WO2016103733A1 - ポリアミド樹脂組成物、ポリアミド樹脂組成物ペレット群、成形体、及びポリアミド樹脂組成物の製造方法 - Google Patents
ポリアミド樹脂組成物、ポリアミド樹脂組成物ペレット群、成形体、及びポリアミド樹脂組成物の製造方法 Download PDFInfo
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- 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
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- 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
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- 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
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- 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
- C08K3/10—Metal compounds
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- 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
- C08K3/16—Halogen-containing compounds
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- 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
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- 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
- C08J2377/06—Polyamides 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a polyamide resin composition, a polyamide resin composition pellet group, a molded body, and a method for producing a polyamide resin composition.
- Polyamide resins and polyester resins are used in various industrial fields because they have excellent mechanical properties (mechanical strength, rigidity, impact resistance, etc.).
- polyamide 66 has a higher molecular weight than ordinary molding polyamide 66 for the purpose of improving mechanical properties and slidability, and is a composition in which it is combined with an inorganic compound filler such as glass fiber, glass flake, alumina fiber or layered inorganic compound. Often used as a product.
- an inorganic compound filler such as glass fiber, glass flake, alumina fiber or layered inorganic compound.
- a glass fiber reinforced polyamide resin composition using glass fibers as an inorganic compound filler has attracted attention because of its high effect of improving mechanical properties.
- the glass fiber used is treated with a glass fiber sizing agent such as a silane coupling agent or a film forming agent in order to improve the interface state when compounded with polyamide. Glass fiber is generally used.
- Patent Document 1 uses a glass fiber surface-treated with a glass fiber sizing agent containing maleic anhydride and an unsaturated monomer copolymer, and a silane coupling agent as a main constituent component.
- a technique for improving anti-freezing liquid resistance by compounding is disclosed.
- Patent Document 2 discloses a technique for improving water resistance between a glass fiber surface and a polyamide resin by using a polycarbodiimide resin, a polyurethane resin, or a silane coupling agent.
- Patent Document 3 discloses a polyamide 66 resin composition comprising a polyamide and glass fiber having a specific sulfuric acid relative viscosity
- Patent Document 4 discloses a polyamide 66, glass fiber and copper having a specific number average molecular weight.
- a polyamide resin composition comprising a compound, potassium halide, and melamine is disclosed.
- JP-A-6-128479 JP-A-9-227173 JP-A-6-128480 International Publication No. 2006/054774
- a polyamide resin composition using a high molecular weight polyamide 66 is known as a technique having a high effect of improving mechanical strength.
- the resin temperature tends to be high during melt kneading, the obtained pellets are decomposed gas. Foaming and variations in physical properties, which are thought to be caused by the inclusion, often occur.
- a polyamide resin composition containing the polymer polyamide 66 is melt-kneaded, there is a problem that the fluctuation range of the torque is large in an apparatus such as an extruder, which may affect the productivity, and thus an improvement is desired. Yes.
- shape such as increasing the size and thickness of molded products.
- the present invention has been made in view of the above circumstances, and is a polyamide resin composition excellent in productivity and excellent in mechanical strength, a polyamide resin composition pellet group, and a molded article obtained by molding the composition. And a method for producing such a polyamide resin composition.
- the present inventors have found that the above-mentioned problems can be solved if the polyamide resin composition includes predetermined conditions and includes glass fibers, and the present invention is completed. It came to do.
- the polyamide resin composition of the present invention is A polyamide resin composition comprising (A) polyamide 66, (B) glass fiber, and (C) a copper compound and a halide, (A)
- the proportion of the component having a molecular weight of 30,000 or less obtained from gel permeation chromatography (GPC) in the polyamide 66 is 30 to 37 mass% of the whole polyamide (A), and the molecular weight is 100,000 or more.
- the ratio of the component is (A) 8 to 15% by mass of the entire polyamide 66.
- the average fiber diameter of the glass fibers is preferably 5 to 9 ⁇ m.
- the polyamide 66 includes one or more types of polyamide 66 (A-1) having a relative viscosity RV of 65 to 250 and one or more types of polyamide 66 (A-2) having a relative viscosity RV of 25 to 65. It is preferable that it contains.
- the mass ratio (A-1) / (A-2) of polyamide 66 (A-1) and polyamide 66 (A-2) is preferably 85/15 to 50/50.
- the copper concentration [Cu] with respect to the polyamide 66 is preferably 40 ppm or more and 300 ppm or less.
- the halogen concentration [X] with respect to the polyamide 66 is preferably 40 ppm or more and 9000 ppm or less.
- the molar ratio of the halogen content to the copper content is preferably 2/1 to 50/1.
- the polyamide resin composition of the present invention preferably has a standard deviation of tensile strength measured according to ISO 527 of 0.50 or less.
- the polyamide resin composition of the present invention preferably has a standard deviation of tensile elongation measured in accordance with ISO 527 of 0.08 or less.
- the polyamide resin composition pellet group of the present invention is an aggregate of pellets made of the polyamide resin composition of the present invention, and the standard deviation of tensile strength measured according to ISO 527 is 0.50 or less.
- the polyamide resin composition pellet group of the present invention preferably has a standard deviation of tensile elongation measured in accordance with ISO 527 of 0.08 or less.
- the method for producing a polyamide resin composition of the present invention is a method for producing the polyamide resin composition of the present invention, wherein (A) polyamide 66 and (C) a copper compound and a halide are melt kneaded at a temperature of kneading.
- the molded product of the present invention is formed by molding the polyamide resin composition of the present invention.
- the polyamide resin composition of the present invention is a polyamide resin composition comprising (A) polyamide 66, (B) glass fiber, and (C) a copper compound and a halide.
- the proportion of the component having a molecular weight of 30,000 or less determined from the relationship chromatography (GPC) is 30 to 37% by mass of the whole polyamide 66 (A) and the proportion of the component having a molecular weight of 100,000 or more is (A ) Since it is characterized in that it is 8 to 15% by mass of the entire polyamide 66, it is possible to provide a polyamide resin composition with less pellet foaming and excellent productivity and mechanical strength.
- the polyamide resin composition of the present invention is a polyamide resin composition comprising (A) polyamide 66, (B) glass fiber, and (C) a copper compound and a halide.
- the proportion of the component having a molecular weight of 30,000 or less, determined from the association chromatography (GPC), is 30 to 37% by mass of the whole (A) polyamide 66, and the proportion of the component having a molecular weight of 100,000 or more is ( A) It is characterized by 8 to 15% by mass of the entire polyamide 66.
