber reinforced resin composition of the present invention is within the above range, the ratio of the glass fibers having a fiber length of 250 μm or more is 40.0. It is preferably at least mass%, more preferably at least 45.0 mass%, even more preferably at least 48.0 mass%. In the molded article made of the glass fiber reinforced resin composition of the present invention, the fiber length of the glass fibers is thus distributed, so that the molded article made of the glass fiber reinforced resin composition has high tensile strength, bending strength, and bending strength. Elastic modulus and impact strength are achieved.

  As a method for measuring the number average fiber length of glass fibers in a molded product made of the glass fiber reinforced resin composition of the present invention, first, a molded product made of the glass fiber reinforced resin composition is, for example, 300 to 650°C. The organic matter is decomposed by heating in a muffle furnace for about 0.5 to 24 hours. Next, the remaining glass fibers are transferred to a glass petri dish and dispersed on the surface of the petri dish using acetone. Next, the fiber length of 500 or more glass fibers dispersed on the surface is measured using a stereoscopic microscope, and the number average fiber length is calculated.

  Examples of the use of the molded product made of the glass fiber reinforced resin composition of the present invention include electronic device housings, electronic parts, vehicle exterior members, vehicle interior members, vehicle engine surrounding members, high pressure tanks and the like. Since it is required to combine tensile strength, flexural strength, flexural modulus, and impact strength at a high level, applications of molded articles made of the glass fiber reinforced resin composition of the present invention include smartphones, tablets, and laptop computers. A portable electronic device housing such as a portable music player or a portable game machine is preferable.

  Next, examples and comparative examples of the present invention will be shown.

[Glass composition]
Four types of glass compositions shown in Table 1 were used. Here, the composition 1 and the composition 2 are glass compositions of the glass fiber used in the glass fiber reinforced resin composition of the present invention, and the composition 3 is Al ₂ O ₃ , CaO and B ₂ O _{3 which} are the glass fiber reinforced resin of the present invention. The composition is out of the glass composition range of the glass fiber used, and the composition 4 corresponds to the E glass composition.

  The fiber elastic modulus of each glass composition was a test piece obtained by adhering one glass filament having no scratches or deterioration due to contact, friction, etc., to a predetermined mount having a hole with a diameter of 50 mm in the center, The test piece was set in the grip of the tensile tester, the end of the backing paper was cut off, and a tensile test was performed at a crosshead speed of 5 mm/min. The tensile strength was calculated from the initial strength variation value and the elongation rate corresponding thereto. The test piece in which the yarn was missing during the measurement was excluded, and the average value of n=15 was used as the measured value of the fiber elastic modulus.

[resin]
UBE NYLON 1015B (trade name, manufactured by Ube Industries, Ltd.) was used as the polyamide resin (PA is shown in the table).

  Panlite L-1250Y (trade name, manufactured by Teijin Limited) was used as the polycarbonate resin (indicated as PC in the table).

[Tensile strength]
The tensile strength of the molded product made of the glass fiber reinforced resin composition was measured according to ISO527.

[Bending strength]
The flexural strength of the molded product made of the glass fiber reinforced resin composition was measured according to ISO178.

[Flexural modulus]
The flexural strength of the molded product made of the glass fiber reinforced resin composition was measured according to ISO178.

[Charpy impact strength]
The Charpy impact strength of the glass fiber reinforced resin composition was measured according to ISO179.

[Example 1-2, Comparative example 1-2]
As shown in Table 2, for a glass fiber reinforced resin composition composed of a glass fiber having a circular cross section each having the compositions 1 to 4 and a polyamide resin, a case where the glass fiber has the composition 1 is described in Example 1, Tensile strength and bending strength of a molded article made of the glass fiber reinforced resin composition, where the composition 2 is provided as Example 2, the composition 3 is provided as Comparative Example 1, and the composition 4 is provided as Comparative Example 2. The flexural modulus and the Charpy impact strength were evaluated.

  In the table, the values in square brackets in the tensile strength, flexural strength, flexural modulus and Charpy impact strength columns mean relative values when the composition 4 (E glass composition) is used as 100. ..

  As shown in Table 2, the molded article made of the glass fiber reinforced resin composition of Example 1 and Example 2 having the glass composition defined in the present invention is the glass fiber reinforced resin of Comparative Example 2 having the E glass composition. The tensile strength, the bending strength, the bending elastic modulus, and the Charpy impact strength all have higher values than those of the molded product made of the composition.

On the other hand, a molded article made of the glass fiber reinforced resin composition of Comparative Example 1 in which Al ₂ O ₃ , CaO and B ₂ O ₃ are out of the glass composition range specified in the present invention has a tensile strength, a bending strength and a The flexural modulus is higher than those in Examples 1 and 2 and Comparative Example 2, but the Charpy impact strength is inferior to Comparative Example 2.

