Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
  • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C13/00—Fibre or filament compositions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/40—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles

Definitions

• the present invention relates to a glass fiber reinforced resin molded product.
• the glass fiber having the E glass composition is most commonly used.
• the E glass composition is a total of 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 glass fiber. It is a composition containing MgO and CaO in the range of 20.0 to 25.0% by mass and B2O 3 in the range of 5.0 to 10.0% by mass.
• Patent Document 2 The applicant has proposed a glass fiber reinforced resin molded product using a glass fiber having a glass composition other than the E glass composition in accordance with the sophistication of the performance required for the glass fiber reinforced resin molded product. 1. See Patent Document 2).
• a glass fiber reinforced resin molded product containing a glass fiber having a glass composition containing Al 2 O 3 , MgO and CaO may have high tensile strength, high bending strength, high bending elasticity, and high impact strength. It is described in Patent Document 1.
• Glass containing glass fibers having a glass composition comprising a range of TiO 2 and less than 1.5% by weight F 2 and a total of less than 0.6% by weight Li 2 O, Na 2 O, and K 2 O. It is described in Patent Document 2 that a fiber-reinforced resin molded product has high tensile strength, high impact strength, low dielectric constant and low dielectric tangent.
• Patent Document 2 describes that the dielectric loss energy in the glass fiber reinforced resin molded product is proportional to the dielectric constant and the dielectric loss tangent of the glass fiber reinforced resin molded product and is expressed by the following equation ( ⁇ ). There is. Generally, it is known that glass absorbs energy as heat with respect to alternating current, and the energy absorbed by glass is dielectric loss energy.
• W kfv 2 ⁇ ⁇ tan ⁇ ⁇ ⁇ ⁇ ( ⁇ )
• W the dielectric loss energy
• k a constant
• f the frequency
• v 2 the potential gradient
• ⁇ the permittivity
• tan ⁇ the dielectric loss tangent
• Glass fiber reinforced resin molded products generally have a greater degree of deformation (shrinkage, expansion) with respect to heat than metal, and this difference in the amount of deformation weakens the bond with metal, which is one factor that causes poor adhesion and equipment defects. Presumed to be. Therefore, the glass fiber reinforced resin molded product needs to have higher dimensional stability than the conventional one, particularly a low coefficient of linear expansion. Further, the importance of suppressing heat generation in the glass fiber reinforced resin molded product is increasing in accordance with the correspondence to the high frequency of the portable electronic device, and it is also necessary to lower the dielectric property of the glass fiber reinforced resin molded product.
• the glass fiber reinforced resin molded product containing the glass fiber having the glass composition described in Patent Document 1 or Patent Document 2 has a disadvantage that it cannot have both high dimensional stability and low dielectric property.
• An object of the present invention is to eliminate such inconvenience and provide a glass fiber reinforced resin molded product having both high dimensional stability and low dielectric properties.
• the glass fiber reinforced resin molded product of the present invention has a glass fiber fiber diameter D contained in the glass fiber reinforced resin molded product in a length in the range of 5.0 to 15.0 ⁇ m.
• the dielectric constant Dk of the glass fiber contained in the glass fiber reinforced resin molded product at a measurement frequency of 1 GHz is in the range of 4.0 to 7.0
• the linear expansion coefficient C of the glass fiber contained in the glass fiber reinforced resin molded product is 2. It is in the range of 0.0 to 6.0 ppm / K
• the number average fiber length L of the glass fibers contained in the glass fiber reinforced resin molded product is in the range of 150 to 400 ⁇ m, and the D, Dk, C and L are described above. Is characterized by satisfying the following equation (1). 57.9 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 70.6 ... (1)
• the glass fiber reinforced resin molded product of the present invention when the D, Dk, C and L are in the above-mentioned range and the condition of the above formula (1) is satisfied, high dimensional stability and low dielectric property are obtained. Can be combined with.
• the fact that the glass fiber reinforced resin molded product has both high dimensional stability and low dielectric property means that the dimensional stability / dielectric property index shown below is 0.85 or less.
• the dimensional stability / dielectric property index is a value obtained by multiplying the dielectric constant MDk of the glass fiber reinforced resin molded product of the present invention at a measurement frequency of 1 GHz by the linear expansion coefficient MC of the glass fiber reinforced resin molded product of the present invention (MDk ⁇ ).
• the reference glass fiber reinforced resin molded product includes glass fibers having an E glass composition and a fiber diameter of 11.0 ⁇ m at the same glass content as the glass fiber reinforced resin molded product of the present invention, and the present invention. It is a glass fiber reinforced resin molded product manufactured under the same molding conditions as the glass fiber reinforced resin molded product.
• the dielectric constant Dk of glass fiber at a measurement frequency of 1 GHz can be measured by the following method. First, the glass fiber reinforced resin molded product is heated in a muffle furnace having a temperature in the range of 300 to 650 ° C. for about 0.5 to 24 hours to decompose organic substances. Next, the remaining glass fiber is placed in a platinum rut pot, kept at a temperature of 1600 ° C. for 6 hours in an electric furnace, and melted while stirring to obtain a homogeneous molten glass. Next, the platinum crucible containing the molten glass is taken out of the electric furnace and the molten glass is cooled.
• the obtained glass block is processed into a test piece having a width of 3 mm, a length of 80 mm, and a thickness of 1 mm by using a cutting machine, for example, a diamond cutter and a polishing machine.
• the dielectric constant Dk of the obtained test piece at the measurement frequency of 1 GHz of the glass fiber can be measured by measuring the dielectric constant at the measurement frequency of 1 GHz in accordance with JIS C 2565: 1992.
