WO2022085584A1 - ポリアミド樹脂組成物およびそれからなる成形体、車載カメラ用部品 - Google Patents

ポリアミド樹脂組成物およびそれからなる成形体、車載カメラ用部品 Download PDF

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WO2022085584A1
WO2022085584A1 PCT/JP2021/038212 JP2021038212W WO2022085584A1 WO 2022085584 A1 WO2022085584 A1 WO 2022085584A1 JP 2021038212 W JP2021038212 W JP 2021038212W WO 2022085584 A1 WO2022085584 A1 WO 2022085584A1
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resin composition
filler
polyamide resin
mass
polyamide
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PCT/JP2021/038212
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English (en)
French (fr)
Japanese (ja)
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聡記 長畑
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ユニチカ株式会社
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Priority to CN202180071575.0A priority Critical patent/CN116323758A/zh
Priority to JP2022557477A priority patent/JPWO2022085584A1/ja
Publication of WO2022085584A1 publication Critical patent/WO2022085584A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • 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
    • 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
    • C08K7/06—Elements
    • 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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a polyamide resin composition, a molded product made of the polyamide resin composition, and parts for an in-vehicle camera.
  • the camera housing is a case part that houses the structural parts of the camera equipment.
  • the camera barrel is a holder component that exists inside the camera housing and holds the lens for the camera. All parts are required to have excellent mechanical properties in order to protect and hold the camera and lens. Further, all the parts are required to have excellent dimensional stability so that the assembled lens is not distorted even when exposed to a high temperature.
  • Patent Document 1 a plate-shaped filler is contained in a polyamide resin in an amount of 0.002 to 0.5% by mass based on the entire polyamide resin composition, so that a molded product obtained can be obtained in a flow direction of the resin at the time of molding. It is disclosed that the coefficient of linear expansion of (MD) becomes smaller.
  • the polyamide resin composition described in Patent Document 1 uses polyamide 66, the obtained molded product is insufficiently improved in dimensional stability, and in particular, the flow direction (MD) of the resin during molding is insufficient. There is a problem that the linear expansion coefficient in the direction orthogonal to (TD) is large. In a molded body used for an in-vehicle camera component or the like, not only the flow direction (MD) of the resin at the time of molding but also the linear expansion coefficient in the orthogonal direction (TD) is required to be small.
  • the present invention provides a polyamide resin composition capable of obtaining a molded product having excellent mechanical properties and excellent dimensional stability in both the flow direction (MD) and the orthogonal direction (TD). The purpose is.
  • the present inventors have found that the above object can be achieved by blending a specific amount of a filler with a semi-aromatic polyamide, and have reached the present invention.
  • the injection-molded article is characterized by having a linear expansion coefficient of 70 ⁇ 10-6 (1 / ° C.) or less at 80 ° C. in a direction orthogonal to the flow direction of the resin during injection molding.
  • the length of burrs generated at the position corresponding to the gas vent portion of the mold during injection molding is preferably 150 ⁇ m or less.
  • the filler (B) is composed of a plate-shaped filler and a fibrous filler.
  • the mass ratio of the plate-like filler to the fibrous filler is preferably 50/50 to 90/10.
  • the plate-shaped filler is glass flakes and the fibrous filler is glass fiber.
  • the plate-shaped filler is glass flakes and the fibrous filler is carbon fiber.
  • the molded product of the present invention is a molded product of the above-mentioned polyamide resin composition.
  • the in-vehicle camera component of the present invention is made of the above-mentioned molded body.
  • a polyamide resin composition capable of obtaining a molded product having excellent mechanical properties and excellent dimensional stability in both the flow direction (MD) and the orthogonal direction (TD) can be obtained. Can be provided.
  • the polyamide resin composition of the present invention contains a semi-aromatic polyamide (A) and a filler (B).
  • the semi-aromatic polyamide (A) used in the present invention is composed of an aromatic dicarboxylic acid component and an aliphatic diamine component.
  • the aromatic dicarboxylic acid component preferably contains terephthalic acid as a main component.
  • "containing terephthalic acid as a main component” means that the aromatic dicarboxylic acid component contains 90 mol% or more of terephthalic acid.
  • the content of terephthalic acid in the aromatic dicarboxylic acid component is preferably 95 mol% or more, more preferably 100 mol%. If the aromatic dicarboxylic acid component does not contain terephthalic acid as a main component, the obtained molded product may have poor dimensional stability.