- polyamide 66 (A) Polyamide 66 (hereinafter sometimes simply referred to as polyamide 66 or component (A)) has an amide bond (—NHCO—) in the main chain, and includes a hexamethylene unit, an adipic acid unit, It is the polymer which consists of.
- the polyamide 66 is not particularly limited.
- a polymer obtained by polycondensation of hexamethylenediamine and adipic acid a polymer obtained by polycondensation of 6-aminocapronitrile and adipic acid
- examples thereof include a polymer obtained by polycondensation of methylenediamine and adipoyl chloride, and a polymer obtained by polycondensation of 6-aminocapronitrile and adipoyl chloride.
- a polymer obtained by polycondensation of hexamethylenediamine and adipic acid is preferred because of the availability of raw materials.
- Polyamide 66 refers to a resin containing 95 mol% or more of polyamide 66 with the total unit being 100 mol%.
- Polyamide 66 includes a homopolymer of polyamide 66 and a copolymer of a monomer copolymerizable with polyamide 66. Although it does not specifically limit as a monomer which can be copolymerized, for example, polyamide components other than the polyamide 66 component, for example, a polymerizable amino acid, a polymerizable lactam, or other polymerizable diamine or dicarboxylic acid can be mentioned. Moreover, a well-known compound can be added for molecular weight adjustment or hot water improvement.
- Examples of such compounds include, but are not limited to, acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like. .
- acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride
- monoisocyanates such as monoacid halides, monoesters, monoalcohols, and the like.
- monocarboxylic acid or monoamine is preferable.
- Polyamide 66 preferably contains one or more types of polyamide 66 (A-1) (hereinafter sometimes simply referred to as component (A-1)) having a relative viscosity RV of 65 to 250. It is more preferable to include one or more types of polyamide 66 (A-1) having a relative viscosity RV of 70 or more and 230 or less, and further to include one or more types of polyamide 66 (A-1) having a relative viscosity RV of 75 to 200. preferable. By including such polyamide 66 (A-1), the resulting polyamide resin composition tends to be more excellent in mechanical properties. Polyamide 66 (A-1) may be used alone or in combination of two or more. In addition, relative viscosity RV can be measured by the method as described in an Example.
- the (A) polyamide 66 may contain one or more types of polyamide 66 (A-2) (hereinafter sometimes simply referred to as component (A-2)) having a relative viscosity RV of 25 or more and less than 65. More preferably, it contains at least one polyamide 66 (A-2) having a relative viscosity RV of 27 or more and 60 or less, and contains at least one polyamide 66 (A-2) having a relative viscosity RV of 30 or more and 55 or less. Is more preferable. By including such polyamide 66 (A-2), it tends to be easier to suppress the extrusion processability and the decrease in the molecular weight of the resulting polyamide resin composition. Polyamide 66 (A-2) may be used alone or in combination of two or more.
- Polyamide 66 preferably includes both polyamide 66 (A-1) and polyamide 66 (A-2). Thereby, it exists in the tendency which is excellent by the balance of a long-term characteristic and fluidity
- the mass ratio ((A-1) / (A-2)) of the component (A-1) to the component (A-2) is preferably 85/15 to 50/50. More preferably 80/20 to 50/50, and still more preferably 75/25 to 50/50.
- a method for polymerizing the polyamide 66 is not particularly limited, and examples thereof include a hot melt polycondensation method, a solid phase polymerization method, and a solution method.
- a hot melt polycondensation method hexamethylene adipamide, which is a raw material of polyamide 66, is blended with an antifoaming agent, if necessary, and heated and concentrated at a temperature of 40 to 300 ° C.
- This is a method in which the pressure is maintained at a pressure between 20 and 20 atmospheres, and finally, the pressure is released and the atmospheric pressure or reduced pressure is used for polycondensation.
- the solid phase polymerization method is a method in which polymerization is performed at a temperature below the melting point of the diamine or dicarboxylate solid salt or polycondensate.
- the solution method is a method in which a dicarboxylic acid halide component and a diamine component are polycondensed in a solution. These methods may be combined as necessary.
- polymerization form a batch type or a continuous type may be sufficient.
- the polymerization apparatus is not particularly limited. For example, an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like can be used.
- a general method such as a method of adjusting the polymerization time by the above-described hot melt polycondensation method, a method of solid phase polymerization below the melting point of the polycondensate, etc. Can be used and is not particularly limited.
- the terminal amino group concentration [NH 2 ] of the polyamide 66 is preferably 10 meq / kg or more and 100 meq / kg or less, more preferably 20 meq / kg or more and 90 meq / kg or less, and 30 meq / kg. / Kg to 80 meq / kg is more preferable.
- the method for measuring the terminal amino group concentration include a method in which a predetermined amount of polyamide 66 sample is dissolved in a 90% aqueous phenol solution and titrated with 1/50 N hydrochloric acid at 25 ° C. to calculate.
- the terminal carboxyl group concentration [COOH] of the polyamide 66 is preferably 10 meq / kg or more and 150 meq / kg or less, more preferably 20 meq / kg or more and 140 meq / kg or less, and 30 meq / kg. More preferably, it is not less than kg and not more than 130 meq / kg.
- the terminal carboxyl group concentration was measured by dissolving a predetermined amount of polyamide 66 sample in 160 ° C. benzyl alcohol, using 1/10 N potassium hydroxide in ethylene glycol, and using phenolphthalein as an indicator. And titrating and calculating. Examples of the appearance of the molded body include roughness due to exposure of glass fibers, smoothness, silver streak, and the like, but are not limited thereto.
- the ratio of the terminal carboxyl group concentration to the total of the terminal carboxyl group concentration [COOH] and the terminal amino group concentration [NH 2 ] of the polyamide 66 is preferably 55 to 85%, preferably 57 to 80% is more preferable, and 60 to 75% is more preferable.
- terminal carboxyl group ratio is within the above range, it tends to be excellent in long-term color stability with little yellowing.
- the polyamide 66 used in the polyamide resin composition of the present invention has a sufficiently high fluidity at the time of melt processing by making the components having a molecular weight of 30,000 or less and the components having a molecular weight of 100,000 or more specific amounts, respectively, and high. Mechanical properties and wear characteristics can be maintained, and the quality of the resulting pellets can be improved. Specifically, from the viewpoint of flowability and suppression of pellet foaming, the component having a molecular weight of 30,000 or less is 30 to 37% by mass with respect to the entire polyamide 66, and the molecular weight is from the viewpoint of mechanical characteristics and wear characteristics. More than 100,000 components are 8 to 15% by mass, more preferably 8 to 14% by mass.