• the coefficient of linear expansion C of glass fiber can be calculated by the following method. First, a glass gob is obtained in exactly the same manner as the above-mentioned method for measuring the dielectric constant of glass fibers. Next, the obtained glass block is processed into a test piece of 4 mm ⁇ 4 mm ⁇ 20 mm using a cutting machine, for example, a diamond cutter and a polishing machine. Next, the obtained test piece was heated at a heating rate of 10 ° C./min, and the elongation was measured at a temperature in the range of 50 to 200 ° C. using a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Co., Ltd.). By calculating the linear expansion coefficient from the elongation amount, the linear expansion coefficient C of the glass fiber can be calculated.
• the dielectric constant of the glass fiber reinforced resin molded product at a measurement frequency of 1 GHz can be measured in accordance with JIS C 2565: 1992.
• the coefficient of linear expansion of the glass fiber reinforced resin molded product can be calculated in accordance with JIS K 7197: 2012 (measurement temperature range: 50 to 200 ° C., temperature rise rate: 10 ° C./min).
• the D, Dk, C and L satisfy the following formula (2). 58.2 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 61.7 ... (2)
• the glass fiber reinforced resin molded product of the present invention if the D, Dk, C and L are in the above-mentioned range and the condition of the above formula (2) is satisfied, the glass fiber reinforced resin molded product can be obtained. It combines high dimensional stability with low dielectric properties at a higher level.
• the fact that the glass fiber reinforced resin molded product has both high dimensional stability and low dielectric property at a higher level means that the dimensional stability / dielectric property index shown below is 0.80 or less. ..
• the dimensional stability / dielectric property index is a value obtained by multiplying the dielectric constant MDk of the glass fiber reinforced resin molded product of the present invention at a measurement frequency of 1 GHz by the linear expansion coefficient MC of the glass fiber reinforced resin molded product of the present invention (MDk ⁇ ).
• the ratio (MC) to the value obtained by multiplying the dielectric constant EDk of the standard glass fiber reinforced resin molded product at a measurement frequency of 1 GHz by the linear expansion coefficient EC of the standard glass fiber reinforced resin molded product ((MDk ⁇ MC) / (EDk ⁇ ). EC)).
• the reference glass fiber reinforced resin molded product includes glass fibers having an E glass composition and a fiber diameter of 11.0 ⁇ m at the same glass content as the glass fiber reinforced resin molded product of the present invention, and the present invention. It is a glass fiber reinforced resin molded product manufactured under the same molding conditions as the glass fiber reinforced resin molded product.
• the glass fiber contained in the glass fiber reinforced resin molded product has SiO 2 in the range of 60.00 to 70.00 mass% with respect to the total amount of the glass fiber.
• Al 2 O 3 in the range of 20.00 to 30.00 mass%
• Mg O in the range of 5.00 to 15.0 mass%
• Fe 2 O 3 in the range of 0.15 to 1.50 mass%.
• the resin contained in the glass fiber reinforced resin molded product is polybutylene terephthalate.
• the fiber diameter D of the glass fiber contained in the glass fiber reinforced resin molded product is in the range of 5.0 to 15.0 ⁇ m, and the glass contained in the glass fiber reinforced resin molded product.
• the dielectric constant Dk at a fiber measurement frequency of 1 GHz is in the range of 4.0 to 7.0, and the linear expansion coefficient C of the glass fiber contained in the glass fiber reinforced resin molded product is in the range of 2.0 to 6.0 ppm / K.
• the number average fiber length L of the glass fibers contained in the glass fiber reinforced resin molded product is in the range of 150 to 400 ⁇ m, and the D, Dk, C and L satisfy the following formula (1). .. 57.9 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 70.6 ... (1)
• the glass fiber reinforced resin molded product of the present embodiment if the D, Dk, C and L are in the above-mentioned range and the condition of the above formula (1) is satisfied, the glass fiber reinforced resin molded product can be obtained. It has both high dimensional stability and low dielectric properties.
• the fiber diameter D of the glass fiber is less than 5.0 ⁇ m, the number of glass fibers is remarkably increased when the resin and the glass fiber are kneaded, so that the productivity is increased. In addition, the fiber length is significantly shortened, so that a sufficient reinforcing effect cannot be obtained.
• the fiber diameter D of the glass fiber exceeds 15.0 ⁇ m, the contact surface area between the resin and the glass fiber becomes small, so that a sufficient reinforcing effect can be obtained. I can't.
• the fiber diameter D of the glass fiber is preferably in the range of 6.0 to 14.0 ⁇ m, and more preferably in the range of 7.0 to 13.0 ⁇ m. It is more preferably in the range of 8.0 to 12.0 ⁇ m, and particularly preferably in the range of 8.5 to 11.5 ⁇ m.
• the fiber diameter D of the glass fiber is determined by, for example, first polishing the cross section of the glass fiber reinforced resin molded product, and then using an electron microscope to per 100 or more glass filaments. , It can be calculated by measuring the length of the diameter of the glass filament and obtaining the average value of these.
• the glass filament usually has a circular cross-sectional shape.
• the glass fiber is usually formed by focusing a plurality of glass filaments, but in the glass fiber reinforced resin molded product, the focused is released by undergoing a molding process, and the glass fiber is in the state of a glass filament. It is dispersed in the glass fiber reinforced resin molded product.
• the glass fiber reinforced resin molded product of the present embodiment the glass fiber having a dielectric constant Dk of less than 4.0 at a measurement frequency of 1 GHz is difficult to use from the viewpoint of economy because its manufacturability is low. On the other hand, if the dielectric constant Dk of the glass fiber at a measurement frequency of 1 GHz exceeds 7.0, the glass fiber reinforced resin molded product cannot have sufficient dielectric properties.
• the dielectric constant Dk of the glass fiber at a measurement frequency of 1 GHz is preferably in the range of 5.1 to 5.9, and preferably in the range of 5.2 to 5.6. It is more preferable that it is in the range of 5.3 to 5.5.
• the glass fiber reinforced resin molded product of the present embodiment the glass fiber having a linear expansion coefficient C of less than 2.0 ppm / K is difficult to use from the viewpoint of economic efficiency because its manufacturability is low. ..