  • the aromatic dicarboxylic acid component may contain an aromatic dicarboxylic acid other than terephthalic acid.
  • aromatic dicarboxylic acids include isophthalic acid and naphthalenedicarboxylic acid.
  • the aliphatic diamine component preferably contains an aliphatic diamine having 8 or more carbon atoms as a main component.
  • "mainly composed of an aliphatic diamine having 8 or more carbon atoms” means that the aliphatic diamine component contains 90 mol% or more of the aliphatic diamine having 8 or more carbon atoms.
  • the content of the aliphatic diamine having 8 or more carbon atoms in the aliphatic diamine component is preferably 95 mol% or more, more preferably 100 mol%. If the aliphatic diamine component does not contain an aliphatic diamine having 8 or more carbon atoms as a main component, the semi-aromatic polyamide (A) may have reduced processability.
  • Examples of the aliphatic diamine having 8 or more carbon atoms include 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, and 1,12-undecanediamine.
  • the semi-aromatic polyamide (A) is more preferable because it has an excellent balance between heat resistance and processability and suppresses water absorption and moisture permeability.
  • the aliphatic diamine component may contain an aliphatic diamine other than the aliphatic diamine having 8 or more carbon atoms.
  • examples of other aliphatic diamines include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, and 1 , 6-Hexanediamine, 1,7-heptanediamine and the like.
  • the semi-aromatic polyamide (A) may contain a dicarboxylic acid other than the aromatic dicarboxylic acid; a diamine other than the aliphatic diamine; lactams; ⁇ -aminocarboxylic acid as long as the effect of the present invention is not impaired.
  • the dicarboxylic acid other than the aromatic dicarboxylic acid include fats such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.
  • Group dicarboxylic acids examples thereof include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
  • diamines other than aliphatic diamines include alicyclic diamines such as 1,4-cyclohexanediamine; and aromatic diamines such as m-xylylenediamine and paraxylylenediamine.
  • lactams include caprolactam and laurolactam.
  • Examples of the ⁇ -aminocarboxylic acid include aminocaproic acid and 11-aminoundecanoic acid.
  • the semi-aromatic polyamide (A) may contain a monocarboxylic acid component in addition to the dicarboxylic acid component and the diamine component.
  • a monocarboxylic acid component examples include aliphatic monocarboxylic acids such as stearate, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and behenic acid; 4-ethylcyclohexanecarboxylic acid, 4-to.
  • Alicyclic monocarboxylic acids such as xylcyclohexanecarboxylic acid and 4-laurylcyclohexanecarboxylic acid; 4-ethylbenzoic acid, 4-hexylbenzoic acid, 4-laurylbenzoic acid, alkylbenzoic acids, 1-naphthoic acid, 2- Examples include aromatic monocarboxylic acids such as naphthoic acid.
  • a molcarboxylic acid having a molecular weight of 140 or more is preferable because the molding processability of the semi-aromatic polyamide (A) is improved, and stearic acid is more preferable because of its high versatility.
  • the molecular weight of the monocarboxylic acid is the molecular weight of the raw material monocarboxylic acid used in the polymerization.
  • the content of the monocarboxylic acid component is preferably 0.3 to 5.0 mol%, preferably 0.6 to 4.0 mol%, based on all the monomers constituting the semi-aromatic polyamide. More preferably, it is more preferably 1.0 to 3.5 mol%.
  • the semi-aromatic polyamide (A) has improved molding processability without significantly reducing the molecular weight.
  • the semi-aromatic polyamide (A) can be produced by using a conventionally known method of heat polymerization method or solution polymerization method.
  • the heat polymerization method is preferably used because it is industrially advantageous.
  • the heat polymerization method include a method including a step (i) of obtaining a reaction product from a dicarboxylic acid component and a diamine component, and a step (ii) of polymerizing the obtained reaction product.
  • the dicarboxylic acid powder is preheated to a temperature equal to or higher than the melting point of the diamine and lower than the melting point of the dicarboxylic acid, and the dicarboxylic acid powder at this temperature is kept in the state of the powdered dicarboxylic acid.
  • a method of adding a diamine without substantially containing water can be mentioned.
  • a suspension consisting of a molten diamine and a solid dicarboxylic acid is stirred and mixed to obtain a mixed solution, and then at a temperature below the melting point of the semi-aromatic polyamide finally produced.