- the molecular weight of the polyamide 66 in the polyamide resin composition it is preferable to use, for example, the above-mentioned polyamide 66 (A-1) and polyamide 66 (A-2) having different molecular weights.
- the resin temperature during extrusion tends to be high, so the melt kneading temperature is preferably 330 ° C. or lower.
- the molecular weight of polyamide 66 is obtained by measurement using gel permeation chromatography (GPC).
- the apparatus is “HLC-8320GPC” manufactured by Tosoh Corporation, the detector is a differential refractometer (RI), the solvent is hexafluoroisopropanol (HFIP) in which 0.1 mol% of sodium trifluoroacetate is dissolved, Used were two “TSKgel-GMHHR-M” and one “G1000HHR” manufactured by Tosoh Corporation.
- the sample concentration was 1 to 3 (mg sample) / 1 (mL solvent), filtered through a filter to remove insolubles, and used as a measurement sample. Based on the obtained elution curve, it computed by polymethylmethacrylate (PMMA) conversion.
- PMMA polymethylmethacrylate
- glass fiber (hereinafter may be simply referred to as glass fiber or component (B)) has a function of imparting excellent mechanical strength, rigidity, and moldability to the polyamide resin composition.
- the glass fiber is not particularly limited as long as it is generally used for polyamide.
- the average fiber diameter of the glass fibers is not particularly limited, but is preferably 4 to 30 ⁇ m, more preferably 5 to 9 ⁇ m, and particularly preferably 5 to 8 ⁇ m.
- the polyamide resin composition tends to be given more excellent mechanical strength, rigidity, and moldability.
- limit especially as a form of glass fiber For example, a chopped strand, roving, a milled fiber, etc. can be used.
- the weight average fiber length of (B) glass fiber is not particularly limited, but when chopped strand is used, it may be appropriately selected within a range of 0.1 to 6 mm.
- the average fiber diameter and the weight average fiber length in this specification are the average values of values obtained by measuring the diameter and length of 500 randomly extracted fibers.
- the content of (B) glass fiber is 1 to 100 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of (A) polyamide 66. If the glass fiber content is in the above range, the resin temperature can be kept low, and a pellet in which foaming is suppressed and / or a resin composition in which variation is suppressed can be obtained (however, the effect is not limited to this).
- a conventionally known sizing agent may be attached to the surface of the glass fiber.
- the sizing agent is not particularly limited.
- the main component is, for example, a copolymer of maleic anhydride and an unsaturated monomer, a silane coupling agent, an acrylic acid copolymer, and / or a urethane polymer.
- a copolymer of maleic anhydride and an unsaturated monomer a silane coupling agent, an acrylic acid copolymer, and / or a urethane polymer.
- those containing a copolymer of maleic anhydride and an unsaturated monomer or an amino group-containing silane coupling agent as a main constituent are preferable.
- the copolymer of maleic anhydride and unsaturated monomer is not particularly limited. Specifically, styrene, ⁇ -methylstyrene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1, Examples thereof include a copolymer of an unsaturated monomer such as 3-pentadiene and cyclooctadiene and maleic anhydride. Among these, a copolymer of butadiene, styrene, and maleic anhydride is preferable. These monomers may be used alone or in combination of two or more.
- the sizing agent may be used as a blend such as a mixture of a maleic anhydride / butadiene copolymer and a maleic anhydride / styrene copolymer.
- the copolymer of maleic anhydride and unsaturated monomer preferably has an average molecular weight of 2,000 or more. Further, the ratio of maleic anhydride and unsaturated monomer is not particularly limited. Further, in addition to the maleic anhydride copolymer, an acrylic acid copolymer or a urethane polymer may be used in combination.
- the silane coupling agent is not particularly limited, and any silane coupling agent that is usually used for surface treatment of glass fibers can be used.
- Such silane coupling agents are not particularly limited, and specific examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxy.
- Aminosilane coupling agents such as silane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane; ⁇ -glycidoxypropylmethyldiethoxysilane, Epoxysilane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxysilane; ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxy Propylmethyldiethoxy And methacryloxysilane coupling agents such as ⁇ -methacryloxypropyltriethoxysilane; vinylsilane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris ( ⁇ methoxye
- aminosilane coupling agents are preferred because of their affinity for polyamide resin, and among them, ⁇ -aminopropyltriethoxysilane and N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane are more preferred. These coupling agents may be used alone or in combination of two or more.
- copper compound used in the present invention examples include copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, and copper stearate. And copper complex salts coordinated to chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid.
- copper corrosion As a copper compound, it has excellent heat aging resistance and can suppress metal corrosion of the screw and cylinder part during extrusion (hereinafter sometimes abbreviated as “metal corrosion”). Cuprous, cupric bromide, cuprous chloride, and copper acetate are preferred, and copper iodide and / or copper acetate are more preferred. As a copper compound, you may use by 1 type and may be used in combination of 2 or more types.
- the content of the copper compound is preferably such that (A) the copper concentration [Cu] with respect to the polyamide 66 is 40 ppm or more and 300 ppm or less, more preferably 50 ppm or more and 275 ppm or less, and more preferably 60 ppm or more and 250 ppm or less. preferable.
- the copper concentration [Cu] with respect to the polyamide 66 is 40 ppm or more and 300 ppm or less, more preferably 50 ppm or more and 275 ppm or less, and more preferably 60 ppm or more and 250 ppm or less. preferable.
- a metal halide is preferable, and a copper halide is excluded. It is preferably at least one selected from the group consisting of metal halides of Group 1 or Group 2 of the Periodic Table of Elements, such as potassium iodide, potassium bromide, potassium chloride, sodium iodide, and sodium chloride. And potassium iodide and potassium bromide are preferable.
- metal halides of Group 1 or Group 2 of the Periodic Table of Elements, such as potassium iodide, potassium bromide, potassium chloride, sodium iodide, and sodium chloride.
- potassium iodide and potassium bromide are preferable.
- the halide one kind may be used, or two or more kinds may be used in combination.
- the halide content (A) is preferably such that the halogen concentration [X] with respect to the polyamide 66 is 40 ppm or more and 9000 ppm or less, more preferably 70 ppm or more and 7000 ppm or less, and more preferably 100 ppm or more and 5000 ppm or less. preferable.