• the coefficient of linear expansion C of the glass fiber exceeds 6.0 ppm / K, the glass fiber reinforced resin molded product cannot have sufficient dimensional stability.
• the linear expansion coefficient C of the glass fiber is preferably in the range of 2.2 to 3.4 ppm / K, and is preferably in the range of 2.5 to 3.1 ppm / K. It is more preferably in the range of 2.6 to 3.0 ppm / K.
• the number average fiber length L of the glass fibers is less than 150 ⁇ m, the reinforcing effect of the glass fiber reinforced resin molded product by the glass fibers becomes insufficient. On the other hand, if the number average fiber length L of the glass fibers is more than 400 ⁇ m, the appearance of the glass fiber reinforced resin molded product is impaired.
• the number average fiber length L of the glass fiber is preferably in the range of 170 to 340 ⁇ m, more preferably in the range of 200 to 320 ⁇ m, and more preferably 210 to 300 ⁇ m. It is more preferably in the range, particularly preferably in the range of 220 to 290 ⁇ m, and most preferably in the range of 225 to 285 ⁇ m.
• the number average fiber length L of the glass fiber can be calculated by, for example, the following method. First, the glass fiber reinforced resin molded product is heated in a muffle furnace at 650 ° C. for 0.5 to 24 hours to decompose organic substances. The remaining glass fibers are then transferred to a glass petri dish and the glass fibers are dispersed on the surface of the petri dish using acetone. Next, the fiber length of 1000 or more glass fibers dispersed on the surface of the petri dish is measured using a stereomicroscope. Then, by obtaining the average value, the number average fiber length L of the glass fiber can be calculated.
• the number average fiber length L of the glass fibers contained in the glass fiber reinforced resin molded product of the present embodiment is, for example, a twin-screw kneader when the glass fiber reinforced resin molded product of the present embodiment is obtained by injection molding. It can be controlled by adjusting the length of the chopped strands charged into the fiberglass and the screw rotation speed of the twin-screw kneader. For example, the length of the chopped strands charged into the twin-screw kneader is adjusted in the range of 1.0 to 100.0 mm. The L can be lengthened by increasing the length of the chopped strands charged into the twin-screw kneader, and the L can be shortened by shortening the length of the chopped strands.
• the screw rotation speed at the time of biaxial kneading is adjusted in the range of 10 to 1000 rpm.
• the glass fiber reinforced resin molded product of the present embodiment has both high dimensional stability and low dielectric properties when the D, Dk, C and L satisfy the following formula (1). 57.9 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 70.6 ... (1)
• the D, Dk, C and L are described as described above. It is preferable to satisfy the following formula (2), more preferably to satisfy the following formula (3), and further preferably to satisfy the following formula (4). 58.2 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 61.7 ... (2) 59.0 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 61.0 ... (3) 59.5 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 60.5 ... (4)
• the glass fibers contained in the glass fiber reinforced resin molded product are SiO 2 in the range of 60.00 to 70.00 mass% with respect to the total amount of glass fibers, and 20.
• Al 2 O 3 in the range of .00 to 30.00 mass%
• Mg O in the range of 5.00 to 15.0 mass%
• Fe 2 O 3 in the range of 0.15 to 1.50 mass%. It is preferable to have a composition containing Li 2 O, Na 2 O and K 2 O in the range of 0.02 to 0.20% by mass in total.
• the content of SiO 2 with respect to the total amount of the glass fiber is preferably in the range of 60.50 to 67.50% by mass, preferably from 61.00 to. It is more preferably in the range of 67.00% by mass, further preferably in the range of 63.00 to 66.50% by mass, and particularly preferably in the range of 64.00 to 66.00% by mass.
• the content of Al 2 O 3 with respect to the total amount of the glass fiber is preferably in the range of 20.50 to 27.50% by mass, and 21. It is more preferably in the range of 00 to 27.00% by mass, further preferably in the range of 23.00 to 26.50% by mass, and particularly preferably in the range of 24.00 to 26.00% by mass. preferable.
• the content of MgO with respect to the total amount of the glass fiber is preferably in the range of 6.00 to 14.00% by mass, preferably 7.00 to 13. It is more preferably in the range of .00% by mass, further preferably in the range of 8.00 to 12.50% by mass, and particularly preferably in the range of 9.00 to 11.00% by mass.
• the content of Fe 2 O 3 with respect to the total amount of the glass fiber is preferably in the range of 0.15 to 0.50% by mass, and 0. It is more preferably in the range of 20 to 0.45% by mass, further preferably in the range of 0.25 to 0.45% by mass, and particularly preferably in the range of 0.30 to 0.40% by mass. preferable.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment contains Fe 2 O 3 in this range, thereby suppressing the coloring of the glass fiber and improving the defoaming property of the molten glass. The manufacturability of the glass can be improved.
• the total content of Li 2 O, Na 2 O and K 2 O with respect to the total amount of the glass fiber is in the range of 0.03 to 0.15% by mass. It is preferably in the range of 0.04 to 0.10% by mass, and more preferably in the range of 0.04 to 0.10% by mass.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment contains Li 2 O, Na 2 O and K 2 O in this range, so that the dielectric constant of the glass fiber is kept low while the molten glass is made of molten glass. It is possible to reduce the melt viscosity and improve the manufacturability of the glass fiber.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment may contain CaO in the range of 0.01 to 0.10% by mass. By including CaO in this range, the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment reduces the melt viscosity of the molten glass while maintaining high strength and elasticity of the glass fiber. The manufacturability of the glass can be improved.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment may contain ZrO 2 in the range of 0.01 to 0.10% by mass.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment contains ZrO 2 in this range, so that the linear expansion coefficient of the glass fiber is kept low and the melt viscosity of the molten glass is reduced to reduce the glass fiber. The manufacturability of the glass can be improved.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment may be substantially free of B 2 O 3 , F 2 and TiO 2 (that is, the content is less than 0.01% by mass). It is preferable that it is not contained at all (that is, the content is 0% by mass).