  • a method of obtaining a mixture of a salt and a low polymer by carrying out a reaction of producing a salt by a reaction of a dicarboxylic acid and a diamine and a reaction of forming a low polymer by polymerizing the produced salt.
  • crushing may be carried out while allowing the reaction, or crushing may be carried out after taking out the reaction once after the reaction.
  • the former is preferable because the shape of the reaction product can be easily controlled.
  • the reaction product obtained in the step (i) is solid-phase polymerized at a temperature lower than the melting point of the finally produced semi-aromatic polyamide to increase the molecular weight to a predetermined molecular weight.
  • the solid phase polymerization is preferably carried out at a polymerization temperature of 180 to 270 ° C. and a reaction time of 0.5 to 10 hours in a stream of an inert gas such as nitrogen.
  • the reaction apparatus for the step (i) and the step (ii) is not particularly limited, and a known apparatus may be used.
  • the step (i) and the step (ii) may be performed by the same device or may be performed by different devices.
  • the heating method in the heat polymerization method is not particularly limited, but for example, a method of heating the reaction vessel with a medium such as water, steam, or a heat medium oil, a method of heating the reaction vessel with an electric heater, or stirring heat generated by stirring.
  • a method of utilizing the frictional heat associated with the movement of the equal contents can be mentioned. Moreover, you may combine these methods.
  • a polymerization catalyst may be used in order to increase the efficiency of polymerization.
  • the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid or salts thereof.
  • the amount of the polymerization catalyst added is usually preferably 2 mol% or less with respect to all the monomers constituting the semi-aromatic polyamide (A).
  • the filler (B) used in the present invention may be made of an organic compound or an inorganic compound.
  • Examples of the form of the filler (B) include plate-like, fibrous, granular, and amorphous, and among them, plate-like, fibrous, and granular are preferable because a molded product having excellent dimensional stability can be obtained. ..
  • the filler (B) may be used alone or in combination of two or more.
  • the content of the filler (B) needs to be 70 to 250 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide (A), and 80 to 200 parts by mass. It is preferably present, and more preferably 90 to 150 parts by mass.
  • the content of the filler (B) in the resin composition is 70 to 250 parts by mass, the obtained molded product can suppress shrinkage due to a temperature change of the semi-aromatic polyamide, so that the coefficient of linear expansion can be reduced. Further, it is possible to suppress burrs generated at the positions corresponding to the gas vent portion of the mold.
  • the obtained molded product has a large linear expansion coefficient, while when the content of the filler (B) exceeds 250 parts by mass, the fragrance is fragrant. It may be difficult to melt-knead with the group polyamide resin, and it may not be possible to produce pellets of the resin composition.
  • Examples of the plate-shaped filler include glass flakes, talc, mica, and scaly graphite.
  • examples of mica include muscovite, phlogopite fluorine, and phlogopite four silicon. Among them, glass flakes and mica are preferable because of their high versatility.
  • the fibrous filler examples include carbon fiber, glass fiber, silica fiber, silica / alumina fiber, zirconia fiber, alumina fiber, silicon carbide fiber, metal fiber (stainless fiber, aluminum oxide fiber, etc.), ceramic fiber, and boron whisker. , Zinc oxide whisker, asbestos, wallastnite, potassium titanate whisker, calcium carbonate whisker, aluminum borate whisker, magnesium sulfate whisker, acicular titanium oxide, sepiolite, zonotrite, milled fiber, cut fiber. Among them, glass fiber and wallastnite are preferable because of their high versatility.
  • the surface of the fibrous filler is preferably surface-treated with an aminosilane-based coupling agent or an epoxy resin in order to enhance the dispersibility in the semi-aromatic polyamide (A), and above all, the mechanical properties and the epoxy resin.
  • an aminosilane-based coupling agent or an epoxy resin in order to enhance the dispersibility in the semi-aromatic polyamide (A), and above all, the mechanical properties and the epoxy resin.
  • the surface is treated with an aminosilane-based coupling agent.
  • Examples of the granular filler include alumina, titanium oxide, boron nitride, silicon carbide, and calcium carbonate. Of these, calcium carbonate is preferable because of its high versatility.
  • the filler (B) is preferably composed of a plate-shaped filler and a fibrous filler.
  • the mass ratio of the plate-like filler to the fibrous filler is preferably 50/50 to 90/10, preferably 55/45 to 85/15. More preferred.
