WO2020137004A1 - ガラス繊維強化樹脂成形品 - Google Patents
ガラス繊維強化樹脂成形品 Download PDFInfo
- Publication number
- WO2020137004A1 WO2020137004A1 PCT/JP2019/034219 JP2019034219W WO2020137004A1 WO 2020137004 A1 WO2020137004 A1 WO 2020137004A1 JP 2019034219 W JP2019034219 W JP 2019034219W WO 2020137004 A1 WO2020137004 A1 WO 2020137004A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass fiber
- resin molded
- reinforced resin
- molded product
- fiber reinforced
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- 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
-
- 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
-
- 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
-
- 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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- the present invention relates to a glass fiber reinforced resin molded product.
- glass fibers have been widely used in various applications to improve the performance of resin molded products.
- one of the main performances improved by the glass fiber is mechanical strength such as tensile strength and bending strength of the glass fiber reinforced resin molded product.
- the fiber diameter of the glass fiber usually, the glass fiber is formed by bundling a plurality of glass filaments, and the average diameter of the glass filaments is called the fiber diameter of the glass fiber
- the glass fiber reinforced resin molded product The effect of various characteristics of glass fiber such as the length of glass fiber in the glass, the glass content in the glass fiber reinforced resin molded product, and the cross-sectional shape of the glass filament on the mechanical strength of the glass fiber reinforced resin molded product was examined. (For example, see Patent Document 1).
- a glass fiber reinforced resin molded product is provided, and the fiber diameter D ( ⁇ m) of the glass fiber contained in the glass fiber reinforced resin molded product is in the range of 3.0 to 12.0 ⁇ m.
- the number average fiber length L ( ⁇ m) of the glass fibers contained in the glass fiber reinforced resin molded product is in the range of 160 to 350 ⁇ m, and the glass fiber volume content V (%) in the glass fiber reinforced resin molded product is 3.0.
- a glass fiber reinforced resin molded article is described, characterized in that it is in the range of up to 50.0%, and that D, L and V satisfy the following formula (6). 300.0 ⁇ D 2 ⁇ L/V ⁇ 1000.0 (6)
- glass fiber reinforced resin molded products for fine and thin parts in the electrical and electronic fields has expanded. Since it is difficult to replace a fine component/thin-walled component when a defect occurs, the glass fiber reinforced resin molded product used for the fine component/thin-walled component is required to have a particularly high static and dynamic strength. Further, since minute parts/thin-walled parts are difficult to process, glass fiber reinforced resin molded products used for the minute parts/thin-walled parts are required to have high moldability under various manufacturing conditions. In particular, since fine parts and thin-walled parts are often manufactured by injection molding, glass fiber reinforced resin molded products used for the fine parts and thin-walled parts are required to have high fluidity under various manufacturing conditions.
- the present invention has been made in view of the above circumstances, and the static and dynamic strength of the glass fiber reinforced resin molded article, and the characteristics of the glass fiber contributing to the fluidity are clarified static and dynamic strength. It is an object of the present invention to provide a glass fiber reinforced resin molded product having excellent balance between dimensional stability and fluidity.
- the glass fiber contained in the glass fiber reinforced resin molded product has a minor axis D1 in the range of 3.0 to 10.5 ⁇ m and a major axis D2.
- the glass fiber content C (wt %) in the reinforced resin molded product is in the range of 40.0 to 75.0 wt %, and the above D1, D2, L and C satisfy the following formula (1).
- the D1, D2, L and C are in the ranges described above, and the glass fiber reinforced resin molded article satisfies the condition of the above formula (1), Excellent balance and static and dynamic strength and fluidity.
- the D1 is in the range of 3.5 to 6.4 ⁇ m
- the D2 is in the range of 14.0 to 26.0 ⁇ m
- the L is 165 to 300 ⁇ m. It is preferable that C is in the range, C is in the range of 42.5 to 65.0%, and D1, D2, L and C satisfy the following formula (3).
- the glass fiber reinforced resin molded product of the present invention has D1, D2, L and C in the range described above and satisfies the condition of the above formula (3), It has excellent static and dynamic strength and fluidity in a well-balanced manner, and has excellent dimensional stability and surface smoothness.
- the resin contained in the glass fiber reinforced resin molded product is a polyamide resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyarylene sulfide resin, a polyarylketone resin and a liquid crystal polymer (LCP). It is preferably a thermoplastic resin for injection molding selected from the group consisting of, and more preferably a polyamide resin.
- thermoplastic resin for injection molding, it is possible to mold minute parts/thin parts relatively easily.
- the glass fibers contained in the glass fiber reinforced resin molded product have a minor axis D1 in the range of 3.0 to 10.5 ⁇ m and a major axis D2 of 11.0 to 29.
- the glass fiber-reinforced resin molded product has a flat cross-sectional shape in the range of 0 ⁇ m, and the number average fiber length L ( ⁇ m) of the glass fibers contained in the glass fiber-reinforced resin molded product is in the range of 150 to 475 ⁇ m.
- the glass fiber content C (wt %) is in the range of 40.0 to 75.0 wt %, and the above D1, D2, L and C satisfy the following formula (1). 260.0 ⁇ C 2 ⁇ L/(D1 ⁇ D2 2 ) ⁇ 400.0 (1)
- the D1, D2, L and C are in the ranges described above, and the glass fiber reinforced resin molded article satisfies the condition of the above formula (1), Excellent balance and static and dynamic strength and fluidity.
- the determination of whether the static and dynamic strengths and the fluidity are excellent in a well-balanced manner is made by, for example, the tensile strength T (GPa)/bending strength B (GPa), the dynamic strength that reflects the static strength.
- the notched Charpy impact strength I (KJ/m 2 ) that reflects the above, and the low-speed flow length F1 (mm) and the high-speed flow length F2 (mm) that reflect the fluidity are given by the following formula (2). It can be judged by whether or not it satisfies. (T ⁇ B) 1/2 ⁇ I ⁇ (F1 ⁇ F2) 1/2 >300.0 (2)
- the tensile strength, bending strength, Charpy impact strength without notch, low-speed flow length, and high-speed flow length can be measured by the following methods.
- the device used for the measurement is not particularly limited as long as it has the same performance as the device described below.
- the minor axis D1 of the glass fiber is less than 3.0 ⁇ m, it adversely affects the health of the manufacturer in the manufacturing process of the glass fiber and the glass fiber-reinforced resin molded product. Is concerned.
- the minor axis D1 of the glass fiber is more than 10.5 ⁇ m, a glass fiber reinforced resin molded product having sufficient strength cannot be obtained.