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment substantially does not contain B 2 O 3 , F 2 and TiO 2 , so that the elastic ratio of the glass fiber is maintained high and the glass fiber is made of glass fiber. Acid resistance can be increased.
• the ratio of the MgO content to the total content of Fe 2 O 3 and CaO is 17 It is preferably in the range of 0.0 to 37.0, more preferably in the range of 20.0 to 34.0, still more preferably in the range of 21.0 to 33.0, and 22.0 to 22.0 to 33.0. It is particularly preferably in the range of 32.0, and most preferably in the range of 23.0 to 31.0.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment contains MgO, Fe 2 O 3 and CaO in a ratio within this range, so that the elasticity of the glass fiber and the manufacturability of the glass fiber are at a high level. Can be compatible with.
• the content of each component described above is measured by using an ICP emission spectrophotometer for Li, which is a light element, and wavelength dispersive for other elements. This can be done using a type fluorescent X-ray analyzer.
• a measuring method first, a molten glass is obtained by making exactly the same as the above-mentioned method for measuring the dielectric constant of glass fiber. Next, the obtained molten glass is poured from a platinum crucible onto a carbon plate to prepare a glass cullet, which is then pulverized and pulverized to obtain a glass powder.
• Li which is a light element, is subjected to quantitative analysis using an ICP emission spectrophotometer after heat-decomposing the glass powder with an acid.
• Other elements are quantitatively analyzed using a wavelength dispersive fluorescent X-ray analyzer after the glass powder is formed into a disk shape with a press machine.
• the content and total amount of each component can be calculated by converting these quantitative analysis results into oxides, and the content (mass%) of each component described above can be obtained from these numerical values.
• the glass fiber having the above-mentioned glass composition can be produced as follows. First, a glass raw material (glass batch) prepared to have the above-mentioned composition is supplied to a melting furnace and melted at a temperature in the range of, for example, 1450 to 1550 ° C. Next, the molten glass batch (molten glass) is drawn from a number of nozzle tips in the range of 1 to 30,000 of the bushings controlled to a predetermined temperature and rapidly cooled to form a glass filament. Next, a sizing agent or a binder is applied to the formed glass filaments using an applicator, which is a coating device, and a winding machine is used to squeeze the glass filaments in the range of 1 to 30,000 using a sizing shoe. It can be used to obtain glass fiber by winding it around a tube at high speed.
• the number of glass filaments constituting the glass fiber is preferably 1 to 20000.
• the number is more preferably 50 to 10000, still more preferably 1000 to 8000
• the length of the glass fiber is preferably 1.0 to 100.0 mm, more preferably. Cut to a length in the range of 1.2 to 51.0 mm, more preferably 1.5 to 30.0 mm, particularly preferably 2.0 to 15.0 mm, and most preferably 2.3 to 7.8 mm.
• chopped strands In addition to the chopped strand, examples of the form in which the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment can be taken before the molding process include roving and cut fiber.
• the roving has a number of glass filaments constituting the glass fiber in the range of 10 to 30,000 and is not cut. Further, the cut fiber has 1 to 20000 glass filaments constituting the glass fiber, and has a length in the range of 0.001 to 0.900 mm by a known method such as a ball mill or a hensyl mixer. It is crushed.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment improves the adhesiveness between the glass fiber and the resin, improves the uniform dispersibility of the glass fiber in the mixture of the glass fiber and the resin or the inorganic material, and the like.
• the surface may be coated with an organic substance.
• organic substances include urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene, particularly carboxylic acid-modified polypropylene, (poly) carboxylic acid, and a copolymer of maleic acid and an unsaturated monomer.
• Resin or silane coupling agent can be mentioned.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment may be coated with a composition containing a lubricant, a surfactant and the like in addition to these resins or silane coupling agents.
• a composition coats the glass fiber at a ratio of 0.1 to 2.0% by mass based on the mass of the glass fiber in the state where it is not coated with the composition.
• a sizing agent or a binder is applied to the glass fiber by using a known method such as a roller type applicator.
• the sizing agent or binder comprises a solution of the resin, the silane coupling agent or the composition.
• the coating of the glass fiber can then be carried out by drying the glass fiber coated with the resin, the silane coupling agent or the solution of the composition.
• examples of the silane coupling agent include aminosilane, chlorsilane, epoxysilane, mercaptosilane, vinylsilane, acrylicsilane, and cationicsilane.
• these compounds may be used alone, or two or more kinds thereof may be used in combination.
• aminosilanes include ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ - (aminoethyl) -N'- ⁇ - (aminoethyl) - ⁇ -.
• aminosilanes include aminopropyltrimethoxysilane and ⁇ -anilinopropyltrimethoxysilane.
• chlorsilane examples include ⁇ -chloropropyltrimethoxysilane.
• epoxy silane examples include ⁇ -glycidoxypropyltrimethoxysilane and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
• Examples of the mercaptosilane include ⁇ -mercaptotrimethoxysilane.
• vinylsilane examples include vinyltrimethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane, and the like.
• acrylic silane examples include ⁇ -methacryloxypropyltrimethoxysilane.
• Examples of the cationic silane include N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N-phenyl-3-aminopropyltrimethoxysilane hydrochloride and the like.
• the lubricants may be used alone or in combination of two or more.
• animal oil examples include beef tallow.
• vegetable oils examples include soybean oil, palm oil, rapeseed oil, palm oil, castor oil and the like.
• animal wax examples include beeswax and lanolin.
• Examples of vegetable wax include candelilla wax and carnauba wax.
• mineral wax examples include paraffin wax, montan wax and the like.