  • the mass ratio is 50/50 to 90/10, the obtained molded product can further reduce the coefficient of linear expansion and improve the mechanical properties.
  • the filler (B) is composed of a plate-shaped filler and a fibrous filler, it is a flow direction (MD) that glass flakes are used as the plate-shaped filler and glass fibers or carbon fibers are used as the fibrous filler.
  • the content of the carbon fibers is preferably less than 100 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide (A).
  • the content of carbon fibers in the polyamide resin composition is 100 parts by mass or more, pellets may not be obtained.
  • the polyamide resin composition of the present invention preferably further contains polyphenylene ether (C).
  • the resin composition contains the polyphenylene ether (C)
  • the obtained molded product can further shorten the burr length generated at the position corresponding to the gas vent portion of the mold during injection molding, and is permeable to water vapor. The amount can also be reduced.
  • the polyamide resin composition of the present invention contains polyphenylene ether (C)
  • the content thereof is preferably 20 to 110 parts by mass, preferably 25 to 110 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide (A). More preferably, it is 100 parts by mass.
  • Examples of commercially available products of polyphenylene ether (C) include Noril PPO640 (manufactured by SABIC) and Upiece PX-100F (manufactured by Mitsubishi Engineering Plastics).
  • the polyamide resin composition of the present invention is a filler other than the filler (B), an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, and a mold release agent, as long as the effects of the present invention are not impaired.
  • Additives such as lubricants, colorants, antioxidants, crystal nucleating agents, and other thermoplastic resins such as amorphous polyamides other than semi-aromatic polyamides (A) and polyphenylene ethers (C). May be good.
  • the content thereof is preferably 2% by mass or less of the polyamide resin composition.
  • the other thermoplastic resin is contained, the content thereof is preferably 50% by mass or less of the polyamide resin composition.
  • the bending strength of the obtained molded product can be 100 MPa or more, preferably 120 MPa or more, and more preferably 140 MPa or more.
  • the flexural modulus can be 10 GPa or more, preferably 12 GPa or more.
  • the injection molded product obtained from the polyamide resin composition of the present invention is excellent in dimensional stability in both the flow direction (MD) and the orthogonal direction (TD) of the resin during injection molding. Therefore, the coefficient of linear expansion at 80 ° C. in either the MD or TD direction can be 70 ⁇ 10-6 (1 / ° C.) or less, preferably 60 ⁇ 10-6 (1 / ° C.) or less. It can be more preferably 45 ⁇ 10 -6 (1 / ° C.) or less. The coefficient of linear expansion of 70 ⁇ 10 -6 (1 / ° C.) or less at 80 ° C.
  • the resin composition constituting the molded product has glass flakes or glass flakes.
  • This can be achieved by containing a plate-shaped filler such as mica, a granular filler, or a plate-shaped filler and a fibrous filler in a specific mass ratio.
  • the burr length generated at the position corresponding to the gas vent portion of the mold during injection molding can be 180 ⁇ m or less, preferably 150 ⁇ m or less. It can be more preferably 135 ⁇ m or less. Generally, if burrs are generated during molding, the production efficiency is lowered, so that the length of the burrs is preferably short.
  • the polyamide resin composition of the present invention is also excellent in low water absorption and low moisture permeability.
  • Water absorption and moisture permeability greatly affect dimensional stability, and in general, the lower the water absorption and moisture permeability, the better the dimensional stability. Further, when used as an in-vehicle camera component material, the lower the water absorption and moisture permeability, the more the lens fogging can be suppressed.
  • the permeated water vapor amount of the plate-shaped molded product obtained by molding the resin composition to a thickness of 1 mm in an atmosphere of 65 ° C. can be 150 mg or less, preferably 130 mg or less, more preferably. Can be 120 mg or less.
  • the method for producing the resin composition by blending each component constituting the resin composition is not particularly limited, but it is preferably produced by the melt-kneading method.
  • the melt-kneading method include a method using a batch type kneader such as lavender, a Banbury mixer, a Henschel mixer, a helical rotor, a roll, a single-screw extruder, a twin-screw extruder and the like.
  • the melt-kneading temperature is selected from the region where the semi-aromatic polyamide (A) does not melt and decompose, and is usually (Tm-20 ° C.) to (Tm + 50 ° C.) with the melting point of the semi-aromatic polyamide (A) as Tm. Is preferable.