- the glass fiber reinforced resin molded product of the present embodiment it is difficult to manufacture a glass fiber having a major axis D2 of less than 11.0 ⁇ m and a flat cross-sectional shape.
- the major axis D2 of the glass fiber is more than 29.0 ⁇ m, a glass fiber reinforced resin molded product having sufficient strength cannot be obtained.
- the surface smoothness of the glass fiber reinforced resin molded product is improved, so that the minor axis D1 of the glass fiber is preferably 3.5 to 6.4 ⁇ m.
- the thickness is more preferably 4.0 to 6.0 ⁇ m, further preferably 4.5 to 5.5 ⁇ m.
- the major axis D2 of the glass fiber is preferably 14.0 to 26.0 ⁇ m, more preferably 16.0 to 24.0 ⁇ m, because the surface smoothness of the glass fiber reinforced resin molded product is improved. More preferably, it is 18.0 to 22.0 ⁇ m.
- the minor axis and major axis of the glass fiber in the glass fiber reinforced resin molded product of the present embodiment are, for example, firstly polishing the cross section of the glass fiber reinforced resin molded product, and then using an electron microscope, for 100 or more glass filaments.
- the longest side that passes through the approximate center of the glass filament cross section is the major axis, and the side orthogonal to the major axis and the approximate center of the glass filament cross section is the minor axis. Each length is measured, and the average value of these is calculated. It can be calculated.
- the glass fiber is usually formed by bundling a plurality of glass filaments, but in a glass fiber reinforced resin molded product, the bundling is released by going through a molding process, in the state of a glass filament, It is present dispersed in the glass fiber reinforced resin molded product.
- the ratio (D2/D1) of the major axis D2 to the minor axis D1 of the glass fiber is, for example, in the range of 1.2 to 10.0 and 1.8 to 8. It is preferably in the range of 0, more preferably in the range of 2.0 to 6.0, further preferably in the range of 2.5 to 5.5, and in the range of 3.0 to 5.0. Is particularly preferable, and the range from 3.3 to 4.5 is most preferable.
- the glass fiber reinforced resin molded article of the present embodiment as the flat cross-sectional shape of the glass fiber contained in the glass fiber reinforced resin molded article, for example, oval (the short side portion of the rectangle, the short side is the diameter and The shape of the ellipse is preferable since it contributes to the improvement of the fluidity of the glass fiber reinforced resin molded product.
- the cross section of the glass fiber means a cross section perpendicular to the fiber length direction of the glass fiber.
- the number average fiber length L of the glass fibers can be in the range of 1 to 10000 ⁇ m, but if the number average fiber length L of the glass fibers is less than 150 ⁇ m, sufficient mechanical properties can be obtained. It is not possible to obtain a glass fiber reinforced resin molded product having a desired strength. On the other hand, when the number average fiber length L of the glass fibers is more than 475 ⁇ m, the workability during molding, especially during biaxial kneading, may be deteriorated.
- the number average fiber length L of glass fibers is preferably 165 to 300 ⁇ m, more preferably 180 to 295 ⁇ m, and more preferably 195 to 290 ⁇ m. More preferably, 210 to 285 ⁇ m is particularly preferable, 220 to 280 ⁇ m is particularly preferable, 230 to 270 ⁇ m is extremely preferable, and 240 to 265 ⁇ m is most preferable.
- the number average fiber length of glass fibers in the glass fiber reinforced resin molded product of the present embodiment can be calculated by 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. Then, the remaining glass fibers are transferred to a glass petri dish, and the glass fibers are dispersed on the surface of the petri dish using acetone. Next, with respect to 1000 or more glass fibers dispersed on the surface of the petri dish, the fiber length is measured using a stereoscopic microscope and averaged to calculate the number average fiber length of the glass fibers.
- the glass fiber reinforced resin molded product of the present embodiment if the glass fiber content rate C is less than 40.0 wt%, a glass fiber reinforced resin molded product having sufficient strength cannot be obtained. On the other hand, in the glass fiber reinforced resin molded product of the present invention, if the glass fiber content C is more than 75.0 wt%, sufficient fluidity cannot be obtained.
- the glass fiber content C is preferably in the range of 40.0 to 75.0 wt% and is preferably 42.5 to 65.0 wt%. It is more preferably from 0 to 60.0 wt%, further preferably from 47.5 to 55.0 wt%.
- the glass fiber content in the glass fiber reinforced resin molded product of the present embodiment can be calculated according to JIS K 7052:1999.
- the glass fiber reinforced resin molded product of the present invention when the glass fiber content C is less than 40.0 wt%, sufficient strength (for example, tensile strength of 0.200 GPa or more, bending strength of 0.300 GPa or more, and It is not possible to obtain a glass fiber reinforced resin molded product having a notchless Charpy impact strength of 90 kJ/m 2 or more). On the other hand, in the glass fiber reinforced resin molded product of the present invention, if the glass fiber content C is more than 75.0 wt%, sufficient fluidity cannot be obtained.
- the short diameter D1 ( ⁇ m) of the glass fiber, the long diameter D2 ( ⁇ m) of the glass fiber, the fiber length L ( ⁇ m) of the glass fiber, and the glass fiber content C (wt%) do not satisfy the above formula (1). That is, when C 2 ⁇ L/(D1 ⁇ D2 2 ) is less than 260, it is not possible to obtain a glass fiber reinforced resin molded product having a good balance of static and dynamic strength and fluidity. .. On the other hand, in the glass fiber reinforced resin molded product of the present embodiment, since C and L are in a trade-off relationship, the glass fiber reinforced resin molded product in which C 2 ⁇ L/(D1 ⁇ D2 2 ) exceeds 400 is It is difficult to manufacture.
- the glass fiber reinforced resin molded product of the present embodiment it is preferable that D1, D2, L and C satisfy the following formula (3).
- C 2 ⁇ L/(D1 ⁇ D2 2 ) satisfies the following formula (3), the glass fiber reinforced resin molded product is excellent in static and dynamic strength and fluidity in an excellent balance, and Excellent in dimensional stability and surface smoothness.
- the determination of whether the static and dynamic strengths and the fluidity are excellent in a well-balanced manner is made by, for example, the tensile strength T (GPa)/bending strength B (GPa), which reflects the static strength, and the dynamic strength.
- the Charpy impact strength without notch I (KJ/m 2 ) that reflects the strength, and the low-speed flow length F1 (mm) and the high-speed flow length F2 (mm) that reflects the fluidity are given by the following formula (4) ) Can be determined by whether or not.
- D1, D2, L and C satisfy the following formula (5). 310.0 ⁇ C 2 ⁇ L/(D1 ⁇ D2 2 ) ⁇ 325.0 (5)
- the glass composition of the glass forming the glass fiber is not particularly limited.