• Examples of the condensate of the higher saturated fatty acid and the higher saturated alcohol include stearic acid esters such as lauryl stearate.
• fatty acid amide examples include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine and fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid.
• quaternary ammonium salt examples include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.
• surfactant examples include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
• the surfactants may be used alone or in combination of two or more.
• Nonionic surfactants include ethylene oxide propylene oxide alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene-block copolymers, alkylpolyoxyethylene-polyoxypropylene-block copolymer ethers, and polyoxyethylene fatty acid esters.
• Cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (acetates, hydrochlorides, etc.), ethylene oxide adducts to higher alkylamines, higher grades.
• alkylamine salts acetates, hydrochlorides, etc.
• ethylene oxide adducts to higher alkylamines higher grades.
• Examples thereof include a condensate of a fatty acid and a polyalkylene polyamine, a salt of an ester of a higher fatty acid and an alkanolamine, a salt of a higher fatty acid amide, an imidazoline type cationic surfactant, an alkylpyridinium salt and the like.
• anionic surfactants include higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, ⁇ -olefin sulfate ester salts, alkylbenzene sulfonates, ⁇ -olefin sulfonates, and reactions of fatty acid halide with N-methyltaurine.
• anionic surfactants include higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, ⁇ -olefin sulfate ester salts, alkylbenzene sulfonates, ⁇ -olefin sulfonates, and reactions of fatty acid halide with N-methyltaurine.
• examples thereof include products, sulfosuccinic acid dialkyl ester salts, higher alcohol phosphate ester salts, and higher alcohol ethylene oxide adduct phosphate ester salts.
• amphoteric tenside examples include an amino acid type amphoteric tenside such as an alkylaminopropionic acid alkali metal salt, a betaine type such as alkyldimethylbetaine, and an imidazoline type amphoteric tenside.
• amino acid type amphoteric tenside such as an alkylaminopropionic acid alkali metal salt
• betaine type such as alkyldimethylbetaine
• imidazoline type amphoteric tenside examples include imidazoline type amphoteric tenside.
• the glass fiber contained in the glass fiber reinforced resin molded product of the present embodiment is not limited to the reinforcing material in the glass fiber reinforced resin molded product, and may be suitably used as a reinforcing material for an inorganic material such as gypsum or cement. can.
• the glass fiber having the above range is in the range of 0.1 to 4.0% by mass with respect to the total mass of gypsum. It can contribute to the improvement of the mechanical strength, fire resistance, dimensional stability, etc. of gypsum.
• the glass fiber can be present with a number average fiber length of 30 to 25,000 ⁇ m.
• thermoplastic resin or a thermosetting resin can be used, but since there are many applications where high dimensional stability and low dielectric properties are required, heat is required. It is preferable to use a plastic resin.
• thermoplastic resin includes polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, and chlorine.
• polyethylene examples include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high-molecular-weight polyethylene.
• HDPE high-density polyethylene
• LDPE low-density polyethylene
• LLDPE linear low-density polyethylene
• ultra-high-molecular-weight polyethylene examples include ultra-high-molecular-weight polyethylene.
• polypropylene examples include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.
• polystyrene examples include general-purpose polystyrene (GPPS) which is an atactic polystyrene having an atactic structure, impact-resistant polystyrene (HIPS) obtained by adding a rubber component to GPPS, and syndiotactic polystyrene having a syndiotactic structure. ..
• GPPS general-purpose polystyrene
• HIPS impact-resistant polystyrene
• methacrylic acid a polymer obtained by homopolymerizing one of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl ester, or two or more thereof.
• examples thereof include a polymer obtained by copolymerizing the above.
• the polyvinyl chloride can be copolymerized with a vinyl chloride homopolymer polymerized by a conventionally known emulsification polymerization method, a suspension polymerization method, a microsuspension polymerization method, a bulk polymerization method, or the like, or a vinyl chloride monomer.
• a copolymer with a monomer a graft copolymer obtained by graft-polymerizing a vinyl chloride monomer to the polymer, and the like.
• polyamide examples include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polytetramethylene sebacamide (polyamide 410), and polypentamethylene adipa.
• Polyundecamethylene terephthalamide (polyamide 11T), polydodecamethylene terephthalamide (polyamide 12T), polytetramethylene isophthalamide (polyamide 4I), polybis (3-methyl-4-aminohexyl) methaneterephthalamide (polyamide PACMT) , Polybis (3-methyl-4-aminohexyl) methaneisophthalamide (polyamide PACMI), polybis (3-methyl-4-aminohexyl) methaneddecamide (polyamide PACM12), polybis (3-methyl-4-aminohexyl) Examples thereof include a copolymer in which one of the components such as methanetetradecamide (polyamide PACM14) or a plurality of two or more components are combined, a mixture thereof, and the like.
• the polyacetal includes a homopolymer having an oxymethylene unit as a main repeating unit and a copolymer containing an oxyalkylene unit having 2 to 8 adjacent carbon atoms in the main chain, which is mainly composed of an oximethylene unit. And so on.
• polyethylene terephthalate examples include a polymer obtained by polycondensing ethylene glycol with terephthalic acid or a derivative thereof.
• polybutylene terephthalate examples include a polymer obtained by polycondensing 1,4-butanediol with terephthalic acid or a derivative thereof.
• polytrimethylene terephthalate examples include a polymer obtained by polycondensing 1,3-propanediol with terephthalic acid or a derivative thereof.
• polycarbonate examples include a polymer obtained by an ester exchange method in which a dihydroxydiaryl compound and a carbonic acid ester such as diphenyl carbonate are reacted in a molten state, or a polymer obtained by a phosgene method in which a dihydroxyaryl compound and phosgene are reacted. be able to.
• polyphenylene sulfide examples include linear polyphenylene sulfide, crosslinked polyphenylene sulfide that has been polymerized by performing a curing reaction after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.