  • a method for processing the polyamide resin composition of the present invention for example, a method of extruding a molten mixture into a strand shape into a pellet shape; a method of hot-cutting or underwater cutting the molten mixture into a pellet shape; Method; A method of extruding into a block shape and crushing into a powder shape can be mentioned.
  • Examples of the method for molding the polyamide resin composition of the present invention include an injection molding method, an extrusion molding method, a blow molding method, and a sintering molding method, which have a large effect of improving mechanical properties and moldability.
  • the molding method is preferable.
  • the injection molding machine is not particularly limited, and examples thereof include a screw in-line type injection molding machine and a plunger type injection molding machine.
  • the polyamide resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled and solidified in a predetermined shape, and then from the mold as a molded body. Taken out.
  • the resin temperature at the time of injection molding is preferably Tm or more, more preferably less than (Tm + 50 ° C.), with the melting point of the semi-aromatic polyamide (A) as Tm. It is preferable that the polyamide resin composition pellets used when the polyamide resin composition is heated and melted are sufficiently dried. If the amount of water contained in the polyamide resin composition pellets is large, the resin may foam in the cylinder of the injection molding machine, making it difficult to obtain an optimum molded product.
  • the water content of the polyamide resin composition pellets used for injection molding is preferably less than 0.3 parts by mass and more preferably less than 0.1 parts by mass with respect to 100 parts by mass of the polyamide resin composition.
  • the molded product obtained from the polyamide resin composition of the present invention has excellent mechanical properties and is also excellent in dimensional stability in both the flow direction (MD) and the orthogonal direction (TD), and thus is an in-vehicle camera. It can be suitably used for parts, and above all, it can be more preferably used for a lens barrel or a housing. In addition, it can also be used for electrical and electronic connectors, switches, aluminum electrolytic capacitor terminal blocks, actuator parts, LED reflectors, sensors, sockets, jacks, fuse holders, relays, coil bobbins, resistors, ICs, LED housings, etc. ..
  • Measurement method (1) Melt point of semi-aromatic polyamide (A) Shave a pellet of semi-aromatic polyamide (A) that has been sufficiently dried, and use 10 mg of the shavings with a differential scanning calorimeter DSC-7 manufactured by PerkinElmer. The measurement was performed under the following conditions under a nitrogen atmosphere.
  • a prismatic test piece (length 10 mm ⁇ width) so that the length direction of the test piece is the resin flow direction (MD) from the central portion of the dumbbell piece obtained in (3) above.
  • a prismatic test piece (length 10 mm x width 5 mm x) is cut out so that the length direction of the test piece is orthogonal to the resin flow direction (MD) (TD). (Thickness 4 mm) was cut out. The measurement was performed under the following conditions under a nitrogen atmosphere using a thermomechanical analyzer (“TMA Q400” manufactured by TA Instruments).
  • a disk-shaped test piece having a diameter of 60 mm and a thickness of 3 mm was produced under the condition of a mold temperature (Tm-190 ° C.).
  • a mold having a gas vent having a thickness of 50 ⁇ m at the end of the flow was used.
  • the length of the burr generated at the position corresponding to the gas vent portion of the mold of the obtained disc-shaped test piece was measured using a microscope.
  • Dicarboxylic acid component ⁇ TPA Terephthalic acid
  • Diamine component ⁇ DDA 1,10-decanediamine
  • NDA 1,9-nonandiamine
  • MODEA 2-methyl-1,8-octanediamine
  • Mono Carboxylic acid component ⁇ STA Steric acid
  • Polymerization catalyst ⁇ SHP Sodium hypophosphate monohydrate
  • Step (i) 4560 parts by mass of TPA powder as a dicarboxylic component, 9 parts by mass of SHP as a polymerization catalyst, and 490 parts by mass of STA as a terminal sealant are placed in a ribbon blender type reactor, and the number of revolutions is increased using a double helical type stirring blade under nitrogen sealing. The mixture was heated to 170 ° C. with stirring at 30 rpm. Then, while keeping the temperature at 170 ° C. and the rotation speed at 30 rpm, the DDA 4950 parts by mass heated to 100 ° C. was heated to 100 ° C. at a rate of 33 parts by mass / minute for 2.5 hours.