- the glass composition that the glass fiber can take is the most general E glass composition (SiO in the range of 52.0 to 56.0 mass% with respect to the total amount of glass fiber). 2 , Al 2 O 3 in the range of 12.0 to 16.0% by mass, MgO and CaO in the range of 20.0 to 25.0% by mass, and 5.0 to 10.0% by mass. Range and composition containing B 2 O 3 ), high-strength and high-modulus glass composition (SiO 2 in the range of 64.0 to 66.0 mass% with respect to the total amount of glass fibers, and 24.0 to 26.0 mass).
- % Al 2 O 3 in a range of 9.0 to 11.0 mass% MgO a high elastic modulus easily-manufacturable glass composition (based on the total amount of glass fibers, 57.0 to 60.
- the above composition) and the low dielectric constant and low dielectric loss tangent glass composition (SiO 2 and B 2 O 3 in the range of 48.0 to 62.0 mass% with respect to the total amount of glass fibers are 17.0 to 26.0).
- the glass composition of the glass fiber is preferably the above-menti
- the glass fiber having the above-mentioned glass composition is manufactured as follows. First, a glass raw material (glass batch) prepared to have the above composition is supplied to a melting furnace and melted at a temperature in the range of 1450 to 1550° C., for example. Next, the molten glass batch (molten glass) is drawn out from 1 to 20000 nozzle tips of a bushing 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 by using an applicator which is an application device, and a focusing shoe is used to converge 1 to 20000 glass filaments and a winder. The glass fiber is obtained by winding it into a tube at a high speed.
- the nozzle tip has a non-circular shape and has a protrusion or a notch for quenching the molten glass, and the temperature condition is controlled to obtain a glass filament having a flat cross-sectional shape.
- the minor diameter D1 ( ⁇ m) and the major diameter D2 ( ⁇ m) of the glass fiber can be adjusted by adjusting the diameter of the nozzle tip, the winding speed, the temperature condition, and the like. For example, by increasing the winding speed, the minor diameter D1 and the major diameter D2 can be reduced, and by decreasing the winding speed, the minor diameter D1 and the major diameter D2 can be increased.
- its surface may be coated with an organic material.
- organic material include urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (especially carboxylic acid modified polypropylene), and (poly)carboxylic acid (especially maleic acid) and an unsaturated monomer. Examples include coalescence.
- the glass fiber may be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, and the like in addition to these resins.
- a resin composition coats the glass fiber at a rate 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 resin composition.
- the coating of the glass fiber with an organic material for example, in the manufacturing process of the glass fiber, by using a known method such as a roller-type applicator, the sizing agent or binder containing the resin solution or the resin composition solution to the glass fiber Can be performed by drying the glass fiber coated with the resin solution or the resin composition solution.
- aminosilane ( ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)-N'- ⁇ is used.
- silane coupling agents may be used alone or in combination of two or more kinds.
- modified silicone oil As the lubricant, modified silicone oil, animal oil (beef tallow, etc.) and its hydrogenated product, vegetable oil (soybean oil, coconut oil, rapeseed oil, palm oil, castor oil, etc.) and this hydrogenated product, animal wax (beeswax, lanolin) Etc.), vegetable wax (candelilla wax, carnauba wax, etc.), mineral wax (paraffin wax, montan wax, etc.), condensation product of higher saturated fatty acid and higher saturated alcohol (stearate ester such as lauryl stearate, etc.) , Polyethyleneimine, polyalkyl polyamine alkyl amide derivative, fatty acid amide (for example, dehydration condensation of polyethylene polyamine such as diethylene triamine, triethylene tetramine, tetraethylene pentamine and fatty acid such as lauric acid, myristic acid, palmitic acid, stearic acid) Substances) and quaternary ammonium salts (al
- surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more.
- nonionic surfactants include ethylene oxide propylene oxide alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene block copolymer, alkyl polyoxyethylene-polyoxypropylene block copolymer ether, and polyoxyethylene fatty acid ester.
- Polyoxyethylene fatty acid monoester Polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester ethylene oxide adduct, polyoxyethylene castor oil ether, hydrogenated castor oil ethylene oxide adduct, alkylamine ethylene oxide adduct , Fatty acid amide ethylene oxide adduct, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyhydric alcohol alkyl ether, fatty acid alkanolamide, acetylene glycol, acetylene alcohol , Ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol, and the like.
- cationic surfactant examples include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (acetic acid salts, hydrochlorides, etc.), ethylene oxide adducts with higher alkylamines, and higher alkylamine salts.
- alkylamine salts acetic acid salts, hydrochlorides, etc.
- ethylene oxide adducts with higher alkylamines examples include condensates of fatty acids and polyalkylenepolyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline type cationic surfactants, alkylpyridinium salts and the like.
- higher alcohol sulfate ester salt higher alkyl ether sulfate ester salt, ⁇ -olefin sulfate ester salt, alkylbenzene sulfonate, ⁇ -olefin sulfonate, reaction of fatty acid halide with N-methyltaurine
- examples thereof include products, sulfosuccinic acid dialkyl ester salts, higher alcohol phosphoric acid ester salts, and higher alcohol ethylene oxide adduct phosphoric acid ester salts.
- amphoteric surfactant examples include amino acid-type amphoteric surfactants such as alkylaminopropionic acid alkali metal salts, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.
- the glass fiber reinforced resin molded product of the present embodiment contains a thermoplastic resin or a thermosetting resin, and an additive other than glass fiber, in addition to the glass fiber described above.
- the content of the thermoplastic resin or the thermosetting resin is, for example, 15.0 to 60.0 wt %.
- the content of additives other than glass fibers is, for example, 0 to 40.0 wt %.
- thermoplastic resin polyethylene, polypropylene, polystyrene, styrene/maleic anhydride resin, styrene/maleimide resin, polyacrylonitrile, acrylonitrile/styrene (AS) resin, acrylonitrile/butadiene/styrene (ABS) resin, chlorine Polyethylene/acrylonitrile/styrene (ACS) resin, acrylonitrile/ethylene/styrene (AES) resin, acrylonitrile/styrene/methyl acrylate (ASA) resin, styrene/acrylonitrile (SAN) resin, methacryl resin, polyvinyl chloride (PVC) , Polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycarbonate, polyarylene sulfide,
- 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 high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and 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, high-impact polystyrene (HIPS) in which a rubber component is added to GPPS, and syndiotactic polystyrene having a syndiotactic structure.
- GPPS general-purpose polystyrene
- HIPS high-impact polystyrene
- syndiotactic polystyrene having a syndiotactic structure examples include general-purpose polystyrene (GPPS), which is an atactic polystyrene having an atactic structure, high-impact polystyrene (HIPS) in which a rubber component is added to GPPS, and syndiotactic polystyrene having a syndiotactic structure.