• Modified polyphenylene ethers include polymer alloys of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, and poly (2,6-dimethyl-1,4-phenylene) ethers and styrene / butadiene copolymers.
• polyaryletherketone examples include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK) and the like.
• the liquid crystal polymer (LCP) has one or more structures selected from aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units and the like, which are thermotropic liquid crystal polyesters. Examples thereof include (co) polymers composed of units.
• fluororesin examples include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluoroethylene propylene resin (FEP), fluoroethylene tetrafluoroethylene resin (ETFE), polyvinylfluorolide (PVF), and polyvinylidene fluoride.
• PTFE polytetrafluoroethylene
• PFA perfluoroalkoxy resin
• FEP fluoroethylene propylene resin
• ETFE fluoroethylene tetrafluoroethylene resin
• PVDF vinylidene
• PCTFE polychlorotrifluoroethylene
• ECTFE ethylene / chlorotrifluoroethylene resin
• ionomer (IO) resin examples include a copolymer of olefin or styrene and an unsaturated carboxylic acid, in which a part of the carboxyl group is neutralized with a metal ion.
• olefin / vinyl alcohol resin examples include ethylene / vinyl alcohol copolymer, propylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer saponified product, and propylene / vinyl acetate copolymer saken product.
• cyclic olefin resin examples include monocyclics such as cyclohexene, polycyclics such as tetracyclopentadiene, and polymers of cyclic olefin monomers.
• polylactic acid examples include polyL-lactic acid, which is an L-form homopolymer, polyD-lactic acid, which is a D-form homopolymer, and stereocomplex-type polylactic acid, which is a mixture thereof.
• cellulose resin examples include methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate and the like.
• thermosetting resin examples include unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenol resin (PF), urethane resin (PU), polyisocyanate, and polyisocyanurate.
• PI polyimide
• UF silicon
• SI silicon
• FR furan
• BR benzoguanamine
• alkyd resin xylene resin
• BT bismaride triazine
• PDAP diallyl phthalate resin
• examples of the unsaturated polyester include a resin obtained by subjecting an aliphatic unsaturated dicarboxylic acid and an aliphatic diol to an esterification reaction.
• vinyl ester resin examples include bis-based vinyl ester resin and novolak-based vinyl ester resin.
• epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene).
• Bisphenol type epoxy resin Bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) Bisphenol type epoxy resin), Bisphenol Z type epoxy resin (4,4'-cyclohexidienbisphenol) Type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolak type epoxy resin, novolak type epoxy resin having a fused ring aromatic hydrocarbon structure, biphenyl type epoxy resin, xylylene type epoxy resin Aralkill type epoxy resin such as phenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalenediol type epoxy resin, bifunctional to tetra
• melamine resin examples include a polymer composed of a polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.
• phenol resin examples include novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, and bisphenol A-type novolak resin, resol-type phenol resins such as methylol-type resol resin and dimethylene ether-type resol resin, or arylalkylene-type phenol resins. Etc., and one of them, or a combination of two or more of them can be mentioned.
• urea resin examples include a resin obtained by condensation of urea and formaldehyde.
• thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more.
• polyamide, polyarylene sulfide or polybutylene terephthalate is preferable, and by containing the glass fiber satisfying the above formula (1), the dimensional stability and the dielectric property are exhibited.
• Polybutylene terephthalate is more preferable because it has a large improving effect.
• the glass fiber content is, for example, in the range of 10.0 to 70.0% by mass, and preferably in the range of 20.0 to 60.0% by mass. It is more preferably in the range of 25.0 to 57.5% by mass, further preferably in the range of 30.0 to 55.0% by mass, and in the range of 40.0 to 52.5% by mass. It is particularly preferable, and most preferably it is in the range of 45.0 to 52.0% by mass.
• the glass fiber content in the glass fiber reinforced resin molded product of this embodiment can be calculated in accordance with JIS K7052: 1999.
• the resin content is, for example, in the range of 30.0 to 90.0% by mass, preferably in the range of 40.0 to 80.0% by mass. It is more preferably in the range of 42.5 to 75.0% by mass, further preferably in the range of 45.0 to 70.0% by mass, and more preferably in the range of 47.5 to 60.0% by mass. Is particularly preferable, and most preferably in the range of 48.0 to 52.0% by mass.
• the glass fiber reinforced resin molded product 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.
• Such components include glass fibers other than the glass fibers (for example, E glass fibers and S glass fibers), reinforcing fibers other than the glass fibers (for example, carbon fibers and metal fibers), and fillers other than the glass fibers (for example).
• Glass powder, talc, mica flame retardant, ultraviolet absorber, heat stabilizer, antioxidant, antistatic agent, fluidity improver, antiblocking agent, lubricant, nucleating agent, antibacterial agent, pigment, etc. be able to.
• the glass fiber reinforced resin molded product of the present invention can contain these components in the range of 0 to 40% by mass in total with respect to the total amount of the glass fiber reinforced resin molded product.
• Examples of the molding method for obtaining the glass fiber reinforced resin molded product of the present embodiment include an injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method, and a foam molding method (including those using a supercritical fluid). Includes), insert molding method, in-mold coating molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, blow molding method, stamping molding method, infusion method, hand Examples thereof include a lay-up method, a spray-up method, a resin transfer molding method, a sheet molding compound method, a bulk molding compound method, a pull-fusion method, and a filament winding method. Among these methods, the injection molding method is preferable because it is excellent in manufacturing efficiency.
• the chopped strand of the glass fiber is kneaded with the resin and then extruded from a nozzle to have a predetermined length (for example, in the range of 1 to 50 mm).
• a predetermined length for example, in the range of 1 to 50 mm.
• the roving of the glass fiber is impregnated with the molten thermoplastic resin, cooled, and then cut to a predetermined length (for example, a length in the range of 1 to 50 mm) to form a pellet.
• the processed product can be used as a molding raw material.