- the halogen concentration [X] with respect to the polyamide 66 is 40 ppm or more and 9000 ppm or less, more preferably 70 ppm or more and 7000 ppm or less, and more preferably 100 ppm or more and 5000 ppm or less. preferable.
- the total content of copper compound and halide is 0.005 to 1 part by mass when (A) polyamide 66 is 100 parts by mass and (B) glass fiber is 1 to 100 parts by mass.
- a copper compound and a metal halogen are added to the polyamide resin composition so that the molar ratio of the halogen content to the copper content (halogen / copper) is 2/1 to 50/1. It is preferable to contain a compound.
- the molar ratio of halogen content to copper content (halogen / copper) is more preferably 2/1 to 40/1, and further preferably 4/1 to 30/1.
- the polyamide resin composition of the present invention when the molar ratio of the halogen content to the copper content is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed. If the molar ratio between the content of copper and the content of copper is 50/1 or less, the problem of corroding the screw of the molding machine can be suppressed without impairing mechanical properties such as toughness and rigidity.
- other components include higher fatty acids such as lauric acid as lubricants, higher fatty acid metal salts of higher fatty acids and metals such as aluminum, higher fatty acid amides such as ethylene bisstearyl amide, and waxes such as polyethylene wax. Can be mentioned.
- the organic compound which has at least 1 amide group is also mentioned.
- a polyamide other than polyamide 66 may be used in combination with (A) polyamide 66.
- the polyamide other than polyamide 66 is not particularly limited, and examples thereof include a polycondensate of dicarboxylic acid and diamine, a ring-opening polymer of cyclic lactam, and a polycondensate of aminocarboxylic acid.
- the polyamide is not particularly limited, and specifically, polycaprolactam (polyamide 6), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodeca Aliphatic polyamides such as polyamide (polyamide 612), polyundecamethylene adipamide (polyamide 116), polyundecalactam (polyamide 11), polydodecalactam (polyamide 12); polymetaxylylene adipamide (polyamide MXD6) Polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polynonamethylene terephthalamide (polyamide 9T), polytetramethylene isophthalamide (polyamide 4I), etc.
- polycaprolactam polyamide 6
- polytetramethylene adipamide polyamide 46
- polyhexamethylene sebacamide polyamide 610
- polyamide 6 a copolymer of polyamide 6 and polyamide 66, or a mixture thereof is preferable from the viewpoint of compatibility with polyamide 66.
- Such other components are not particularly limited, but include phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, sulfur-based heat stabilizers, ultraviolet absorbers, photodegradation inhibitors, plasticizers, Lubricants, crystal nucleating agents, mold release agents, flame retardants, colorants, dyeing agents, pigments, and the like may be added, and other thermoplastic resins may also be mentioned.
- the other components described above have greatly different properties, the preferred content ratios of the components vary. A person skilled in the art can easily set a suitable content for each of the other components described above.
- the standard deviation of the tensile strength measured according to ISO 527 is preferably 0.50 or less, more preferably 0.40 or less, and 0.30 or less. More preferably. When the standard deviation of the tensile strength is 0.50 or less, there is little variation between the pellets, and the resulting molded product is suppressed in silver streak and is excellent in appearance.
- the standard deviation of tensile elongation measured according to ISO 527 is preferably 0.08 or less, and more preferably 0.07 or less.
- the standard deviation of the tensile elongation is 0.08 or less, there is little variation between the pellets, and the resulting molded product is suppressed in silver streak and is excellent in appearance.
- the tensile strength and tensile elongation can be measured by the methods described in the examples.
- the polyamide resin composition of the present invention comprises (A) polyamide 66, (B) glass fiber, (C) a copper compound and a halide, and the melt kneading temperature of the melt kneader is set to a specific range. Can be manufactured.
- all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports. .
- (A) polyamide 66, (B) glass fiber, (C) copper compound and halide are mixed using a Henschel mixer or the like, and supplied to a melt kneader, Method of kneading, (A) After mixing (C) copper compound and halide with polyamide 66 and making it molten by a single screw or twin screw extruder equipped with a decompression device, (B) glass fiber from side feeder And the like.
- the term “in the polyamide polymerization process” means any process from the raw material monomer to the completion of the polymerization of the polyamide, and may be in any stage.
- the melt kneader is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a melt kneader such as a mixing roll, or the like can be used. Of these, a twin screw extruder is preferably used.
- the melt kneading temperature is important, and it is preferably about 280 to 350 ° C.
- the “melt kneading temperature” means a preset heating temperature of the container when the components are melt kneaded.
- the temperature of the barrel is controlled within the range of the heating set temperature ⁇ 5 ° C.
- the die head of an extruder can be arbitrarily set according to the resin temperature of the resin composition obtained.
- step (1-2) glass fiber is added to the kneaded product obtained in the step (1-1), and the melt kneading temperature is preferably 280 to 350 ° C. More preferably, the temperature is ⁇ 300 ° C.
- polyamide 66, (C) copper compound and halide are melt-kneaded in the above temperature range, and then (B) component is added to improve long-term characteristics.
- component is added to improve long-term characteristics.
- the amount of the high molecular weight component of the polyamide 66 which is effective for the above can be maintained even during melt kneading, and the operational stability in the twin screw extruder can be improved.
- the polyamide resin composition pellet group of the present invention uses the above production method to prevent the resin temperature during melt-kneading from becoming high and to suppress foaming.
- the pellet group preferably has a standard deviation of tensile strength measured according to ISO 527 of 0.50 or less, and more preferably 0.40 or less. When the standard deviation of the tensile strength is 0.50 or less, there is little variation between the pellets, and the resulting molded product is suppressed in silver streak and is excellent in appearance.
- the pellet group is an aggregate of pellets, and generally refers to a container or a container such as a paper bag.
- the standard deviation of tensile elongation measured according to ISO 527 is preferably 0.08 or less, and more preferably 0.07 or less.
- the standard deviation of the tensile elongation is 0.08 or less, there is little variation between the pellets, and the resulting molded product is suppressed in silver streak and is excellent in appearance.
- the tensile strength and tensile elongation can be measured by the methods described in the examples.
- the molded article of the present invention is obtained by molding the above-described polyamide resin composition of the present invention, and can be obtained, for example, by injection molding the polyamide resin composition of the present invention.