- GPPS general-purpose polystyrene
- HIPS high-impact polystyrene
- the methacrylic resin acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, a polymer obtained by homopolymerizing one of vinyl ester fatty acid, or two or more. And the like.
- polyvinyl chloride a vinyl chloride homopolymer polymerized by a conventionally known method such as an emulsion polymerization method, a suspension polymerization method, a micro suspension polymerization method, a bulk polymerization method, or a copolymerizable with a vinyl chloride monomer.
- Polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), polypentamethylene adipamide.
- nylon 56 polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), poly Decamethylene sebacamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polyundecane amide (nylon 11), polyundecamethylene adipamide (nylon 116), polydodecanamide (nylon 12), polyxylene Adipamide (nylon XD6), polyxylene sebacamide (nylon XD10), polymethaxylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polytetramethylene terephthalamide (nylon 4T) , Polypentamethylene terephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon
- polyacetal a homopolymer having an oxymethylene unit as a main repeating unit, and a copolymer mainly composed of an oxymethylene unit and containing an oxyalkylene unit having 2 to 8 adjacent carbon atoms in the main chain Etc.
- polyethylene terephthalate examples include a polymer obtained by polycondensing terephthalic acid or a derivative thereof and ethylene glycol.
- polybutylene terephthalate examples include polymers obtained by polycondensing terephthalic acid or its derivative and 1,4-butanediol.
- polytrimethylene terephthalate examples include polymers obtained by polycondensing terephthalic acid or its derivative and 1,3-propanediol.
- polycarbonate examples include a polymer obtained by a transesterification method in which a dihydroxydiaryl compound and a carbonic acid ester such as diphenylcarbonate are reacted in a molten state, or a polymer obtained by a phosgene method in which a dihydroxyaryl compound and phosgene are reacted.
- polyarylene sulfide examples include linear polyphenylene sulfide, cross-linked polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone, which have been polymerized to have a high molecular weight by performing a curing reaction after polymerization.
- modified polyphenylene ether a polymer alloy of poly(2,6-dimethyl-1,4-phenylene)ether and polystyrene, poly(2,6-dimethyl-1,4-phenylene)ether and styrene/butadiene copolymer And a polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and a styrene/maleic anhydride copolymer, and a poly(2,6-dimethyl-1,4-phenylene) ether Examples thereof include polymer alloys with polyamide, polymer alloys with poly(2,6-dimethyl-1,4-phenylene) ether and styrene/butadiene/acrylonitrile copolymer, and the like.
- polyarylketone examples include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).
- the liquid crystal polymer (LCP) is one or more structures selected from thermotropic liquid crystal polyesters, such as aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, and aliphatic dicarbonyl units. Examples thereof include (co)polymers composed of units.
- PTFE polytetrafluoroethylene
- PFA perfluoroalkoxy resin
- FEP fluorinated ethylene propylene resin
- ETFE fluorinated ethylene tetrafluoroethylene resin
- PVDF polyvinyl fluoride
- 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, saponified ethylene/vinyl acetate copolymer, saponified propylene/vinyl acetate copolymer and the like.
- cyclic olefin resins include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.
- polylactic acid examples include poly L-lactic acid which is an L-form homopolymer, poly D-lactic acid which is a D-form homopolymer, and a stereocomplex 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 unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenol resin (PF), urethane resin (PU), polyisocyanate, polyisocyanurate, Polyimide (PI), urea (UF) resin, silicon (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleimide triazine (BT) resin, diallyl phthalate resin (PDAP), etc. Can be mentioned.
- the unsaturated polyester includes a resin obtained by subjecting an aliphatic unsaturated dicarboxylic acid and an aliphatic diol to an esterification reaction.
- vinyl ester resins include bis vinyl ester resins and novolac vinyl ester resins.
- epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4′-(1,3-phenylene diisopropylidene)) Bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexylidene bisphenol type epoxy) Resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane novolac type epoxy resin, novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure, biphenyl type epoxy resin, xylylene type epoxy resin and phenylaralkyl.
- -Type epoxy resin and other aralkyl-type epoxy resins naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalene diol-type epoxy resins, bifunctional or tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalene aralkyl-type epoxy resins, anthracene Type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin and the like.
- Examples of the melamine resin include a polymer formed by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.
- Examples of the phenol resin include phenol novolac resin, cresol novolac resin, novolac type phenol resin such as bisphenol A type novolac resin, methylol type resole resin, resole type phenol resin such as dimethylene ether type resole resin, or aryl alkylene type phenol resin. And the like, and one of them or a combination of two or more thereof.
- urea resins examples include resins obtained by condensation of urea and formaldehyde.
- thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more kinds.
- the resin used in the glass fiber reinforced resin molded product of the present embodiment is preferably a thermoplastic resin because the excellent fluidity of the glass fiber contributes greatly to the improvement of molding processability.
- a thermoplastic resin is more preferable, and a resin selected from the group consisting of a polyamide resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyarylene sulfide resin, a polyarylketone resin and a liquid crystal polymer (LCP) is further preferable.
- Polyamide resin is particularly preferable.
- reinforcing fibers other than glass fibers for example, carbon fibers, metal fibers, etc.
- fillers other than glass fibers for example, glass powder, talc, mica, etc.
- flame retardants ultraviolet absorption
- examples thereof include agents, heat stabilizers, antioxidants, antistatic agents, fluidity improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents and pigments.
- the glass fiber reinforced resin molded article of the present embodiment is a mixture of the above-mentioned glass fiber, the above-mentioned thermoplastic resin or thermosetting resin, and an additive other than the above-mentioned glass fiber, injection molding method, injection compression molding.
- Method two-color molding method, hollow molding method, foam molding method (including supercritical fluid foam molding method), insert molding method, in-mold coating molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, Lamination molding method, press molding method, blow molding method, stamping molding method, infusion method, hand lay-up method, spray-up method, resin transfer molding method, sheet molding compound method, bulk molding compound method, pultrusion method, filament winding method It can be obtained by molding from a known molding method such as a method by a molding method appropriately selected according to the characteristics of the resin and the additive and the use of the glass fiber reinforced resin molded product.
- a known molding method such as a method by a molding method appropriately selected according to the characteristics of the resin and the additive and the use of the glass fiber reinforced resin molded product.
- the glass fiber-reinforced resin molded product of the present embodiment is a glass fiber-reinforced resin injection molded product obtained by the injection molding method. It is preferable to have.
- the injection molding method using a thermoplastic resin pellet containing glass fiber is preferably adopted.