• Glass fiber reinforced resin molded product of the present embodiment include parts such as housings and frames of portable electronic devices represented by smartphones, automobile electrical components such as battery tray covers and sensors, coil bobbins, and portable electronic devices. Examples include electronic device parts, electrical connection terminal parts, and the like.
• Glass composition Four kinds of glass compositions of compositions 1 to 4 shown in Table 1 were used.
• composition 2 corresponds to the E glass composition.
• the glass fiber dielectric constant and the glass fiber linear expansion coefficient at a measurement frequency of 1 GHz are values calculated by the above method.
• the glass fiber strength can be measured by the following method. First, the molten glass is obtained in exactly the same manner as the above-mentioned method for measuring the glass fiber dielectric constant. Next, the obtained molten glass was poured onto a carbon plate to prepare a glass cullet, and then the obtained glass cullet was placed in a small tubular platinum bushing having one circular nozzle tip at the bottom of the container. The bushing is heated to a predetermined temperature so that the viscosity of the added glass cullet becomes 1000 ⁇ 150 poisons, and the glass cullet is melted to obtain molten glass.
• the molten glass discharged from the nozzle tip of the platinum bushing is wound at a predetermined speed by a winder so that the glass fiber diameter is 13 ⁇ 2 ⁇ m, and is cooled and solidified while being stretched to have a perfect circular cross section.
• a single fiber (monofilament) between the nozzle tip of the platinum bushing and the winder is sampled, and the glass fiber in a state where deterioration due to contact or friction is suppressed as much as possible is used as a sample for tensile strength evaluation.
• the obtained monofilament is arranged and adhered in the long side direction along the line connecting the center points of the short sides of the mount provided with the two grip portions and the two support portions described later, and the monofilament test piece is bonded.
• the diameter of the obtained monofilament is measured with a scanning electron microscope (manufactured by Hitachi, Ltd., trade name: S-3400), and the cross-sectional area of the monofilament is calculated from the obtained diameter.
• the two grips in the mount are vertically gripped with the distance between the grips of the tensile tester (manufactured by A & D Co., Ltd., trade name: desktop material tester STB-1225S) set to 25 mm.
• a tensile test is performed at a crosshead speed of 5 mm / min.
• the tensile strength is calculated by dividing the maximum load value when the monofilament is broken by the cross-sectional area of the monofilament.
• the mount has a short side of 25 mm and a long side of 50 mm, and a cutout portion having a short side of 15 mm and a long side of 25 mm is provided in the center of the inside thereof with the short side and the long side of the mount.
• the short side and the long side of the cutout portion are provided so as to be parallel to each other, and a grip portion set on the grip tool of the tensile tester is provided between the short side of the cutout portion and the short side of the mount.
• a support portion for connecting and supporting the two grip portions is provided between the long side of the cutout portion and the long side of the mount.
• the elastic modulus of glass fiber can be measured by the following method. First, a monofilament is obtained in exactly the same manner as the above-mentioned method for measuring glass fiber strength. Next, the obtained monofilament is arranged and adhered in the long side direction along the line connecting the center points of the short sides of the mount provided with the two grip portions and the two support portions described later, and the monofilament test piece is bonded. To make. Next, the diameter of the obtained monofilament is measured with a scanning electron microscope (manufactured by Hitachi, Ltd., trade name: S-3400), and the cross-sectional area of the monofilament is calculated from the obtained diameter.
• a scanning electron microscope manufactured by Hitachi, Ltd., trade name: S-3400
• the two grips in the mount are vertically gripped with the distance between the grips of the tensile tester (manufactured by A & D Co., Ltd., trade name: desktop material tester STB-1225S) set to 50 mm.
• a tensile test is performed at a crosshead speed of 5 mm / min.
• the mount has a short side of 25 mm and a long side of 75 mm, and a cutout portion having a short side of 15 mm and a long side of 50 mm is provided in the center of the inside thereof with the short side and the long side of the mount.
• the short side and the long side of the cutout portion are provided so as to be parallel to each other, and a grip portion set on the grip tool of the tensile tester is provided between the short side of the cutout portion and the short side of the mount.
• a support portion for connecting and supporting the two grip portions is provided between the long side of the cutout portion and the long side of the mount.
• Fortron KPS W-203A (trade name, manufactured by Kureha Corporation) was used as polyphenylene sulfide (indicated as PPS in the table).
• the bending strength and flexural modulus of the glass fiber reinforced resin molded product are measured by using a precision universal testing machine (manufactured by Shimadzu Corporation, trade name: Autograph AG-5000B) under the condition of a test temperature of 23 ° C., JIS K 7171. : Measured according to 2016.
• Examples 1 to 3, Comparative Examples 1 to 4 The fiber diameter of the glass fiber, the number average fiber length of the glass fiber, and the glass fiber content in the glass fiber reinforced resin molded product correspond to Examples 1 to 3 shown in Table 2 and Comparative Examples 1 to 4 shown in Table 3. As described above, the fiber diameter, cutting length (3 mm), and blending amount of the glass fibers of the chopped strands having the above-mentioned compositions 1 to 4 were adjusted. Next, the chopped strand and the polyamide were kneaded with a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., trade name: TEM-26SS) at a screw rotation speed of 100 rpm to prepare resin pellets.
• a twin-screw kneader manufactured by Toshiba Machine Co., Ltd., trade name: TEM-26SS
• the mass of the glass fiber in the glass fiber reinforced resin molded product is determined by the composition of the glass fiber, the fiber diameter, the number of focused fibers, and the cutting length and the number of the glass fibers.
• injection molding was performed by an injection molding machine (manufactured by Nissei Resin Industry Co., Ltd., trade name: NEX80) at a mold temperature of 90 ° C. and an injection temperature of 270 ° C., and Examples 1 to 3 were performed.
• the glass fiber reinforced resin molded products of Comparative Examples 1 to 4 were obtained.