- the molded article of the present invention has less foaming and excellent mechanical properties, for example, for automobiles, machine industry, electrical / electronic, residential equipment, industrial materials, industrial materials, daily / household goods, etc. It can be suitably used as various molded articles and parts.
- the polyamide resin composition of the present invention includes an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, a throttle body, a chain cover, a thermostat housing, and an outlet. It can be suitably used for automobile engine room parts such as pipes, radiator tanks, oil naters and delivery pipes, and sliding parts such as gears, cams and bearings of electric power steering.
- C Copper compound and halide
- Copper compound Copper iodide (CuI) (trade name: Copper iodide (I) manufactured by Wako Pure Chemical Industries, Ltd.)
- Halide Potassium iodide (KI) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: potassium iodide)
- the test piece thus obtained was subjected to a reciprocating friction and wear tester “AFT-15MS type” manufactured by Toyo Seimitsu Co., Ltd., with a load of 1 kg, a linear velocity of 50 mm / sec, a reciprocating distance of 20 mm, an environmental temperature of 23 ° C., an environmental The coefficient of friction was measured by reciprocating 5000 times at a humidity of 50%. Moreover, the abrasion depth of the test piece after a test was measured using the Tokyo Seimitsu Co., Ltd. surface roughness measuring machine (Surfcom), and the largest value was set to the abrasion depth among three places measurement. An SUS (Steel Use Stainless) 304 test piece (sphere having a diameter of 5 mm) was used as a counterpart material used for evaluating the sliding characteristics of the test piece.
- AFT-15MS type manufactured by Toyo Seimitsu Co., Ltd.
- the pressure in the autoclave was about 1.8 MPa (G) in terms of gauge pressure, but water was discharged from the system as needed so that the pressure did not exceed 1.8 MPa (G).
- the polymerization time was adjusted so that the relative viscosity of polyamide 66 (measured in accordance with RV, ASTM D789) was about 45.
- the polyamide 66 was sent out in a strand form from the lower nozzle, and water-cooling and cutting were performed to obtain a pellet-like polyamide 66.
- This polyamide 66 resin was put into a 10,000 L solid phase polymerization apparatus, and sufficient nitrogen substitution was performed.
- the pressure in the autoclave was about 1.8 MPa (G) in terms of gauge pressure, but water was discharged from the system as needed so that the pressure did not exceed 1.8 MPa (G).
- the polymerization time was adjusted so that the relative viscosity of polyamide 66 (measured in accordance with RV, ASTM D789) was about 45.
- the polyamide 66 was sent out in a strand form from the lower nozzle, and after water cooling and cutting, a pellet-like polyamide 66 polymer (a-2) was obtained.
- Example 5 (B) Except that (b-2) was used for the glass fiber, it was melt kneaded in the same manner as in Example 1 to produce a resin composition pellet.
- polyamide resin composition containing (A) polyamide 66, (B) glass fiber, (C) copper compound and halide, and (A) gel permeation chromatography (GPC) in polyamide 66. ),