- the number of glass filaments constituting the glass fibers is preferably 1 to 20,000, more preferably 50 to 10,000, and further preferably 1,000 to 8,000.
- the length of the glass fiber (also referred to as a glass fiber bundle or glass strand) of the book is preferably 1.0 to 30,000 mm, more preferably 2.0 to 15.0 mm, and further preferably 2.3 to 7.8 mm. Chopped strands cut into pieces are preferably adopted.
- the number average fiber length L ( ⁇ m) of the glass fibers contained in the glass fiber reinforced resin molded product is the length of the chopped strands contained in the thermoplastic resin pellets, the kneading conditions from pellet formation to injection molding, and injection molding. It can be adjusted according to the conditions. For example, the number average fiber length L ( ⁇ m) of the glass fibers contained in the glass fiber reinforced resin molded product can be increased by lowering the screw rotation speed during biaxial kneading in the range of 10 to 1000 rpm, It can be shortened by increasing the screw rotation speed during biaxial kneading.
- the number of glass fillers forming the glass fibers is 10 to 30000, and the number of glass filaments forming the glass fibers is not cut and is not cut. 1 to 20,000, and cut fibers pulverized by a known method such as a ball mill or a Hensyl mixer to a length of 0.001 to 0.900 mm.
- Glass fiber reinforced resin molded product of the present embodiment include fine or thin-walled electronic components (connectors), but not necessarily fine or thin-walled, electronic device housings, other electronic components (sockets, LEDs, Encapsulation products), vehicle exterior parts (bumpers, fenders, bonnets, air dams, wheel covers, etc.), vehicle interior parts (door trims, ceiling materials, etc.), vehicle engine parts (oil pans, engine covers, intake manifolds, exhaust manifolds) Etc.), vehicle mechanism parts (pulleys, seal rings, gears, bearings), muffler-related members (noise reduction members, etc.), and high-pressure tanks.
- connectors but not necessarily fine or thin-walled, electronic device housings, other electronic components (sockets, LEDs, Encapsulation products), vehicle exterior parts (bumpers, fenders, bonnets, air dams, wheel covers, etc.), vehicle interior parts (door trims, ceiling materials, etc.), vehicle engine parts (oil pans, engine covers,
- Examples 1 and 2 Comparative Examples 1 to 5
- Table 1 the minor axis/major axis of glass fiber, the cross-sectional shape of glass fiber, the number average fiber length of glass fiber and the glass fiber content in the glass fiber reinforced resin molded product are shown. 1 to 5 so that the glass fiber has a minor axis/major axis, a cross-sectional shape of the glass fiber, a cutting length (usually about 1 to 5 mm) and a compounding amount (glass fiber composition/minor axis/major axis/cross-sectional shape/focusing).
- the glass chopped strand of E glass composition in which the number of glass fibers and the cut length/number of glass fibers determine the weight of the glass fibers in the glass fiber reinforced resin molded product, and polyamide resin PA6 (Ube Industries Ltd. Co., Ltd., trade name: UBE Nylon 1015B) is adjusted by adjusting the screw rotation speed with a twin-screw kneader (Toshiba Machinery Co., Ltd., trade name: TEM-26SS) to prepare resin pellets. did.
- injection molding was performed by an injection molding machine (manufactured by Nisshin Plastic Industry Co., Ltd., trade name: NEX80), and an A-type dumbbell test piece (thickness) according to JIS K 7165:2008 was prepared.
- 4 mm was prepared as a test piece for measuring tensile strength, bending strength, and Charpy impact strength without notch.
- a warp measurement test piece a flat plate having dimensions of 60 mm in length ⁇ 40 mm in width ⁇ 1 mm in thickness was prepared by injection molding using the injection molding machine.
- a surface roughness measuring test piece a flat plate having dimensions of 60 mm in length ⁇ 40 mm in width ⁇ 2 mm in thickness was prepared by injection molding using the injection molding machine.
- the number average fiber length of the glass fibers contained in the molded product, the tensile strength of the molded product, the bending strength, the Charpy impact strength without notch, the flow length at low speed in injection molding, And the flow length at high speed were measured.
- the warpage and surface roughness were measured by the following methods. The results are shown in Table 1.
- warp With respect to the test piece for measuring warpage, the distance from a flat surface at one corner on a diagonal line when one corner of the test piece was grounded on a flat surface was measured with a caliper to obtain a warp amount.
- the surface roughness measuring test piece was measured using a surface roughness meter (Small surface roughness measuring instrument Surftest SJ-301 manufactured by Mitutoyo Co., Ltd.) in accordance with JIS B 0601:1982 to obtain an arithmetic mean roughness Ra. was measured.
- the glass fibers contained in the glass fiber reinforced resin molded product shown in Examples 1 and 2 have a minor axis D1 in the range of 3.0 to 10.5 ⁇ m and a major axis D2.
- the glass fiber has a flat cross-sectional shape in the range of 11.0 to 29.0 ⁇ m, and the number average fiber length L ( ⁇ m) of the glass fibers contained in the glass fiber reinforced resin molded product is in the range of 150 to 475 ⁇ m.
- the glass fiber content C (wt %) in the fiber reinforced resin molded product is in the range of 40.0 to 75.0 wt %, and the above D1, D2, L and C satisfy the following formula (1).