  • Step (ii) The reactant obtained in step (i) was subsequently heated to 230 ° C. under a nitrogen stream in the ribbon blender type reactor used in step (i) and heated at 230 ° C. for 5 hours for polymerization. Polyamide 10T was obtained. The obtained polyamide 10T had a melting point of 317 ° C. and a relative viscosity of 2.25.
  • the obtained polyamide 9T had a melting point of 300 ° C. and a relative viscosity of 2.31.
  • Example 1 100 parts by mass of semi-aromatic polyamide (polyamide 10T) is supplied to the main supply port of a twin-screw extruder (TEM37BS manufactured by Toshiba Machine Co., Ltd.) having a screw diameter of 37 mm and L / D40, and a plate-like filler (plate-like filler) is supplied from a side feeder. Glass flakes A) 100 parts by mass were supplied and melt-kneaded. The cylinder temperature was (melting point of polyamide 10T + 10 ° C.), screw rotation speed was 250 rpm, and discharge rate was 35 kg / hour. Then, after taking it into a strand shape, it was cooled and solidified by passing it through a water tank, and it was cut with a pelletizer to obtain a polyamide resin composition pellet.
  • TEM37BS manufactured by Toshiba Machine Co., Ltd.
  • Comparative Examples 1 to 8 The same operation as in Example 1 was carried out except that the composition of the resin composition was changed as shown in Tables 1 and 2, to obtain polyamide resin composition pellets. In Comparative Example 7, pellets could not be obtained because the content of the filler was high.
  • Example 18 A mixture was obtained by dry blending 100 parts by mass of a semi-aromatic polyamide (polyamide 10T) and 25 parts by mass of polyphenylene ether.
  • the above mixture is supplied to the main supply port of a twin-screw extruder (TEM37BS manufactured by Toshiba Machine Co., Ltd.) having a screw diameter of 37 mm and L / D40, and 125 parts by mass of a plate-shaped filler (glass flake A) is supplied from a side feeder. Then, melt kneading was performed.
  • the cylinder temperature was (melting point of polyamide 10T + 10 ° C.), screw rotation speed was 250 rpm, and discharge rate was 35 kg / hour.
  • After taking it into a strand shape it was cooled and solidified by passing it through a water tank, and it was cut with a pelletizer to obtain a polyamide resin composition pellet.
  • Examples 19-29, Comparative Example 9 The same operation as in Example 18 was carried out except that the resin composition was changed as shown in Table 1, to obtain polyamide resin composition pellets.
  • Tables 1 and 2 show the resin composition of the polyamide resin compositions obtained in Examples and Comparative Examples and their characteristic values.
  • the polyamide resin compositions of Examples 1 to 41 had a bending strength of 100 MPa or more, a flexural modulus of 10 GPa or more, and were excellent in mechanical properties. Further, the obtained molded product has a linear expansion coefficient of 70 ⁇ 10-6 (1 / ° C.) or less at 80 ° C. in either the flow direction (MD) or the orthogonal direction (TD), and is excellent in dimensional stability. Was there. Further, the burr length was 150 ⁇ m or less, and the moldability was excellent. In addition, the amount of water vapor permeation was 150 mg or less, and it was excellent in low moisture permeability.
  • the filler can be used as a filler. Even if the content is the same, when the plate-shaped filler and the fibrous filler are used together, the obtained molded product is dimensionally stable in both the flow direction (MD) and the orthogonal direction (TD). It can be seen that the sex is improved.
  • Examples 1, 2, 4, 5, 11, 13 to 17 with Examples 18 to 27 when a part of the polyamide 10T is changed to polyphenylene ether, the bending strength is increased and the mechanical properties are improved. It can be seen that the coefficient of linear expansion is lowered and the dimensional stability is improved.
  • the polyamide resin compositions of Comparative Examples 1 to 3 and 6 had a low bending strength because the content of the filler was small, the molded product had a high coefficient of linear expansion, and the burr length was long. Since the polyamide resin compositions of Comparative Examples 4 to 5 used only the fibrous filler, the molded product had a high coefficient of linear expansion of TD and a long burr length. In the polyamide resin compositions of Comparative Examples 8 and 9, the mass ratio of the plate-like filler to the fibrous filler was not in the preferable range, so that the molded product had a high coefficient of linear expansion of TD.
  • Test piece 2 Packing 3 Test jig 4 Test liquid

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JP2001106908A (ja) * 1999-08-02 2001-04-17 E I Du Pont De Nemours & Co 成形用芳香族ポリアミド組成物
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