- the proportion of the component having a molecular weight of 30,000 or less is 30 to 37% by mass of the whole (A) polyamide 66, and the proportion of the component having a molecular weight of 100,000 or more is 8 of the whole polyamide 66 (A). It was found that a polyamide resin composition of ⁇ 15% by mass was excellent in mechanical strength and suppressed pellet foaming. It was also found that the torque fluctuation of the extruder was suppressed and the productivity was excellent.
- the resin composition of the present invention has industrial applicability to molded articles that require a high level appearance such as automobile parts.
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Abstract
Description
そこで、本発明は、上記事情に鑑みてなされたものであり、生産性に優れ、かつ機械的強度に優れるポリアミド樹脂組成物、ポリアミド樹脂組成物ペレット群、その組成物を成形してなる成形体、及びそのようなポリアミド樹脂組成物の製造方法を提供することを目的とするものである。
(A)ポリアミド66と、(B)ガラス繊維と、(C)銅化合物及びハロゲン化物と、を含むポリアミド樹脂組成物であって、
(A)ポリアミド66においてゲルパーミエーションクロマトグラフィー(GPC)から求められる、分子量30,000以下の成分の割合が(A)ポリアミド66全体の30~37質量%であり、かつ、分子量100,000以上の成分の割合が(A)ポリアミド66全体の8~15質量%であることを特徴とする。
[ポリアミド樹脂組成物]
本発明のポリアミド樹脂組成物は、(A)ポリアミド66と、(B)ガラス繊維と、(C)銅化合物およびハロゲン化物とを含むポリアミド樹脂組成物であって、(A)ポリアミド66においてゲルパーミエーションクロマトグラフィー(GPC)から求められる、分子量30,000以下の成分の割合が、(A)ポリアミド66全体の30~37質量%であり、かつ、分子量100,000以上の成分の割合が、(A)ポリアミド66全体の8~15質量%であることを特徴としている。
((A)ポリアミド66)
(A)ポリアミド66(以下、単にポリアミド66又は(A)成分と記載する場合がある。)とは、主鎖中にアミド結合(-NHCO-)を有し、ヘキサメチレン単位とアジピン酸単位とから成る重合体である。ポリアミド66としては、特に限定されないが、例えば、ヘキサメチレンジアミンとアジピン酸を重縮合して得られた重合体、6-アミノカプロニトリルとアジピン酸を重縮合して得られた重合体、ヘキサメチレンジアミンと塩化アジポイルを重縮合して得られた重合体、6-アミノカプロニトリルと塩化アジポイルを重縮合して得られた重合体等が挙げられる。これらのうち、原料の入手容易性から好ましくはヘキサメチレンジアミンとアジピン酸を重縮合して得られた重合体が好ましい。なお、ポリアミド66とは、全単位を100モル%としてポリアミド66を95モル%以上含む樹脂をいう。
所定の相対粘度RVを有するポリアミド66を得るには、例えば上記の熱溶融重縮合方法にて重合時間を調節する方法、重縮合物の融点以下で固相重合する方法、等の一般的な方法が使用でき、特に限定されない。
本発明のポリアミド樹脂組成物に用いるポリアミド66は、分子量30,000以下の成分、及び100,000以上の成分をそれぞれ特定の量とすることにより、溶融加工時に十分高い流動性を有し、高い機械物性、摩耗特性を保持し、さらには得られるペレットの品位を高めることができる。具体的には、流動性、ペレットの発泡抑制の観点から、ポリアミド66全体に対して、分子量30,000以下の成分が30~37質量%であって、機械的特性、摩耗特性の観点から分子量100,000以上の成分が8~15質量%、より好ましくは8~14質量%である。
ポリアミド樹脂組成物中のポリアミド66の分子量を特定量とするためには、例えば、上述の分子量の異なるポリアミド66(A-1)及びポリアミド66(A-2)を用いることが好ましい。原料に高分子量ポリアミドを含むことにより、押出時の樹脂温度が高くなる傾向があるため、溶融混練温度は330℃以下とすることが好ましい。
(B)ガラス繊維(以下、単にガラス繊維又は(B)成分と記載する場合がある。)は、ポリアミド樹脂組成物に、優れた機械的強度、剛性、及び成形性を付与する機能を有する。(B)ガラス繊維としては、一般的にポリアミドに使用されているものであれば特に制限はない。
また、ガラス繊維の形態としては、特に制限されず、例えば、チョップドストランド、ロービング、又はミルドファイバー等を用いることができる。また、(B)ガラス繊維の重量平均繊維長については、特に限定されるものではないが、チョップドストランドを用いる場合、0.1~6mmの範囲で適宜選択すればよい。なお、本明細書における平均繊維径及び重量平均繊維長は、無作為に抽出した500本の繊維の直径及び長さを測定して得られた値の平均値である。
(B)ガラス繊維の含有量は、(A)ポリアミド66が100質量部に対し、1~100質量部、好ましくは5~80質量部、より好ましくは10~50質量部である。ガラス繊維の含有量が上記範囲であれば、樹脂温度が低く抑えられ、発泡が抑制されたペレットおよび/またはバラつきが抑制された樹脂組成物を得られる(ただし、効果はこれに限らない)。
本発明に用いられる銅化合物としては、例えば、ハロゲン化銅、酢酸銅、プロピオン酸銅、安息香酸銅、アジピン酸銅、テレフタル酸銅、イソフタル酸銅、サリチル酸銅、ニコチン酸銅、及びステアリン酸銅などや、エチレンジアミン、及びエチレンジアミン四酢酸などのキレート剤に配位した銅錯塩などが挙げられる。
本発明のポリアミド樹脂組成物において、ハロゲンの含有量と銅の含有量とのモル比が2/1以上である場合には銅析出及び金属腐食の抑制をすることができるため好ましく、また、ハロゲンの含有量と銅の含有量とのモル比が50/1以下であれば靭性及び剛性などの機械物性を損なうことなく、成形機のスクリューなどを腐食するという問題を抑制することができる。
他の成分としては、例えば、滑剤としてラウリル酸などの高級脂肪酸、高級脂肪酸とアルミニウムなどの金属との高級脂肪酸金属塩、エチレンビスステアリルアミドなどの高級脂肪酸アミド、及びポリエチレンワックスなどのワックス類などが挙げられる。また、少なくとも1つのアミド基を有する有機化合物も挙げられる。
上記した成分の他に、(A)ポリアミド66とともに、ポリアミド66以外のポリアミドを併用してもよい。ポリアミド66以外のポリアミドとしては、特に限定されないが、例えば、ジカルボン酸とジアミンとの重縮合物、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物等が挙げられる。このようなポリアミドとしては、特に限定されないが、具体的には、ポリカプロラクタム(ポリアミド6)、ポリテトラメチレンアジパミド(ポリアミド46)、ポリヘキサメチレンセバカミド(ポリアミド610)、ポリヘキサメチレンドデカミド(ポリアミド612)、ポリウンデカメチレンアジパミド(ポリアミド116)、ポリウンデカラクタム(ポリアミド11)、ポリドデカラクタム(ポリアミド12)等の脂肪族ポリアミド;ポリメタキシリレンアジパミド(ポリアミドMXD6)、ポリヘキサメチレンテレフタルアミド(ポリアミド6T)、ポリヘキサメチレンイソフタルアミド(ポリアミド6I)、ポリノナメチレンテレフタルアミド(ポリアミド9T)、ポリテトラメチレンイソフタルアミド(ポリアミド4I)等の芳香族成分を含むポリアミド;及び上記の脂肪族ポリアミド同士、芳香族成分を含むポリアミド同士及び脂肪族ポリアミドと芳香族成分を含むポリアミドとの共重合体;これら混合物が挙げられる。これらのうち、ポリアミド66との相溶性の観点からポリアミド6、ポリアミド6とポリアミド66の共重合体又はその混合物が好ましい。
本発明のポリアミド樹脂組成物は、ISO527に準拠して測定した引張強度の標準偏差が、0.50以下であることが好ましく、0.40以下であることがより好ましく、0.30以下であることがさらに好ましい。引張強度の標準偏差が、0.50以下であることにより、ペレット間のバラつきが少なく、得られる成形体は、シルバーストリークの発生が抑えられ、外観に優れる。
本発明のポリアミド樹脂組成物は、ISO527に準拠して測定した引張伸びの標準偏差が、0.08以下であることが好ましく、0.07以下であることがより好ましい。引張伸びの標準偏差が、0.08以下であることにより、ペレット間のバラつきが少なく、得られる成形体は、シルバーストリークの発生が抑えられ、外観に優れる。
引張強度及び引張伸びは、実施例記載の方法により測定することができる。
本発明のポリアミド樹脂組成物は、(A)ポリアミド66と、(B)ガラス繊維と、(C)銅化合物及びハロゲン化物とを配合し、溶融混練機の溶融混練温度を特定の範囲にすることで製造することができる。
溶融混練機としては、特に限定されるものではなく、公知の装置、例えば、単軸又は二軸押出機、バンバリーミキサー、及びミキシングロールなどの溶融混練機などを用いることができる。中でも二軸押出機が好ましく用いられる。樹脂組成物中の(A)ポリアミド66の分子量を特定範囲とするためには、溶融混練温度が重要であり、280~350℃程度が好ましい。ここで、「溶融混練温度」とは、構成成分を溶融混練する際の容器の加熱設定温度を意味する。(A)ポリアミド66樹脂の分子量が高い場合、(B)ガラス繊維の平均繊維径が小さい場合は、溶融混練する際に、樹脂温度が高くなる傾向があるため、溶融混練温度は330℃以下とすることが好ましい。
(A)ポリアミド66と、(C)銅化合物及びハロゲン化物とを、溶融混練温度を300℃以上330℃以下で溶融混練し、混練物を得る工程(1-1)と、工程(1-1)で得られた混練物に(B)ガラス繊維を添加し、溶融混練する工程(1-2)とを有するものである。
二軸押出機において、加熱設定温度に対し、容器(バレル)の温度をその温度に維持しようとする通常モードでは、バレルは加熱設定温度±5℃の範囲内で温度制御される。
なお、押出機のダイヘッドは、得られる樹脂組成物の樹脂温度に応じて任意で設定できる。
本発明のポリアミド樹脂組成物ペレット群は、上記製造方法を用いることにより、溶融混練時の樹脂温度が高くなることを防ぎ、発泡が抑制されたものである。
ペレット群は、ISO527に準拠して測定した引張強度の標準偏差が、0.50以下であることが好ましく、0.40以下であることがより好ましい。引張強度の標準偏差が、0.50以下であることにより、ペレット間のバラつきが少なく、得られる成形体は、シルバーストリークの発生が抑えられ、外観に優れる。
ここで、ペレット群とは、ペレットの集合体であり、通常、コンテナー、紙袋等の容器に入ったものを指す。
更に、ISO527に準拠して測定した引張伸びの標準偏差が、0.08以下であることが好ましく、0.07以下であることがより好ましい。引張伸びの標準偏差が、0.08以下であることにより、ペレット間のバラつきが少なく、得られる成形体は、シルバーストリークの発生が抑えられ、外観に優れる。
引張強度及び引張伸びは、実施例記載の方法により測定することができる。
本発明の成形体は、上述した本発明のポリアミド樹脂組成物を成形してなり、例えば、本発明のポリアミド樹脂組成物を射出成形することにより得ることができる。
(A)ポリアミド66
(a-1):下記製造例1のポリアミド66 相対粘度RV:130
(a-2):下記製造例2のポリアミド66 相対粘度RV:45
(b-1):ガラス繊維(以下、GFと略記する。)ガラス繊維平均径7μm、ガラス繊維平均長さ3mm(CPIC社製、商品名「ECS301HP(E)」)
(b-2):GF ガラス繊維平均径13μm、ガラス繊維平均長さ3mm(CPIC社製、商品名「ECS301HP(K)」)
(C-1)銅化合物:ヨウ化銅(CuI)(和光純薬工業(株)製、商品名:ヨウ化銅(I))
(C-2)ハロゲン化物:ヨウ化カリウム(KI)(和光純薬工業(株)製、商品名:ヨウ化カリウム)
<相対粘度RV>
ポリアミド66(a-1,a-2)の相対粘度RVを、ASTMD789に準じて測定した。具体的には、溶媒として90%ギ酸を用いて、3gサンプル/30mlギ酸の濃度で、25℃の温度条件下で測定した。
分子量30,000以下の成分、及び分子量100,000以上の成分の定量は以下のGPCにより測定した。
装置:東ソー(株)製、「HLC-8320GPC」
検出器:示差屈折計(RI)
溶媒:トリフルオロ酢酸ナトリウムを0.1モル%溶解させたヘキサフルオロイソプロパノール(HFIP)
カラム:東ソー(株)製、「TSKgel-GMHHR-M」2本、及び「G1000HHR」1本を直列接続して使用して、得られた溶出曲線をもとに、ポリメタクリル酸メチル(PMMA)換算により算出した。
<引張強度>
射出成形機(PS-40E:日精樹脂株式会社製)を用いて、実施例及び比較例で得られたポリアミド樹脂組成物のペレットを、4mm厚みISO成形片に成形した。その際、射出及び保圧の時間25秒、冷却時間15秒、金型温度80℃、溶融樹脂温度290℃に設定した。得られた成形片を用いて、ISO 527に準拠し、引張速度5mm/分で引張試験を行い、引張強度および引張伸びを測定した。このとき、試験片10本の値から標準偏差を計算した。
上記で得られた4mm厚のISO成形片を、長さ80mm×幅10mm×厚さ4mmの試験片に切削した。得られた試験片を用いて、ISO 179/1eAに準拠し、ノッチ付きシャルピー衝撃強度を測定した。
射出成形機(FN-3000、スクリュー直径40mm、日精樹脂工業(株)製)を用いて、シリンダー温度290℃、金型温度80℃、射出圧力65MPa、射出時間15秒、冷却時間15秒、及びスクリュー回転数200rpmの成形条件で、ポリアミド66樹脂組成物ペレットから幅80mm×長さ120mm×厚さ8mmの平板を成形した。この平板の中心部から成形流動方向に対して直角方向に切削を行い、幅8mm×長さ80mm×厚さ4mmの試験片を得た。
実施例及び比較例で得られたポリアミド樹脂組成物のペレットを、1kg秤量した後、ペレットの発泡の様子を目視観察し、下記基準に基づいて評価した。
良:ペレットの発泡個数が0以上10個未満である
可:ペレットの発泡個数が10個以上20個未満である
不可:ペレットの発泡個数が20個以上である