- the glass fiber reinforced resin molded products shown in Examples 1 and 2 are excellent in balance of static and dynamic strength and fluidity. 260.0 ⁇ C 2 x L/(D1 x D2 2 ) ⁇ 400.0 (1) On the other hand, in the glass fiber reinforced resin molded products of Comparative Examples 1 to 5, since the above formula (1) is not satisfied, it cannot be said that the static and dynamic strengths and the fluidity are excellent in good balance.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
300.0 ≦ D2×L/V ≦ 1000.0 ・・・(6)
260.0≦C2×L/(D1×D22)≦ 400.0 ・・・(1)
本発明のガラス繊維強化樹脂成形品によれば、前記D1、D2、L及びCが上述した範囲にあり、かつ、上記式(1)の条件を満たすことで、ガラス繊維強化樹脂成形品は、静的及び動的な強度、並びに流動性がバランス良く優れる。
300.0≦C2×L/(D1×D22)≦ 335.0 ・・・(3)
本発明のガラス繊維強化樹脂成形品によれば、前記D1、D2、L及びCが上述した範囲にあり、かつ、上記式(3)の条件を満たすことで、ガラス繊維強化樹脂成形品は、静的及び動的な強度、並びに流動性が極めてバランス良く優れており、かつ、寸法安定性及び表面平滑性に優れている。
260.0≦C2×L/(D1×D22)≦ 400.0 ・・・(1)
(T×B)1/2×I×(F1×F2)1/2>300.0 ・・・(2)
JIS K 7165:2008に準じたA型ダンベル試験片(厚さ4mm)について、試験温度23℃の条件で、精密万能試験機((株)島津製作所製、商品名:オートグラフAG-5000B)を用いて、JIS K 7165:2008に準拠した静的引張試験を行い、引張強度を測定する。
前記試験片について、試験温度23℃の条件で、精密万能試験機((株)島津製作所製、商品名:オートグラフAG-5000B)を用いて、JIS K 7171:2016に準拠した静的引張試験を行い、曲げ強度を測定する。
前記試験片について、試験温度23℃の条件で、デジタル衝撃試験機((株)東洋精機製作所製、DG-UB型)を用いて、ISO 179-1に準拠したノッチ無シャルピー衝撃試験を行い、ノッチ無シャルピー衝撃強さを測定する。
ガラス繊維強化樹脂成形品を得るために調製されたガラス繊維含有樹脂ペレットを、小型電動射出成型機(住友重機械工業(株)製SE18-DUZ)でスパイラル巾5mm、スパイラル厚み3mmの寸法の金型に速度25mm/sの条件で射出し、圧力が50MPaとなる際のスパイラル長を測定する。
ガラス繊維強化樹脂成形品を得るために調製されたガラス繊維含有樹脂ペレットを、小型電動射出成型機(住友重機械工業(株)製 SE18-DUZ)でスパイラル巾5mm、スパイラル厚み3mmの寸法の金型に速度50mm/sの条件で射出し、圧力が50MPaとなる際のスパイラル長を測定する。
300.0≦C2×L/(D1×D22)≦ 335.0 ・・・(3)
(T×B)1/2×I×(F1×F2)1/2>330.0 ・・・(4)
また、寸法安定性に優れるかどうかの判断は、例えば、ガラス繊維強化樹脂成形品の反りが、4.0mm未満であるかどうかで判断することができる。また、表面平滑性に優れるかどうかの判断は、例えば、ガラス繊維強化樹脂成形品の算術平均粗さが、0.15mm未満であるかどうかで判断することができる。
310.0≦C2×L/(D1×D22)≦ 325.0 ・・・(5)
まず、ガラス繊維強化樹脂成形品におけるガラス繊維の短径・長径、ガラス繊維の断面形状、ガラス繊維の数平均繊維長及びガラス繊維含有率が、表1に示される実施例1~2及び比較例1~5となるように、ガラス繊維の短径・長径、ガラス繊維の断面形状、切断長(通常、1~5mm程度)及び配合量(ガラス繊維の組成・短径・長径・断面形状・集束本数、及び、ガラス繊維の切断長さ・本数により、ガラス繊維強化樹脂成形品中のガラス繊維の重量は決定される)を調整したEガラス組成のガラスチョップドストランドと、ポリアミド樹脂PA6(宇部興産(株)製、商品名:UBEナイロン1015B)とを、スクリュ回転数を調整して、二軸混練機(東芝機械(株)製、商品名:TEM-26SS)にて混練し、樹脂ペレットを作製した。次に、得られた樹脂ペレットを用い、射出成形機(日清樹脂工業(株)製、商品名:NEX80)により射出成形を行い、JIS K 7165:2008に準じたA型ダンベル試験片(厚さ4mm)を作成し、引張強度・曲げ強度・ノッチ無しシャルピー衝撃強さ測定用試験片とした。また、反り測定用試験片として、寸法が縦60mm×横40mm×厚さ1mmの平板を、前記射出成形機による射出成形にて作成した。また、表面粗さ測定用試験片として、寸法が縦60mm×横40mm×厚さ2mmの平板を、前記射出成形機による射出成形にて作成した。
前記反り測定用試験片について、試験片の一角を平坦面に接地した際の対角線上の一角の平坦面からの距離をノギスで測定し、反り量とした。
前記表面粗さ測定用試験片について、表面粗さ計((株)ミツトヨ社製小型表面粗さ測定器サーフテストSJ-301)を用いて、JIS B 0601:1982に準拠し算術平均粗さRaを測定した。
260.0 ≦ C2×L/(D1×D22)≦ 400.0 ・・・(1)
一方、比較例1~5のガラス繊維強化樹脂成形品においては、上記式(1)が満たされないため、静的及び動的な強度、並びに流動性がバランス良く優れているとはいえない。
Claims (4)
- ガラス繊維強化樹脂成形品であって、前記ガラス繊維強化樹脂成形品に含まれるガラス繊維は、短径D1が3.0~10.5μmの範囲にあり、長径D2が11.0~29.0μmの範囲にある扁平な断面形状を備え、前記ガラス繊維強化樹脂成形品に含まれるガラス繊維の数平均繊維長L(μm)が150~475μmの範囲にあり、前記ガラス繊維強化樹脂成形品におけるガラス繊維含有率C(wt%)が40.0~75.0wt%の範囲にあり、前記D1、D2、L及びCが下記式(1)を満たすことを特徴とするガラス繊維強化樹脂成形品。
260.0 ≦ C2×L/(D1×D22)≦ 400.0 ・・・(1) - 前記D1が3.5~6.4μmの範囲にあり、前記D2が14.0~26.0μmの範囲にあり、前記Lが165~300μmの範囲にあり、前記Cが42.5~65.0wt%の範囲にあり、前記D1、D2、L及びCが下記式(3)を満たすことを特徴とする請求項1記載のガラス繊維強化樹脂成形品。
300.0 ≦ C2×L/(D1×D22)≦ 335.0 ・・・(3) - 前記ガラス繊維強化樹脂成形品に含まれる樹脂は、ポリアミド樹脂、ポリブチレンテレフタレート樹脂、ポリカーボネート樹脂、ポリアリーレンサルファイド樹脂、ポリアリールケトン樹脂及び液晶ポリマー(LCP)からなる群から選択される射出成形用熱可塑性樹脂であることを特徴とする請求項2記載のガラス繊維強化樹脂成形品。
- 前記ガラス繊維強化樹脂成形品に含まれる樹脂は、ポリアミド樹脂であることを特徴とする請求項3記載のガラス繊維強化樹脂成形品。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020504043A JP6750753B1 (ja) | 2018-12-27 | 2019-08-30 | ガラス繊維強化樹脂成形品 |
US17/049,505 US11091596B2 (en) | 2018-12-27 | 2019-08-30 | Glass fiber-reinforced resin molded article |
KR1020207028593A KR102283574B1 (ko) | 2018-12-27 | 2019-08-30 | 유리 섬유 강화 수지 성형품 |
CN201980049149.XA CN112469784B (zh) | 2018-12-27 | 2019-08-30 | 玻璃纤维强化树脂成型品 |
EP19903366.3A EP3795642B1 (en) | 2018-12-27 | 2019-08-30 | Glass fiber-reinforced resin molded article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018245155A JP2019052323A (ja) | 2018-12-27 | 2018-12-27 | ガラス繊維強化樹脂成形品 |
JP2018-245155 | 2018-12-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020137004A1 true WO2020137004A1 (ja) | 2020-07-02 |