• the bending strength of the molded product, the bending elasticity of the molded product, the notched charmy impact strength of the molded product, and the molded product are obtained by the above-mentioned methods.
• the dielectric constant and the linear expansion coefficient of the molded product were evaluated.
• the results are shown in Tables 2 and 3.
• the dimensional stability / dielectric property index in the table is the value obtained by multiplying the dielectric constant MDk of the molded product by the linear expansion coefficient MC of the molded product (MDk ⁇ MC) and the reference glass fiber reinforced resin molded product.
• the standard glass fiber reinforced resin molded product is manufactured under the same molding conditions as the molded product, having an E glass composition and containing glass fiber having a fiber diameter of 11.0 ⁇ m at the same glass content as the molded product. It is a glass fiber reinforced resin molded product.
• Examples 4 to 5, Comparative Examples 5 to 7 The fiber diameter of the glass fiber, the number average fiber length of the glass fiber, and the glass fiber content in the glass fiber reinforced resin molded product are described above so as to be in Examples 4 to 5 and Comparative Examples 5 to 7 shown in Table 4.
• the fiber diameter, cutting length (3 mm), and blending amount of the glass fibers of the chopped strands having the compositions 1 to 4 were adjusted.
• the chopped strand and the polyphenylene sulfide were kneaded with a twin-screw kneader (manufactured by Shibaura Machine Co., Ltd., trade name: TEM-26SS) at a screw rotation speed of 100 rpm to prepare resin pellets.
• a twin-screw kneader manufactured by Shibaura Machine Co., Ltd., trade name: TEM-26SS
• the mass of the glass fiber in the glass fiber reinforced resin molded product is determined by the composition of the glass fiber, the fiber diameter, the number of focused fibers, and the cutting length and the number of the glass fibers.
• injection molding was performed by an injection molding machine (manufactured by Nissei Resin Industry Co., Ltd., trade name: NEX80) at a mold temperature of 140 ° C. and an injection temperature of 330 ° C., and Examples 4 to 5 were performed. And the glass fiber reinforced resin molded products of Comparative Examples 5 to 7 were obtained.
• the bending strength of the molded product, the bending elasticity of the molded product, the notched charmy impact strength of the molded product, and the molded product are obtained by the above-mentioned methods.
• the dielectric constant and the linear expansion coefficient of the molded product were evaluated. The results are shown in Table 4.
• the dimensional stability / dielectric property index in the table is the value obtained by multiplying the dielectric constant MDk of the molded product by the linear expansion coefficient MC of the molded product (MDk ⁇ MC) and the reference glass fiber reinforced resin molded product.
• the standard glass fiber reinforced resin molded product is manufactured under the same molding conditions as the molded product, having an E glass composition and containing glass fiber having a fiber diameter of 11.0 ⁇ m at the same glass content as the molded product. It is a glass fiber reinforced resin molded product.
• the fiber diameter of the glass fiber, the number average fiber length of the glass fiber, and the glass fiber content in the glass fiber reinforced resin molded product are Examples 6 to 8 shown in Table 5 and Comparative Examples 8 to 11 shown in Table 6.
• the fiber diameter, cutting length (3 mm), and blending amount of the glass fibers of the chopped strands having the above-mentioned compositions 1 to 4 were adjusted.
• the chopped strand and the polybutylene terephthalate were kneaded with a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., trade name: TEM-26SS) at a screw rotation speed of 100 rpm to prepare resin pellets.
• the mass of the glass fiber in the glass fiber reinforced resin molded product is determined by the composition of the glass fiber, the fiber diameter, the number of focused fibers, and the cutting length and the number of the glass fibers.
• injection molding was performed by an injection molding machine (manufactured by Nissei Resin Industry Co., Ltd., trade name: NEX80) at a mold temperature of 90 ° C. and an injection temperature of 250 ° C., and Examples 6 to 8 were performed. And the glass fiber reinforced resin molded products of Comparative Examples 8 to 11 were obtained.
• the bending strength of the molded product, the bending elasticity of the molded product, the notched charmy impact strength of the molded product, and the molded product are obtained by the above-mentioned methods.
• the dielectric constant and the linear expansion coefficient of the molded product were evaluated.
• the results are shown in Tables 5 and 6.
• the dimensional stability / dielectric property index in the table is the value obtained by multiplying the dielectric constant MDk of the molded product by the linear expansion coefficient MC of the molded product (MDk ⁇ MC) and the reference glass fiber reinforced resin molded product.
• the standard glass fiber reinforced resin molded product is manufactured under the same molding conditions as the molded product, having an E glass composition and containing glass fiber having a fiber diameter of 11.0 ⁇ m at the same glass content as the molded product. It is a glass fiber reinforced resin molded product.
• the fiber diameter D of the glass fiber contained in the glass fiber reinforced resin molded product is in the range of 5.0 to 15.0 ⁇ m.
• the dielectric constant Dk of the glass fiber contained in the glass fiber reinforced resin molded product at a measurement frequency of 1 GHz is in the range of 4.0 to 7.0
• the linear expansion coefficient C of the glass fiber contained in the glass fiber reinforced resin molded product is C. Is in the range of 2.0 to 6.0 ppm / K
• the number average fiber length L of the glass fibers contained in the glass fiber reinforced resin molded product is in the range of 150 to 400 ⁇ m
• the D, Dk, C and L are It is clear that the following equation (1) is satisfied.
• the glass fiber reinforced resin molded products of Examples 1 to 8 have both high dimensional stability and low dielectric property. 57.9 ⁇ Dk x C 1/4 x L 1/2 / D 1/4 ⁇ 70.6 ... (1)
• the glass fiber reinforced resin molded products of Comparative Examples 1 to 11 do not satisfy the above formula (1). Since the dimensional stability / dielectric property index exceeds 0.85, it cannot be said that the product has both high dimensional stability and low dielectric property.

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