射出成型機(日精樹脂(株)製PS-40E)を用いて、シリンダー温度290℃、金型温度80℃に設定し、射出7秒、冷却12秒の射出成型条件で2mm厚みの短冊片を得た。前記短冊片表面のシルバーストリーク発生の有無を目視観察し、下記基準に基づいて評価した。
良:シルバーストリークの発生が無い
不可:シルバーストリーク発生が認められる
実施例及び比較例のポリアミド樹脂組成物を二軸押出機で製造する際、15分間での押出機のトルクの変動を下記基準に基づいて評価した。
良:トルクの変動幅が0%以上4%未満である
可:トルクの変動幅が4%以上6%未満である
不可:トルクの変動幅が6%以上である
〔製造例1〕a-1の製造
ヘキサメチレンジアミン及びアジピン酸の等モル塩を50質量部含有する水溶液15kgを調製した。次に、撹拌装置を有し、かつ下部に抜き出しノズルを有する40L容のオートクレーブ中に、上記の水溶液を仕込み、50℃で十分に水溶液を攪拌した。オートクレーブ内を充分に窒素で置換した後、水溶液を撹拌しながらオートクレーブ内の温度を50℃から約270℃まで昇温した。その際、オートクレーブ内の圧力は、ゲージ圧で約1.8MPa(G)であったが、かかる圧力が1.8MPa(G)以上にならないよう、水を随時系外に排出した。また、重合時間は、ポリアミド66の相対粘度(RV、ASTMD789に従った方法で測定)が45程度となるように調整した。オートクレーブ内での重合終了後、下部ノズルからストランド状にポリアミド66を送り出し、水冷及びカッティングを経て、ペレット状のポリアミド66を得た。
このポリアミド66樹脂を10000L固相重合装置へ投入し、充分な窒素置換を行った。その後、装置の内温180℃~190℃、窒素を500L/分で流しながら固相重合を所定の時間行い、(a-1)である相対粘度RVが130となったポリアミド66を得た。
ヘキサメチレンジアミン及びアジピン酸の等モル塩を50質量部含有する水溶液15kgを調製した。次に、撹拌装置を有し、かつ下部に抜き出しノズルを有する40L容のオートクレーブ中に、上記の水溶液を仕込み、50℃で十分に水溶液を攪拌した。オートクレーブ内を充分に窒素で置換した後、水溶液を撹拌しながらオートクレーブ内の温度を50℃から約270℃まで昇温した。その際、オートクレーブ内の圧力は、ゲージ圧で約1.8MPa(G)であったが、かかる圧力が1.8MPa(G)以上にならないよう、水を随時系外に排出した。また、重合時間は、ポリアミド66の相対粘度(RV、ASTMD789に従った方法で測定)が45程度となるように調整した。オートクレーブ内での重合終了後、下部ノズルからストランド状にポリアミド66を送り出し、水冷及びカッティングを経て、(a-2)であるペレット状のポリアミド66重合体を得た。
押出機の上流側から1番目のバレルに備えられた上流側供給口と、下流側供給口とを有する、L/D(押出機のシリンダーの長さ/押出機のシリンダー径)=48(バレル数:12)の二軸押出機(ZSK-40MC:コペリオン社製(ドイツ))を用いた。上記二軸押出機において、上流側供給口を有するバレルから下流側供給口を有するバレルの手前のバレルまで(バレル数:7個)を310~320℃に設定し、下流側供給口を有するバレルから最終バレルまで(バレル数:5個)を290℃に設定し、スクリュー回転数200rpm、減圧度-0.08MPa及び吐出量80kg/時間に設定した。
かかる条件下で、下記表1に記載された割合となるように、上流側供給口より(A)ポリアミド66と、(C)銅化合物及びハロゲン化物とを供給し、下流側供給口より(B)ガラス繊維を供給した。そして、これらを溶融混練することで樹脂組成物のペレットを製造した。得られたペレットを用いて、分子量、およびペレットの発泡を評価した。また、得られた樹脂組成物を、樹脂温度290℃及び金型温度80℃で成形し、各物性を評価した。これらの評価結果などを下記表1に記載した。
(B)ガラス繊維に(b-2)を用いた以外は、実施例1と同様に溶融混錬し、樹脂組成物のペレットを製造した。
二軸押出機のバレル温度を全て290℃に設定し、配合量を表1のようにした以外は、実施例1と同様に溶融混練したが、押出機のトルクが上限付近となったため、押出し不可と判定した。
二軸押出機のバレル温度を全て290℃、吐出量40kg/時間に設定し、配合量を表1のようにした以外は、実施例1と同様に溶融混練し、樹脂組成物のペレットを製造した。
(B)ガラス繊維に(b-2)を用いた以外は、比較例3と同様に溶融混錬し、樹脂組成物のペレットを製造した。
Claims (14)
- (A)ポリアミド66と、(B)ガラス繊維と、(C)銅化合物及びハロゲン化物と、を含むポリアミド樹脂組成物であって、前記(A)ポリアミド66においてゲルパーミエーションクロマトグラフィー(GPC)から求められる、分子量30,000以下の成分の割合が、前記(A)ポリアミド66全体の30~37質量%であり、かつ、分子量100,000以上の成分の割合が、前記(A)ポリアミド66全体の8~15質量%であるポリアミド樹脂組成物。
- 前記(B)ガラス繊維の平均繊維径が5~9μmである請求項1に記載のポリアミド樹脂組成物。
- 前記(A)ポリアミド66が、相対粘度RVが65以上250以下のポリアミド66(A-1)を1種類以上と、相対粘度RVが25以上65未満のポリアミド66(A-2)を1種類以上とを含む請求項1または2に記載のポリアミド樹脂組成物。
- 前記ポリアミド66(A-1)と前記ポリアミド66(A-2)の質量比(A-1)/(A-2)が、85/15~50/50である請求項3に記載のポリアミド樹脂組成物。
- 前記(A)ポリアミド66を100質量部と、前記(B)ガラス繊維を1~100質量部と、前記(C)銅化合物及びハロゲン化物を0.005~1質量部とを含む請求項1~4いずれか1項に記載のポリアミド樹脂組成物。
- 前記(A)ポリアミド66に対する銅の濃度[Cu]が、40ppm以上300ppm以下である請求項1~5いずれか1項に記載のポリアミド樹脂組成物。
- 前記(A)ポリアミド66に対するハロゲンの濃度[X]が、40ppm以上9000ppm以下である請求項1~6いずれか1項に記載のポリアミド樹脂組成物。
- ハロゲンの含有量と銅の含有量とのモル比(ハロゲン/銅)が、2/1~50/1である請求項6または7に記載のポリアミド樹脂組成物。
- ISO527に準拠して測定した引張強度の標準偏差が、0.50以下である請求項1~8いずれか1項に記載のポリアミド樹脂組成物。
- ISO527に準拠して測定した引張伸びの標準偏差が、0.08以下である請求項1~9いずれか1項に記載のポリアミド樹脂組成物。
- 請求項1~10いずれか1項に記載のポリアミド樹脂組成物からなるペレットの集合体であって、ISO527に準拠して測定した引張強度の標準偏差が、0.50以下であるポリアミド樹脂組成物ペレット群。
- ISO527に準拠して測定した引張伸びの標準偏差が、0.08以下である請求項11に記載のポリアミド樹脂組成物ペレット群。
- 請求項1~10いずれか1項に記載のポリアミド樹脂組成物を製造するポリアミド樹脂組成物の製造方法であって、
前記(A)ポリアミド66と、前記(C)銅化合物及びハロゲン化物とを、溶融混練温度を300℃以上330℃以下で溶融混練し、混練物を得る工程(1-1)と、
前記工程(1-1)で得られた前記混練物に前記(B)ガラス繊維を添加し、溶融混練する工程(1-2)と、を有するポリアミド樹脂組成物の製造方法。 - 請求項1~10のいずれか1項に記載のポリアミド樹脂組成物を成形してなる成形体。
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