Family
ID=66014332
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/034219 WO2020137004A1 (ja) | 2018-12-27 | 2019-08-30 | ガラス繊維強化樹脂成形品 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11091596B2 (ja) |
EP (1) | EP3795642B1 (ja) |
JP (2) | JP2019052323A (ja) |
KR (1) | KR102283574B1 (ja) |
CN (1) | CN112469784B (ja) |
TW (1) | TWI734191B (ja) |
WO (1) | WO2020137004A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022054660A1 (ja) * | 2020-09-11 | 2022-03-17 | 日東紡績株式会社 | ガラス繊維強化樹脂板 |
WO2022075273A1 (ja) * | 2020-10-08 | 2022-04-14 | 日東紡績株式会社 | ガラス繊維強化樹脂成形品 |
WO2022080330A1 (ja) * | 2020-10-15 | 2022-04-21 | 日東紡績株式会社 | ガラス繊維強化樹脂板 |
WO2023153007A1 (ja) * | 2022-02-10 | 2023-08-17 | Jnc株式会社 | 繊維状無機フィラーを含む樹脂組成物及び成形体 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6439027B1 (ja) * | 2017-11-27 | 2018-12-19 | 住友化学株式会社 | 液晶ポリエステル樹脂組成物および成形体 |
CN112759923A (zh) * | 2020-12-25 | 2021-05-07 | 金发科技股份有限公司 | 一种具有特定玻纤长度的玻纤增强半芳香族聚酰胺模塑组合物及模塑品 |
CN115835948B (zh) * | 2021-05-31 | 2023-06-09 | 日东纺绩株式会社 | 玻璃纤维增强树脂成型品 |
WO2022254914A1 (ja) * | 2021-05-31 | 2022-12-08 | 日東紡績株式会社 | ガラス繊維強化樹脂成形品 |
JPWO2022254918A1 (ja) * | 2021-05-31 | 2022-12-08 | ||
JP7385980B1 (ja) * | 2022-08-18 | 2023-11-24 | 日東紡績株式会社 | 扁平断面ガラス繊維、及び、ガラス再生材料を含むガラス原料からの扁平断面ガラス繊維の製造方法 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007161898A (ja) * | 2005-12-14 | 2007-06-28 | Ueno Technology:Kk | 液晶ポリエステル樹脂組成物 |
WO2007091293A1 (ja) * | 2006-02-06 | 2007-08-16 | Nitto Boseki Co., Ltd. | 扁平ガラス繊維含有ペレット、扁平ガラス繊維含有熱可塑性樹脂成型物及びこれらの製造方法 |
JP2008088377A (ja) * | 2006-10-05 | 2008-04-17 | Mitsubishi Engineering Plastics Corp | ブレーカー筐体用ポリアミド樹脂組成物及びブレーカー筐体 |
JP2009269952A (ja) | 2008-05-01 | 2009-11-19 | Mitsubishi Engineering Plastics Corp | ねじ部材用ポリアミド樹脂組成物 |
JP2010111816A (ja) * | 2008-11-07 | 2010-05-20 | Mitsubishi Engineering Plastics Corp | ウエルド部を有するポリブチレンテレフタレート樹脂成形品 |
JP2012025844A (ja) * | 2010-07-23 | 2012-02-09 | Toyobo Co Ltd | ガラス繊維強化ポリアミド樹脂組成物 |
JP2013194196A (ja) * | 2012-03-22 | 2013-09-30 | Toray Ind Inc | ポリアミド樹脂組成物およびそれを成形してなる成形品 |
JP2014040555A (ja) * | 2012-08-24 | 2014-03-06 | Mitsubishi Engineering Plastics Corp | ポリカーボネート樹脂組成物及び成形体 |
JP2014040556A (ja) * | 2012-08-24 | 2014-03-06 | Mitsubishi Engineering Plastics Corp | ポリカーボネート樹脂組成物及び成形体 |
WO2014171363A1 (ja) * | 2013-04-16 | 2014-10-23 | 東洋紡株式会社 | ガラス繊維強化ポリアミド樹脂組成物 |
WO2015001996A1 (ja) * | 2013-07-04 | 2015-01-08 | 東洋紡株式会社 | 吸水時の振動性に優れた高融点ポリアミド樹脂組成物 |
JP2015105359A (ja) * | 2013-12-02 | 2015-06-08 | 東レ株式会社 | ガラス繊維強化熱可塑性樹脂組成物およびその成形品 |
WO2018159861A2 (ja) | 2017-10-06 | 2018-09-07 | 日東紡績株式会社 | ガラス繊維強化樹脂成形品 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2020282B1 (en) * | 2006-05-25 | 2014-08-13 | Mitsubishi Engineering-Plastics Corporation | Moldings of fiber-reinforced thermoplastic resin |
JP5058878B2 (ja) * | 2008-05-16 | 2012-10-24 | 出光興産株式会社 | 熱可塑性樹脂組成物及び鏡筒用射出成形体 |
WO2010087192A1 (ja) * | 2009-01-29 | 2010-08-05 | 東洋紡績株式会社 | ガラス繊維強化ポリアミド樹脂組成物 |
EP2570454B1 (en) * | 2010-05-10 | 2019-09-18 | Nitto Boseki CO., LTD. | Method of foam molding of resin reinforced with flat glass fibers |
CN103946272B (zh) * | 2011-12-23 | 2017-03-08 | 埃姆斯·帕特恩特股份有限公司 | 聚酰胺模塑材料、其用途,以及由其制备的模制部件 |
CN102675863A (zh) * | 2012-05-11 | 2012-09-19 | 金发科技股份有限公司 | 一种低翘曲聚酰胺复合材料 |
DK2927263T3 (en) * | 2014-04-01 | 2016-05-09 | Ems Patent Ag | Polyamide castings, especially for the manufacture of molded parts in the drinking water field |
US20170240727A1 (en) * | 2014-10-24 | 2017-08-24 | Dsm Ip Assets B.V. | Reinforced polymer molding composition |
DE112016004623T5 (de) * | 2015-10-09 | 2018-06-21 | Ube Industries, Ltd. | Polyamidharzzusammensetzung |
CN109071941A (zh) * | 2016-05-04 | 2018-12-21 | Ems专利股份公司 | 聚酰胺模塑组合物和由此制成的模塑品 |
JP6790812B2 (ja) * | 2016-12-26 | 2020-11-25 | 日東紡績株式会社 | ガラス繊維強化樹脂成形品 |
EP3730534B1 (en) * | 2017-12-21 | 2021-11-10 | Teijin Limited | Polycarbonate-polydiorganosiloxane copolymer, resin composition of polycarbonate-polydiorganosiloxane copolymer, and production method for resin composition of polycarbonate-polydiorganosiloxane copolymer |