[Example 3-4, Comparative Example 3-4]
As shown in Table 3, with respect to a glass fiber reinforced resin composition composed of a glass fiber having an oval cross section having the compositions 1 to 4 and a polyamide resin, a case where the glass fiber has the composition 1 is described in Example 3, Tensile strength and bending of a molded article made of the glass fiber reinforced resin composition, where the composition 2 is provided as Example 4, the composition 3 is provided as Comparative Example 3, and the composition 4 is provided as Comparative Example 4. The strength, flexural modulus and Charpy impact strength were evaluated.

  In the table, the values in square brackets in the tensile strength, flexural strength, flexural modulus and Charpy impact strength columns mean relative values when the composition 4 (E glass composition) is used as 100. ..

  As shown in Table 3, the molded article made of the glass fiber reinforced resin composition of Example 3 and Example 4 having the glass composition defined in the present invention was the glass fiber reinforced resin of Comparative Example 4 having the E glass composition. The tensile strength, the bending strength, the bending elastic modulus, and the Charpy impact strength all have higher values than those of the molded product made of the composition. Further, from the comparison between Table 2 and Table 3, when the cross-sectional shape of the glass fiber is a flat cross section (oval), a molded article made of the glass fiber reinforced resin composition containing the glass fiber having the E glass composition was used as a reference. The rate of improvement in tensile strength etc. is extremely high.

On the other hand, a molded article made of the glass fiber reinforced resin composition of Comparative Example 3 in which Al ₂ O ₃ , CaO and B ₂ O ₃ are out of the glass composition range defined in the present invention has a tensile strength, a bending strength and a The flexural modulus is higher than that of Comparative Example 4, but the Charpy impact strength is equivalent to that of Comparative Example 4.

  Further, from the comparison between Table 2 and Table 3, when the cross-sectional shape of the glass fiber is circular, the molded article made of the glass fiber reinforced resin composition that is composed of the glass fiber having the composition 1 or 2 has a composition Although the tensile strength, the bending strength and the bending elastic modulus are slightly inferior to those of the molded product formed of the glass fiber reinforced resin composition including the glass fiber having the glass composition including the glass composition of 3, the glass fiber has a flat cross section ( On the contrary, these values are excellent in the case of (oval).

[Example 5, Comparative Example 5-6]
As shown in Table 4, with respect to a glass fiber reinforced resin composition comprising a glass fiber having an oval cross section having the compositions 2 to 4 and a polycarbonate resin, a case where the glass fiber has the composition 2 is described in Example 5, The tensile strength, the bending strength, the bending elastic modulus and the Charpy impact strength of a molded article made of the glass fiber reinforced resin composition are shown as Comparative Example 5 including the composition 3 and Comparative Example 6 including the composition 4. evaluated.

  In the table, the values in square brackets in the tensile strength, bending strength, flexural modulus and Charpy impact strength columns are relative to the tensile strength when composition 4 (E glass composition) is used as 100. Means a value.

  As shown in Table 4, the molded article made of the glass fiber reinforced resin composition of Example 2 having the glass composition defined in the present invention is made of the glass fiber reinforced resin composition of Comparative Example 6 having the E glass composition. The tensile strength, the bending strength, the bending elastic modulus, and the Charpy impact strength are all higher than those of the molded product.

On the other hand, a molded article made of the glass fiber reinforced resin composition of Comparative Example 5 in which Al ₂ O ₃ , CaO and B ₂ O ₃ are out of the glass composition range specified in the present invention has a tensile strength, a bending strength and a The flexural modulus is higher than that of Comparative Example 6, but the Charpy impact strength is inferior to that of Comparative Example 6.

Claims (4)

A glass fiber reinforced resin composition containing glass fibers in the range of 10 to 90 mass% and resin in the range of 90 to 10 mass% with respect to the total amount of the glass fiber reinforced resin composition,
The glass fiber is composed of SiO _{2 in} the range of 57.0 to 60.0% by mass, Al ₂ O _{3 in} the range of 17.5 to 20.0% by mass, and 8.5 to 12. It contains MgO in the range of 0% by mass, CaO in the range of 10.0 to 13.0% by mass, and B ₂ O _{3 in} the range of 0.5 to 1.5% by mass, and SiO ₂ and Al. ₂ O _3, the total amount of MgO and CaO is Ri der 98.0 mass% or more, content of _B 2 _{O 3} with respect to the content of _Al 2 _{O 3} (wt%) (wt%) and the CaO content ( Mass%) and the ratio ((B ₂ O ₃ (mass %)×CaO (mass %))/Al ₂ O ₃ (mass %)) is in the range of 0.25 to 0.75. A glass fiber reinforced resin composition characterized by the above.   The glass fiber reinforced resin composition according to claim 1, wherein the glass fiber has a ratio of a major axis to a minor axis of the cross-sectional shape (major axis/minor axis) in a range of 2.0 to 10.0 and a true cross-sectional area. A glass fiber reinforced resin composition having a flat cross section in which the fiber diameter when converted to a circle is in the range of 3.0 to 35.0 μm.   The glass fiber reinforced resin composition according to claim 1 or 2, wherein the glass fiber is coated with a urethane resin, an epoxy resin, or a mixture of these resins. object.   A molded article comprising the glass fiber reinforced resin composition according to any one of claims 1 to 3.