WO2019122142A1 (en) * | 2017-12-21 | 2019-06-27 | Rhodia Operations | Polyamide formulations comprising semi-crystalline copolyamide and flat glass fibers |
-
2018
- 2018-12-27 JP JP2018245155A patent/JP2019052323A/ja active Pending
-
2019
- 2019-08-30 EP EP19903366.3A patent/EP3795642B1/en active Active
- 2019-08-30 WO PCT/JP2019/034219 patent/WO2020137004A1/ja unknown
- 2019-08-30 CN CN201980049149.XA patent/CN112469784B/zh active Active
- 2019-08-30 KR KR1020207028593A patent/KR102283574B1/ko active IP Right Grant
- 2019-08-30 JP JP2020504043A patent/JP6750753B1/ja active Active
- 2019-08-30 US US17/049,505 patent/US11091596B2/en active Active
- 2019-09-11 TW TW108132696A patent/TWI734191B/zh active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007161898A (ja) * | 2005-12-14 | 2007-06-28 | Ueno Technology:Kk | 液晶ポリエステル樹脂組成物 |
WO2007091293A1 (ja) * | 2006-02-06 | 2007-08-16 | Nitto Boseki Co., Ltd. | 扁平ガラス繊維含有ペレット、扁平ガラス繊維含有熱可塑性樹脂成型物及びこれらの製造方法 |
JP2008088377A (ja) * | 2006-10-05 | 2008-04-17 | Mitsubishi Engineering Plastics Corp | ブレーカー筐体用ポリアミド樹脂組成物及びブレーカー筐体 |
JP2009269952A (ja) | 2008-05-01 | 2009-11-19 | Mitsubishi Engineering Plastics Corp | ねじ部材用ポリアミド樹脂組成物 |
JP2010111816A (ja) * | 2008-11-07 | 2010-05-20 | Mitsubishi Engineering Plastics Corp | ウエルド部を有するポリブチレンテレフタレート樹脂成形品 |
JP2012025844A (ja) * | 2010-07-23 | 2012-02-09 | Toyobo Co Ltd | ガラス繊維強化ポリアミド樹脂組成物 |
JP2013194196A (ja) * | 2012-03-22 | 2013-09-30 | Toray Ind Inc | ポリアミド樹脂組成物およびそれを成形してなる成形品 |
JP2014040555A (ja) * | 2012-08-24 | 2014-03-06 | Mitsubishi Engineering Plastics Corp | ポリカーボネート樹脂組成物及び成形体 |
JP2014040556A (ja) * | 2012-08-24 | 2014-03-06 | Mitsubishi Engineering Plastics Corp | ポリカーボネート樹脂組成物及び成形体 |
WO2014171363A1 (ja) * | 2013-04-16 | 2014-10-23 | 東洋紡株式会社 | ガラス繊維強化ポリアミド樹脂組成物 |
WO2015001996A1 (ja) * | 2013-07-04 | 2015-01-08 | 東洋紡株式会社 | 吸水時の振動性に優れた高融点ポリアミド樹脂組成物 |
JP2015105359A (ja) * | 2013-12-02 | 2015-06-08 | 東レ株式会社 | ガラス繊維強化熱可塑性樹脂組成物およびその成形品 |
WO2018159861A2 (ja) | 2017-10-06 | 2018-09-07 | 日東紡績株式会社 | ガラス繊維強化樹脂成形品 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3795642A4 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022054660A1 (ja) * | 2020-09-11 | 2022-03-17 | 日東紡績株式会社 | ガラス繊維強化樹脂板 |
WO2022075273A1 (ja) * | 2020-10-08 | 2022-04-14 | 日東紡績株式会社 | ガラス繊維強化樹脂成形品 |
US11827770B2 (en) | 2020-10-08 | 2023-11-28 | Nitto Bosekl Co., Ltd. | Glass fiber-reinforced resin molded product |
WO2022080330A1 (ja) * | 2020-10-15 | 2022-04-21 | 日東紡績株式会社 | ガラス繊維強化樹脂板 |
JP7063424B1 (ja) * | 2020-10-15 | 2022-05-09 | 日東紡績株式会社 | ガラス繊維強化樹脂板 |
WO2023153007A1 (ja) * | 2022-02-10 | 2023-08-17 | Jnc株式会社 | 繊維状無機フィラーを含む樹脂組成物及び成形体 |
Also Published As
Publication number | Publication date |
---|---|
CN112469784A (zh) | 2021-03-09 |
US20210087344A1 (en) | 2021-03-25 |
KR102283574B1 (ko) | 2021-07-29 |
US11091596B2 (en) | 2021-08-17 |
CN112469784B (zh) | 2021-09-07 |
TW202024196A (zh) | 2020-07-01 |
EP3795642B1 (en) | 2022-08-17 |
EP3795642A1 (en) | 2021-03-24 |
TWI734191B (zh) | 2021-07-21 |
JP6750753B1 (ja) | 2020-09-02 |
JP2019052323A (ja) | 2019-04-04 |
EP3795642A4 (en) | 2021-08-18 |
JPWO2020137004A1 (ja) | 2021-02-18 |
KR20200121897A (ko) | 2020-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6750753B1 (ja) | ガラス繊維強化樹脂成形品 | |
KR102403724B1 (ko) | 유리 섬유 강화 수지 성형품 | |
JP7410411B2 (ja) | ガラス繊維強化樹脂成形品 | |
CN111183174B (zh) | 玻璃纤维增强树脂成型品 | |
JP7201016B2 (ja) | ガラス繊維強化樹脂成形品 | |
JP7070819B1 (ja) | ガラス繊維強化樹脂成形品 | |
WO2017171102A1 (ja) | ガラス繊維強化樹脂組成物及び成形品 | |
CN114829504B (zh) | 玻璃纤维强化树脂组合物及玻璃纤维强化树脂成型品 | |
WO2024157412A1 (ja) | 扁平断面ガラス繊維、ガラス繊維強化樹脂組成物およびガラス繊維強化樹脂成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2020504043 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19903366 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20207028593 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2019903366 Country of ref document: EP Effective date: 20201021 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |