WO2023181711A1 - Composition de résine polyamide, matériau composite de résine de matériau magnétique et article moulé correspondant - Google Patents

Composition de résine polyamide, matériau composite de résine de matériau magnétique et article moulé correspondant Download PDF

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WO2023181711A1
WO2023181711A1 PCT/JP2023/004979 JP2023004979W WO2023181711A1 WO 2023181711 A1 WO2023181711 A1 WO 2023181711A1 JP 2023004979 W JP2023004979 W JP 2023004979W WO 2023181711 A1 WO2023181711 A1 WO 2023181711A1
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polyamide
mass
polyamide resin
resin composition
resin
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Japanese (ja)
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幸一郎 倉知
勇摩 入佐
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Ｕｂｅ株式会社
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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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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

Definitions

  • the present invention relates to a polyamide resin composition, a magnetic resin composite material, and a molded article thereof.
  • Patent Documents 1 and 2 Polyamide resin compositions in which a polyamide elastomer is blended with a polyamide resin are known for the purpose of improving the flexibility and impact resistance of the polyamide resin (see Patent Documents 1 and 2).
  • magnetic powder is mixed into a composition containing a polyamide resin and a polyamide monomer to form a magnetic material-resin composite material known as a plastic magnet (see Patent Document 3).
  • a magnetic resin composite material containing a polyamide elastomer, a thermoplastic resin such as a polyamide resin, and magnetic powder has excellent flexibility, impact resistance, and hydrolysis resistance (patent (See references 4 and 5).
  • Patent Documents 1, 3, and 4 studies on polyamide resins from the viewpoint of moldability and impact resistance of molded products of polyamide resin compositions were insufficient.
  • Patent Documents 1 and 2 do not examine the mechanical properties of the polyamide resin composition when mixed with magnetic powder.
  • polyamide resins such as aliphatic resins, aromatic resins, homopolymers, and copolymers, and depending on the selection, the physical properties and the range of applicable products vary greatly.
  • Patent Documents 3 to 5 studies on polyamide resins from the viewpoint of mechanical properties of molded articles made of magnetic resin composite materials were insufficient.
  • a first aspect of the present invention aims to provide a polyamide resin composition that has excellent moldability and impact resistance.
  • a second aspect of the present invention aims to provide a magnetic resin composite material having excellent strength and toughness.
  • the first aspect of the present invention is, for example, the following [1] to [11].
  • [1] In 100% by mass of the polyamide resin composition, 10 to 50% by mass of polyamide elastomer (A), and 40 to 75% by mass of aliphatic homopolyamide resin (B) having an average number of carbon atoms per amide group of more than 6. %, and 0.5 to 30% by mass of aliphatic copolymerized polyamide resin (C), and substantially free of aromatic polyamide resin.
  • the mass ratio (C)/((B)+(C)) of the aliphatic copolyamide resin (C) to the total of the aliphatic homopolyamide resin (B) and the aliphatic copolyamide resin (C) is , 0.1 to 0.4, the polyamide resin composition according to [1] or [2].
  • the polyamide elastomer (A) contains a structural unit derived from an aminocarboxylic acid compound represented by the following formula (1) and/or a lactam compound represented by the following formula (2), and a structural unit derived from the following formula (3).
  • Any of [1] to [4] which is a polymer containing a structural unit derived from the XYX type triblock polyether diamine compound represented by the formula (4) and a structural unit derived from the dicarboxylic acid compound represented by the following formula (4).
  • the polyamide resin composition [However, R 1 represents a linking group containing a hydrocarbon chain. ] [However, R 2 represents a linking group containing a hydrocarbon chain.
  • the aliphatic copolymerized polyamide resin (C) is at least one selected from the group consisting of polyamide 6/66, polyamide 6/12 and polyamide 6/66/12 [1] to [6] Any polyamide resin composition.
  • the terminal amino group concentration of the polyamide resin mixture which is a combination of the polyamide elastomer (A), aliphatic homopolyamide resin (B), and aliphatic copolyamide resin (C), is 15 ⁇ mol/g or more [1
  • a magnetic resin composite material comprising the polyamide resin composition according to any one of [1] to [8] and magnetic powder.
  • the second aspect of the present invention is, for example, the following ⁇ 1> to ⁇ 10>.
  • a magnetic material resin composite material comprising a polyamide resin composition (X) and magnetic powder (Y), In a total of 100% by mass of the polyamide resin composition (X) and magnetic powder (Y), 5 to 30% by mass of the polyamide resin composition (X) and 70 to 95% by mass of the magnetic powder (Y).
  • aliphatic homopolyamide resin (B) having an average number of carbon atoms of more than 6 per amide group 40 to 75% % by mass and 0.5 to 30% by mass of aliphatic copolymerized polyamide resin (
  • the mass ratio (C)/((B)+(C)) of the aliphatic copolyamide resin (C) to the total of the aliphatic homopolyamide resin (B) and the aliphatic copolyamide resin (C) is , 0.1 to 0.4, ⁇ 1> or ⁇ 2> magnetic material resin composite material.
  • the polyamide resin composition (X) has an MFR of 12.0 g/10 minutes or more and less than 18.0 g/10 minutes when measured at 190° C. and a load of 1.00 kg in accordance with ISO 1133 ⁇ 1> ⁇
  • the polyamide elastomer (A) contains a structural unit derived from an aminocarboxylic acid compound represented by the following formula (1) and/or a lactam compound represented by the following formula (2), and a structural unit derived from the following formula (3).
  • Any of ⁇ 2> to ⁇ 4> which is a polymer containing a structural unit derived from the XYX type triblock polyether diamine compound represented by the formula (4) and a structural unit derived from the dicarboxylic acid compound represented by the following formula (4).
  • a magnetic resin composite material is any of ⁇ 2> to ⁇ 4> which is a polymer containing a structural unit derived from the XYX type triblock polyether diamine compound represented by the formula (4) and a structural unit derived from the dicarboxylic acid compound represented by the following formula (4).
  • R 1 represents a linking group containing a hydrocarbon chain.
  • R 2 represents a linking group containing a hydrocarbon chain.
  • x represents an integer from 1 to 20
  • y represents an integer from 4 to 50
  • z represents an integer from 1 to 20.
  • R 3 represents a linking group containing a hydrocarbon chain, and m is 0 or 1.
  • aliphatic homopolyamide resin (B) is at least one member selected from the group consisting of polyamide 11, polyamide 12, polyamide 612, polyamide 611, and polyamide 610. Material resin composite material.
  • the aliphatic copolymerized polyamide resin (C) is at least one selected from the group consisting of polyamide 6/66, polyamide 6/12, and polyamide 6/66/12 of ⁇ 1> to ⁇ 6>. Any magnetic material resin composite material.
  • the terminal amino group concentration of the polyamide resin mixture comprising the polyamide elastomer (A), aliphatic homopolyamide resin (B) and aliphatic copolyamide resin (C) is 15 ⁇ mol/g or more ⁇ 1
  • the molded article of the magnetic resin composite material of ⁇ 9> which is an electromagnetic device, an in-vehicle electromagnetic device, a toy, an office device, or an audio device, or a part thereof.
  • the polyamide resin composition of the first aspect of the present invention has excellent moldability and impact resistance.
  • the magnetic resin composite material of the second aspect of the present invention has excellent strength and toughness.
  • the first aspect of the present invention is an aliphatic homopolyamide resin containing 10 to 50% by mass of a polyamide elastomer (A) and an average number of carbon atoms per amide group of more than 6 in 100% by mass of the polyamide resin composition.
  • B) 40 to 75% by mass, and an aliphatic copolymerized polyamide resin (C) 0.5 to 30% by mass, and relates to a polyamide resin composition substantially free of aromatic polyamide resin.
  • a second aspect of the present invention is a magnetic material resin composite material comprising a polyamide resin composition (X) and magnetic powder (Y), In a total of 100% by mass of the polyamide resin composition (X) and magnetic powder (Y), 5.0 to 30.0% by mass of the polyamide resin composition (X) and 70% of the magnetic powder (Y). Contains .0 to 95.0% by mass, In 100% by mass of polyamide resin composition (X), 10 to 50% by mass of polyamide elastomer (A), and 40 to 75% by mass of aliphatic homopolyamide resin (B) having an average number of carbon atoms per amide group of more than 6. %, and 0.5 to 30% by mass of aliphatic copolymerized polyamide resin (C), and substantially free of aromatic polyamide resin.
  • the polyamide resin composition (X) of the second aspect of the invention corresponds to the polyamide resin composition of the first aspect of the invention.
  • both the polyamide resin composition of the first embodiment and the polyamide resin composition (X) of the second embodiment will be referred to as polyamide resin compositions.
  • the polyamide resin composition of the first embodiment and the polyamide resin composition (X) of the second embodiment are both referred to as polyamide resin composition (X).
  • substantially not contained means that it is not contained to the extent that it changes the properties of the polyamide resin composition or the functions and properties of the molded product obtained from the polyamide resin composition, and This does not preclude its inclusion to the extent that it does not impair its characteristics.
  • the content of the polyamide elastomer (A), aliphatic homopolyamide resin (B) and aliphatic copolyamide resin (C) in which the average number of carbon atoms per amide group is more than 6, is determined by the first decimal place. The value is rounded off, but if the content is less than 1% by mass, the value is rounded off to the second decimal place.
  • the contents of the polyamide resin composition (X) and the magnetic powder (Y) are values rounded to the second decimal place. When described as 0% by mass, it means not included.
  • the polyamide resin composition contains a polyamide elastomer (A). Since the polyamide resin composition contains the polyamide elastomer (A) (hereinafter also referred to as "component (A)"), the molded product thereof exhibits excellent flexibility.
  • the polyamide elastomer (A) has a hard segment and a soft segment, and the hard segment has a polyamide structure.
  • the soft segment of the polyamide elastomer preferably has a polyether structure, and more preferably has a structural unit derived from a polyether diamine compound.
  • Examples of the polyamide elastomer having a polyether structure as a soft segment include a polyether ester amide elastomer in which a hard segment and a soft segment are bonded together through an ester bond, and a polyether polyamide elastomer in which a hard segment and a soft segment are bonded together through an amide bond. From the viewpoint of exhibiting the effects of the present invention and from the viewpoint of excellent hydrolysis resistance, a polyether polyamide elastomer in which a hard segment and a soft segment are bonded by an amide bond is preferred.
  • the polyamide structure in the hard segment is a polycondensate having a structural unit derived from a polyamide-forming monomer that is at least one selected from the group consisting of a nylon salt consisting of a diamine and a dicarboxylic acid, an aminocarboxylic acid compound, and a lactam compound. preferable.
  • the aminocarboxylic acid compound is preferably represented by the following general formula (1).
  • R 1 represents a linking group containing a hydrocarbon chain.
  • the lactam compound is preferably represented by the following general formula (2). [However, R 2 represents a linking group containing a hydrocarbon chain. ]
  • R 1 is preferably a divalent hydrocarbon group containing an aliphatic group, an alicyclic group, and/or an aromatic group having 2 to 20 carbon atoms, and more preferably a carbon
  • aminocarboxylic acid compounds include aliphatic compounds having 5 to 20 carbon atoms such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
  • Examples include ⁇ -aminocarboxylic acid. These can be used alone or in combination of two or more.
  • R 2 is preferably a divalent hydrocarbon group containing an aliphatic group, an alicyclic group, and/or an aromatic group having 2 to 20 carbon atoms, and more preferably a carbon
  • lactam compound examples include aliphatic lactams having 4 to 20 carbon atoms such as ⁇ -caprolactam, ⁇ -enantholactam, ⁇ -undecalactam, ⁇ -lauryllactam, 2-pyrrolidone, and ⁇ -butyrolactam. These can be used alone or in combination of two or more.
  • aminocarboxylic acid compounds and lactam compounds ⁇ -lauryllactam, 11-aminoundecanoic acid, or 12-aminododecanoic acid is preferred from the viewpoint of dimensional stability due to low water absorption, chemical resistance, and mechanical properties.
  • the diamine in the nylon salt at least one diamine selected from aliphatic, alicyclic and aromatic diamines or derivatives thereof can be used.
  • Diamines in the nylon salt include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Aliphatic compounds having 2 to 20 carbon atoms such as 2,2,4-trimethylhexane-1,6-diamine, 2,4,4-trimethylhexane-1,6-diamine, and 3-methylpentane-1,5-diamine Examples include diamine compounds such as diamine. These can be used alone or in combination of two or more.
  • dicarboxylic acid in the nylon salt at least one dicarboxylic acid selected from aliphatic, alicyclic, and aromatic dicarboxylic acids or derivatives thereof can be used.
  • dicarboxylic acids include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. dicarboxylic acid compounds. These can be used alone or in combination of two or more.
  • the lactam compound becomes a unit constituting the polyamide structure by ring-opening polymerization, and the aminocarboxylic acid compound and nylon salt by polycondensation.
  • the polyamide structure preferably has carboxyl groups at both ends.
  • the hard segment includes the polyamide structure and a structural unit derived from at least one dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids or derivatives thereof. It's also a segment.
  • a polyamide structure having carboxyl groups at both ends can be obtained by ring-opening polymerization or polycondensation of the above polyamide-forming monomer in the presence of a dicarboxylic acid by a conventional method.
  • the dicarboxylic acid is preferably represented by the following general formula (4).
  • R 3 represents a linking group containing a hydrocarbon chain, and m is 0 or 1.
  • dicarboxylic acid (4) at least one dicarboxylic acid selected from aliphatic, alicyclic, and aromatic dicarboxylic acids or derivatives thereof can be used.
  • R 3 is preferably a divalent hydrocarbon group containing an aliphatic group, an alicyclic group, and/or an aromatic group having 1 to 20 carbon atoms, more preferably a carbon number
  • the above hydrocarbon group has 1 to 15 carbon atoms, more preferably the above hydrocarbon group has 2 to 12 carbon atoms, even more preferably the above hydrocarbon group has 4 to 10 carbon atoms, particularly preferably 4 carbon atoms. ⁇ 10 alkylene groups.
  • dicarboxylic acid represented by the above general formula (4) examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc. having 2 carbon atoms.
  • aliphatic dicarboxylic acids aliphatic dicarboxylic acids, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.
  • dimer acid and hydrogenated dimer acid products such as “Pripol 1004", “Pripol 1006”, “Pripol 1009”, and “Pripol 1013” manufactured by Croda Corporation can be used. These can be used alone or in combination of two or more. Among these, adipic acid, sebacic acid, and dodecanedioic acid are preferred.
  • the number average molecular weight of the hard segment is preferably 300 to 15,000, more preferably 300 to 6,000 from the viewpoint of flexibility and moldability.
  • the number average molecular weight is a value determined by gel permeation chromatography.
  • the hard segment includes structural units derived from dicarboxylic acids at both arbitrary ends.
  • the soft segment preferably has a polyether structure, and the constituent unit of the polyether structure is preferably oxyalkylene having 2 to 4 carbon atoms.
  • the alkylene group of oxyalkylene is preferably a linear or branched alkylene group having 2 to 4 carbon atoms, such as ethylene group, n-propylene group, i-propylene group, 1-methylethylene group, 2-methylethylene group. , n-butylene group, 1-methylpropylene group, 2-methylpropylene group, dimethylethylene group, ethylethylene group, etc.
  • the structural units of the polyether structure may be one type alone or two or more types, but two or more types are preferable.
  • polyether structure of the soft segment examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and XYX type triblock polyether. These can be used alone or in combination of two or more.
  • XYX type triblock polyether examples include a structure represented by the following general formula (5).
  • x represents an integer from 1 to 20
  • y represents an integer from 4 to 50
  • z represents an integer from 1 to 20.
  • x and z are each independently preferably an integer of 1 to 18, more preferably an integer of 1 to 16, even more preferably an integer of 1 to 14, and an integer of 1 to 12. Particularly preferred.
  • y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, even more preferably an integer of 7 to 35, particularly preferably an integer of 8 to 30.
  • x and z are within the above range, and it is preferable from the viewpoint of rubber elasticity that y is within the above range. Moreover, it is preferable that x, y, and z are in the above ranges from the viewpoint of the toughness of the elastomer.
  • the number average molecular weight of the soft segment is preferably 200 to 6,000, more preferably 650 to 2,000.
  • the polyether structure preferably has amino groups at both ends.
  • the soft segment is also a segment that includes the above polyether structure and has amino groups at both ends.
  • the XYX type triblock polyether diamine compound having amino groups at both ends is represented by, for example, the following general formula (3).
  • x represents an integer of 1 to 20
  • y represents an integer of 4 to 50
  • z represents an integer of 1 to 20.
  • x and z are each independently preferably an integer of 1 to 18, more preferably an integer of 1 to 16, even more preferably an integer of 1 to 14, and an integer of 1 to 12. Particularly preferred.
  • y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, even more preferably an integer of 7 to 35, particularly preferably an integer of 8 to 30.
  • Examples of the combination of the hard segment and the soft segment include the combinations of the hard segment and soft segment listed above. Among these, combinations of ring-opened polycondensates of lauryllactam/polyethylene glycol, ring-opened polycondensates of lauryllactam/components derived from dicarboxylic acid/polypropylene glycol, and ring-opened polycondensates of lauryllactam/combinations of dicarboxylic acid-derived constituent units are included.
  • Particularly preferred is a combination of XYX type triblock polyethers.
  • the polyether is preferably a structural unit derived from a polyether diamine compound as represented by the above general formula (3).
  • the hard segment/soft segment (mass ratio) is more preferably 95/5 to 25/75.
  • the ratio (mass ratio) of the hard segment to the soft segment is a value calculated based on the blending amount of the monomer components constituting each segment.
  • the ratio (mass ratio) of the hard segment to the soft segment of the obtained polyamide-based elastomer is equal to the value calculated based on the blending amount of the monomer components constituting each segment.
  • the terminal group used for bonding the hard segment and the soft segment shall be included in the monomer component having the terminal group.
  • the two amino groups of the XYX type triblock polyether diamine compound are calculated as being included in the monomer components constituting the soft segment, and the carboxyl groups in the polyamide structure when both ends are carboxyl groups are Calculated as included in the segment.
  • the hard segment/soft segment (mass ratio) is smaller than the above range, the crystallinity of the polyamide component may decrease, which may be undesirable because mechanical properties such as strength and elastic modulus may decrease. If the hard segment/soft segment (mass ratio) is larger than the above range, it may be undesirable because it becomes difficult to exhibit functions and performance as an elastomer such as rubber elasticity and flexibility.
  • polyamide elastomers as described above include, for example, the "Diamide (registered trademark)” series manufactured by Polypla Evonik, the “Pebax” series manufactured by ARKEMA, and the “Grill” series manufactured by M-Chemie Japan. Examples include “Flex (registered trademark) EBG”, “Grill Flex (registered trademark) ELG”, “Grillon (registered trademark) ELX”, and the "UBESTA XPA (registered trademark)” series manufactured by UBE Corporation.
  • the "UBESTA XPA (registered trademark)" series manufactured by UBE Co., Ltd. under the trade name is preferred among commercially available products from the viewpoint of exhibiting the effects of the present invention and from the viewpoint of excellent hydrolysis resistance.
  • the polyamide elastomer (A) may be used alone or in combination of two or more.
  • the relative viscosity is preferably 1.10 to 5.00, more preferably 1.50 to 4.50, particularly preferably 1.50 to 3.00.
  • the hardness (Shore D) of the polyamide elastomer (A) is preferably in the range of 15 to 70, more preferably in the range of 18 to 70, more preferably in the range of 20 to 70, and particularly preferably in the range of 20 to 70. It is in the range of 25-70.
  • Hardness (Shore D) is the median value of hardness measurements at five points measured using a type D durometer in accordance with ISO868.
  • a preferred embodiment of the polyamide elastomer (A) is a structural unit derived from an aminocarboxylic acid compound represented by the above general formula (1) and/or a lactam compound represented by the above general formula (2), and a structural unit derived from the above general formula (3).
  • It is a polymer containing a structural unit derived from an XYX type triblock polyether diamine compound represented by the formula (4) and a structural unit derived from a dicarboxylic acid compound represented by the above general formula (4).
  • One example of a preferred method for producing the polyamide elastomer (A) is to melt-polymerize the three components of a polyamide-forming monomer, an XYX type triblock polyether diamine, and a dicarboxylic acid under pressure and/or normal pressure. If necessary, a method comprising a step of further melt polymerization under reduced pressure can be used, and the three components of polyamide-forming monomer, XYX type triblock polyether diamine and dicarboxylic acid are simultaneously added under pressure and/or normal pressure. A method comprising the steps of melt polymerizing under reduced pressure and, if necessary, further melt polymerizing under reduced pressure can be used.
  • the polyamide elastomer can be produced at a polymerization temperature of preferably 150 to 300°C, more preferably 160 to 280°C, particularly preferably 180 to 250°C. If the polymerization temperature is lower than the above temperature, the polymerization reaction tends to be slow, and if it is higher than the above temperature, thermal decomposition tends to occur and a polymer with good physical properties may not be obtained.
  • the polyamide elastomer can be produced by a method consisting of the steps of normal pressure melt polymerization or normal pressure melt polymerization followed by reduced pressure melt polymerization.
  • a lactam compound a compound synthesized from a diamine compound and a dicarboxylic acid compound, and/or a salt thereof as a polyamide-forming monomer
  • an appropriate amount of water is allowed to coexist and a pressure of 0.1 to 5 MPa is used. It can be produced by a method consisting of melt polymerization followed by normal pressure melt polymerization and/or reduced pressure melt polymerization.
  • a polyamide elastomer can be produced with a polymerization time of usually 0.5 to 30 hours. If the polymerization time is shorter than the above range, the increase in molecular weight tends to be insufficient, and if it is longer, coloring due to thermal decomposition tends to occur, and in either case, a polyamide elastomer having desired physical properties may not be obtained.
  • polyamide elastomers can be carried out either batchwise or continuously, and can be carried out using batch-type reactors, single-vessel or multi-vessel continuous reactors, tubular continuous reactors, etc. alone or in appropriate combinations. Can be used.
  • monoamines and diamines such as laurylamine, stearylamine, hexamethylene diamine, metaxylylene diamine, acetic acid, and benzoic acid are used as necessary to adjust the molecular weight and stabilize the melt viscosity during molding.
  • Acid, monocarboxylic acid such as stearic acid, adipic acid, sebacic acid, dodecanedioic acid, or dicarboxylic acid can be added. It is preferable to add these in appropriate amounts so that the relative viscosity of the elastomer finally obtained is in the range of 1.10 to 5.00.
  • the amounts of the above-mentioned monoamines and diamines, monocarboxylic acids, dicarboxylic acids, etc. added be within a range that does not impede the properties of the resulting polyamide elastomer.
  • phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are used as catalysts as necessary, and phosphorous acid, hypophosphorous acid, and these are used as catalysts and heat-resistant agents.
  • Inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts can be added.
  • the catalysts may be used alone or in combination of two or more. The amount added is usually 50 to 3000 ppm based on the raw materials.
  • a heat resistant agent may be used when producing the polyamide elastomer.
  • Organic or inorganic heat-resistant agents can be used depending on the purpose. Examples of the organic heat-resistant agent include phenolic compounds, phosphorus compounds, sulfur compounds, nitrogen compounds, and the like. Examples of inorganic heat-resistant agents include copper compounds and potassium halides. The heat resistant agents may be used alone or in combination of two or more.
  • the content of the polyamide elastomer (A) in 100% by mass of the polyamide resin composition is 10 to 50% by mass, preferably 15 to 45% by mass, and more preferably 20 to 40% by mass.
  • the content of the polyamide elastomer (A) is within the above range, a molded article with excellent impact resistance can be obtained.
  • the polyamide resin composition is an aliphatic homopolyamide resin (B) having an average number of carbon atoms per amide group of more than 6 (hereinafter referred to as "aliphatic homopolyamide resin (B)", “component (B)” or " (B).)
  • aliphatic homopolyamide resin (B) having an average number of carbon atoms per amide group of more than 6
  • component (B) or " (B).
  • Aliphatic homopolyamide resin is a polyamide resin consisting of one type of structural unit derived from an aliphatic monomer.
  • the aliphatic homopolyamide resin may be made of at least one of one type of lactam and an aminocarboxylic acid that is a hydrolyzate of the lactam, or may be made of a combination of one type of diamine and one type of dicarboxylic acid. It may be something. Here, the combination of diamine and dicarboxylic acid is considered to be one type of monomer.
  • Aliphatic also includes alicyclic.
  • lactam examples include enantholactam, undecanelactam, dodecanelactam, ⁇ -pyrrolidone, ⁇ -piperidone, and the like. Among these, from the viewpoint of polymerization productivity, one selected from the group consisting of undecane lactam and dodecane lactam is preferred.
  • aminocarboxylic acids include 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
  • diamines examples include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecane diamine, tetradecane diamine, pentadecane diamine. , hexadecane diamine, heptadecane diamine, octadecane diamine, nonadecane diamine, eicosane diamine, 2-methyl-1,8-octanediamine, 2,2,4/2,4,4-trimethylhexamethylene diamine, etc.
  • Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, and pentadecane.
  • Aliphatic dicarboxylic acids such as dionic acid, hexadecanedionic acid, octadecanedioic acid, and eicosanedioic acid; 1,3-/1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornanedicarboxylic acid
  • Examples include alicyclic dicarboxylic acids such as.
  • An aliphatic homopolyamide resin in which the average number of carbon atoms per amide group is more than 6 means that when the constituent units are lactams and aminocarboxylic acids, the number of carbon atoms in all of the constituent units exceeds 6. means.
  • the structural unit is a combination of diamine and dicarboxylic acid, the sum of all the carbon atoms contained in the diamine and all the carbon atoms contained in the dicarboxylic acid divided by 2 exceeds 6. .
  • Aliphatic homopolyamide resins having an average number of carbon atoms per amide group of more than 6 include polyundecane lactam (polyamide 11), polylauryllactam (polyamide 12), polytetramethylene dodecamide (polyamide 412), and polypentamethylene.
  • Azelamide Polyamide 59), Polypentamethylene Sebaamide (Polyamide 510), Polypentamethylene Dodecamide (Polyamide 512), Polyhexamethylene Sveramide (Polyamide 68), Polyhexamethylene Azeramide (Polyamide 69), Polyhexamide Methylene sebaamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecamide (polyamide 614), polyhexamethylene hexadecamide (polyamide 616) ), polyhexamethylene octadecamide (polyamide 618), polynonamethylene adipamide (polyamide 96), polynonamethylene sveramide (polyamide 98), polynonamethylene azelamide (polyamide 99), polynonamethylene sebaamide (Polyamide 910), Polynonamethylene Dodecamide (Polyamide
  • the aliphatic homopolyamide resin (B) preferably has an average number of carbon atoms of 8 to 12 per amide group, more preferably 10 to 12. Particularly preferred is at least one selected from the group consisting of polyamide 11, polyamide 12, polyamide 612, polyamide 611, and polyamide 610.
  • the degree of polymerization of the aliphatic homopolyamide resin (B) is not particular limit to the degree of polymerization of the aliphatic homopolyamide resin (B), but according to JIS K 6920-2, 1 g of polyamide resin is dissolved in 100 ml of 96% concentrated sulfuric acid, and the relative viscosity measured at 25 ° C. It is preferably from 1.1 to 10.0, more preferably from 1.2 to 8.0, particularly preferably from 1.5 to 5.0.
  • the aliphatic homopolyamide resin (B) contains two or more types of polyamide resins having different relative viscosities, it is preferable to measure the relative viscosity of the aliphatic homopolyamide resin (B). The average value calculated by summing up the values obtained by multiplying the relative viscosity of the resin by its mixing ratio can be taken as the relative viscosity of the aliphatic homopolyamide resin (B).
  • the content of the aliphatic homopolyamide resin (B) having an average number of carbon atoms of more than 6 per amide group is 40 to 75% by mass, preferably 40 to 70% by mass. , more preferably 40 to 60% by mass.
  • the content of the aliphatic homopolyamide resin (B) is within the above range, a molded article having both flexibility and toughness and excellent impact resistance can be obtained. Moreover, moldability is also good.
  • the polyamide resin composition includes an aliphatic copolymerized polyamide resin (C).
  • the aliphatic copolymerized polyamide resin (C) (hereinafter also referred to as “component (C)” or “(C)”) is a polyamide resin composed of two or more types of structural units derived from aliphatic monomers.
  • the aliphatic copolymerized polyamide resin (C) is a copolymer of monomers selected from the group consisting of combinations of diamines and dicarboxylic acids, lactams, and aminocarboxylic acids.
  • the combination of diamine and dicarboxylic acid is considered to be one type of monomer.
  • Aliphatic also includes alicyclic.
  • diamine examples include ethylenediamine in addition to the same diamines as those exemplified as raw materials for the aliphatic homopolyamide resin.
  • dicarboxylic acid the same ones as those exemplified as raw materials for the aliphatic homopolyamide resin can be mentioned.
  • lactam examples include ⁇ -caprolactam in addition to those exemplified as raw materials for the aliphatic homopolyamide resin.
  • the aliphatic copolymerized polyamide resin (C) includes caprolactam/hexamethylene diamino adipic acid copolymer (polyamide 6/66), caprolactam/hexamethylene diamino azelaic acid copolymer (polyamide 6/69), and caprolactam.
  • polyamide 6/66, polyamide 6/12, and polyamide 6/66/12 are selected from the group consisting of polyamide 6/66, polyamide 6/12, and polyamide 6/66/12. At least one type is preferred.
  • the relative viscosity is determined by the same method as explained in the section of the aliphatic homopolyamide resin (B). .
  • the content of the aliphatic copolymerized polyamide resin (C) is 0.5 to 30% by mass, preferably 2 to 30% by mass, and 5 to 25% by mass. It is more preferable that there be.
  • the content of the aliphatic copolyamide resin (C) is within the above range, the effects of the present invention such as strength and toughness can be exhibited.
  • the mass ratio (C)/((B)+(C)) of the aliphatic copolyamide resin (C) to the total of the aliphatic homopolyamide resin (B) and the aliphatic copolyamide resin (C) is 0. It is preferably 1 to 0.4 (a value rounded to the second decimal place), and more preferably 0.15 to 0.35 (a value rounded to the third decimal place). It is preferable that the mass ratio is within the above range from the viewpoint of achieving both flexibility and toughness of the molded product.
  • Polyamide resin manufacturing equipment includes batch reaction vessels, single-vessel or multi-vessel continuous reaction apparatuses, tubular continuous reaction apparatuses, kneading reaction extruders such as single-screw kneading extruders, twin-screw kneading extruders, etc.
  • kneading reaction extruders such as single-screw kneading extruders, twin-screw kneading extruders, etc.
  • known polyamide manufacturing equipment can be mentioned.
  • known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure, and pressurization operations. These polymerization methods can be used alone or in combination as appropriate.
  • the terminal amino group concentration of the polyamide resin mixture which is a combination of polyamide elastomer (A), aliphatic homopolyamide resin (B), and aliphatic copolyamide resin (C) in the polyamide resin composition, is the same as that of phenol and methanol.
  • the terminal amino group concentration determined by neutralization titration after dissolving in a mixed solvent is preferably 15 ⁇ mol/g or more, more preferably 15 ⁇ mol/g or more and 110 ⁇ mol/g or less, and even more preferably 15 ⁇ mol/g or more and 70 ⁇ mol/g or less. , 15 ⁇ mol/g or more and 20 ⁇ mol/g or less is particularly preferable. Within the above range, the polyamide resin composition has good moldability.
  • the terminal amino group concentration of the polyamide resin mixture which is a combination of aliphatic homopolyamide resin (B) and aliphatic copolyamide resin (C) in the polyamide resin composition, is determined by dissolving it in a mixed solvent of phenol and methanol and neutralizing it.
  • the terminal amino group concentration determined by titration is preferably 30 ⁇ mol/g or more, more preferably 30 ⁇ mol/g or more and 110 ⁇ mol/g or less, and even more preferably 30 ⁇ mol/g or more and 70 ⁇ mol/g or less. Within the above range, the polyamide resin composition has good moldability.
  • the terminal amino group concentration in the polyamide resin mixture is determined by the neutralization determination described above. However, if the terminal amino group concentration and mixing ratio of each polyamide resin are known, the average value calculated by summing the values obtained by multiplying each terminal amino group concentration by the mixing ratio is It may also be the terminal amino group concentration of the resin.
  • the polyamide resin composition is substantially free of aromatic polyamide resin.
  • the aromatic polyamide resin In 100% by mass of the polyamide resin composition, the aromatic polyamide resin is preferably less than 0.1% by mass, more preferably less than 0.05% by mass, particularly preferably less than 0.02% by mass. Charpy impact strength tends to decrease when aromatic polyamide resin is included. Furthermore, if the aromatic polyamide resin contained in 100% by mass of the polyamide resin composition is less than 0.1% by mass, it is generally assumed that there will be no significant change in the function or characteristics of the molded product. .
  • aromatic polyamide resins include aromatic homopolyamide resins and aromatic copolyamide resins.
  • Aromatic homopolyamide resin refers to aromatic polyamide resin containing at least one type of structural unit derived from an aromatic compound, such as aliphatic dicarboxylic acid and aromatic diamine, aromatic dicarboxylic acid and aliphatic diamine, or aromatic It is a polyamide resin obtained by polycondensation of dicarboxylic acid and aromatic diamine as raw materials.
  • the aromatic copolyamide resin is an aromatic polyamide resin containing at least one kind of structural unit derived from an aromatic compound, and is a polyamide resin composed of two or more kinds of monomers.
  • the combination of diamine and dicarboxylic acid is considered to be a combination of one type of diamine and one type of dicarboxylic acid as one type of monomer, and has a structural unit derived from diamine and a structural unit derived from dicarboxylic acid.
  • aromatic polyamide resins include polynonane methylene terephthalamide (polyamide 9T), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene adipamide/polyhexamethylene terephthalamide Copolymer (Polyamide 66/6T), Polyhexamethylene terephthalamide/Polycaproamide copolymer (Polyamide 6T/6), Polyhexamethylene adipamide/Polyhexamethylene isophthalamide copolymer (Polyamide 66/6I), Polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 6I/6), polydodecamide/polyhexamethylene terephthalamide copolymer (polyamide 12/6T), polyhexamethylene adipamide/polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (polyamide 66
  • the polyamide resin composition may contain a polyamide elastomer and a thermoplastic resin other than the polyamide resin, as long as the object of the present invention is not impaired.
  • the thermoplastic resin other than the polyamide elastomer and polyamide resin is preferably 2% by mass or less, more preferably 0 to 1.5% by mass, based on 100% by mass of the polyamide resin composition.
  • the polyamide resin composition may optionally contain dyes, pigments, fibrous reinforcements, particulate reinforcements, plasticizers, antioxidants, heat resistant agents, blowing agents, Functionality imparting agents such as weathering agents, crystal nucleating agents, crystallization promoters, mold release agents, lubricants, antistatic agents, flame retardants, flame retardant aids, colorants, etc. may be contained as appropriate.
  • the magnetic powder is a component other than the polyamide resin composition.
  • the content of the optional component is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass based on 100% by mass of the polyamide resin composition.
  • the method for producing the polyamide resin composition is not particularly limited, and for example, the following method can be applied.
  • a commonly known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll is used.
  • a method of simply mixing the raw materials of each component using a commonly known mixer such as a tumbler mixer or a blender can also be applied.
  • the mixing temperature is preferably higher than the melting point of the polyamide resin, but is preferably 190 to 290°C from the viewpoint of controlling side reactions.
  • all raw materials are blended and then melt-kneaded, some of the raw materials are blended and then melt-kneaded, and the remaining raw materials are further blended and melt-kneaded, or one method is used. Any method may be used, such as mixing the remaining raw materials using a side feeder during melt-kneading after blending part of the raw materials, but it is preferable to melt-knead after blending all the raw materials.
  • the MFR (melt flow rate) of the polyamide resin composition measured at a temperature of 190°C and a load of 1.00 kg is preferably 12.0 g/10 minutes or more and less than 18.0 g/10 minutes, and 12. More preferably 5 g/10 minutes or more and less than 17.0 g/10 minutes, and even more preferably 13.0 g/10 minutes or more and less than 16.0 g/10 minutes.
  • the polyamide resin has good moldability and does not impair the toughness of the resulting molded product.
  • the polyamide resin composition can be suitably used for producing injection molded products by injection molding, extrusion molded products by extrusion molding, blow molded products by blow molding, and rotation molded products by rotation molding. Since the polyamide resin composition has good injection moldability, it can be more suitably used for injection molded products.
  • the method for producing an extrusion molded product from a polyamide resin composition by extrusion molding is not particularly limited, and any known method can be used.
  • Injection molded products by injection molding, extrusion molded products by extrusion molding, blow molded products by blow molding, and rotary molded products by rotation molding include, but are not particularly limited to, spoilers, air intake ducts, intake manifolds, resonators, fuel tanks, Automotive parts such as gas tanks, hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, and various other hoses, tubes, and tanks, mechanical parts such as power tool housings, pipes, and electrical equipment such as tanks, tubes, hoses, films, etc. ⁇ Various uses include electronic parts, household and office supplies, building material-related parts, and furniture parts.
  • the polyamide resin composition has excellent gas barrier properties, it is suitably used for molded products that come into contact with high-pressure gas, such as tanks, tubes, hoses, and films that come into contact with high-pressure gas.
  • high-pressure gas such as tanks, tubes, hoses, and films that come into contact with high-pressure gas.
  • the type of gas is not particularly limited and includes hydrogen, nitrogen, oxygen, helium, methane, butane, propane, etc. Gases with low polarity are preferred, and hydrogen, nitrogen, and methane are particularly preferred.
  • the polyamide resin composition can be used as a magnetic resin composite material by blending it with magnetic powder.
  • the magnetic powder (Y) is not particularly limited as long as it is a known magnetic powder that has the function of imparting magnetism and can be used in plastic magnets, such as ferrite magnetic powder, alnico magnetic powder, etc. , rare earth magnetic powder, etc.
  • the ferrite magnetic powder include barium ferrite magnetic powder such as iron oxide and barium carbonate, iron oxide such as magnetite, and strontium ferrite magnetic powder such as strontium carbonate.
  • alnico-based magnetic powder examples include alnico made of nickel, aluminum, cobalt, and copper, and alnico made of nickel, aluminum, cobalt, copper, and titanium.
  • the rare earth magnetic powder examples include samarium cobalt, rare earth cobalt magnets in which the cobalt component of samarium cobalt is replaced with copper, iron, titanium, zirconium, hafnium, niobium, tantalum, etc., and neodymium-iron-boron magnets. These can be used alone or in combination of two or more. Among these, ferrite magnetic powder is preferred, and strontium ferrite magnetic powder and magnetite are preferred.
  • the average particle size of the magnetic powder (Y) is 0. It is preferably 1 to 300 ⁇ m, more preferably 0.1 to 200 ⁇ m, and 0.1 to 200 ⁇ m. More preferably, the thickness is 5 to 100 ⁇ m. If the average particle size of the magnetic powder exceeds the above value, the fluidity of the magnetic resin composite material and the mechanical strength of the molded product may decrease.
  • the magnetic powder (Y) may be pre-treated with a coupling agent or a surface modifier in order to improve the dispersibility or adhesion when blended into the polyamide resin composition (X).
  • a coupling agent or surface modifier conventional coupling agents or surface modifiers such as silane, titanate, aluminum, phosphite and other organic phosphorus compounds, chromium, methacrylate, etc. can be used. . These types are appropriately selected depending on the type of resin used as the binder. Among these, amino group-containing silane compounds and titanate compounds are more preferred in order to improve compatibility with the polyamide resin. In addition to these, it is also possible to use additives such as lubricants and stabilizers to improve the fluidity, moldability, and magnetic properties of the magnetic resin composite material.
  • the polyamide resin composition (X) contains 5.0 to 30.0% by mass, preferably 5.0% by mass. -25.0% by mass, more preferably 5.0-20.0% by mass, and magnetic powder (Y) is 70.0-95.0% by mass, preferably 75.0-95.0% by mass , more preferably 80.0 to 95.0% by mass.
  • the content of the magnetic powder (Y) in the total of the polyamide resin composition (X) and the magnetic powder (Y) is less than the above value, the residual magnetic flux density is low and the practicality as a permanent magnet is reduced. is small and may have a small effect on the flow properties of the resin.
  • the content of the magnetic powder (Y) exceeds the above value, the magnetic field orientation will be poor, and the residual magnetic flux density will not improve due to the reduction of the resin component, and the amount of resin will be small, so the fluidity will be poor. This may cause problems such as insufficient filling during kneading and molding processes, and may lack practicality.
  • the magnetic resin composite material may contain dyes, pigments, fibrous reinforcements, particulate reinforcements, plasticizers, antioxidants, heat resistant agents, blowing agents, weatherproofing agents, etc. It may also contain a functional agent such as a crystal nucleating agent, a crystallization accelerator, a mold release agent, a lubricant, a stabilizer, an antistatic agent, a flame retardant, a flame retardant aid, a coloring agent, etc., as appropriate.
  • a functional agent such as a crystal nucleating agent, a crystallization accelerator, a mold release agent, a lubricant, a stabilizer, an antistatic agent, a flame retardant, a flame retardant aid, a coloring agent, etc., as appropriate.
  • the magnetic resin composite material is produced by mixing a polyamide resin composition and magnetic powder in a mixing step, and then performing a kneading step.
  • each component of the polyamide resin composition and magnetic powder are directly mixed in a mixing process, and then a kneading process is performed.
  • the mixing step the magnetic powder, the polyamide resin composition or each component of the polyamide resin composition, and various additives as necessary are blended and mixed by a known method.
  • the mixing step is preferably performed before the kneading step described below. Further, using a solvent during mixing is an effective means for uniformly adding coupling agents and lubricants when using them, but it is not always necessary.
  • the mixer is not particularly limited, and examples thereof include a ribbon mixer, a V-type mixer, a rotary mixer, a Henschel mixer, a flash mixer, a Nauta mixer, a tumbler, and the like. It is also effective to add, pulverize and mix using a rotary ball mill, vibrating ball mill, planetary ball mill, wet mill, jet mill, hammer mill, cutter mill or the like.
  • the shape of the polyamide resin composition for molding the magnetic material-resin composite may be pellets, beads, powder, paste, etc., but it is preferably in the form of fine particles in order to improve the homogeneity of the mixture.
  • the mixed magnetic powder, the polyamide resin composition, and any various additives, or the mixed magnetic powder, each component of the polyamide resin composition, and any various additives are mixed using a batch method such as Brabender.
  • This is a process of kneading in a temperature range of 50 to 400°C using a kneader, Banbury mixer, Henschel mixer, helical rotor, roll, single screw extruder, twin screw extruder, etc.
  • the kneading temperature is generally selected from a temperature range in which the polyamide resin melts and does not decompose.
  • the kneaded material is extruded into strands or sheets and then cut, hot cut, cut under water, or cooled and solidified into a block that is passed through a pulverizer to form pellets or powder and then subjected to molding. Ru. In this way, a magnetic resin composite material can be obtained.
  • a molding step is further performed in which a molding treatment is performed.
  • One-stage molding method in which the mixture is melted and kneaded and then molded into the desired shape
  • two-stage molding in which after the kneading process, the mixture is molded using a conventional method such as injection molding, extrusion molding, or compression molding while applying a magnetic field. It can be manufactured using either method.
  • pellets or powdered magnetic resin composite materials are heated and melted, and then subjected to injection molding, extrusion molding, and compression while applying a magnetic field as necessary.
  • One example is a method of molding.
  • kneading can also be carried out together with kneading.
  • injection molding is particularly useful because it yields a magnetic material-resin composite with excellent surface smoothness and magnetic properties.
  • the molding temperature is the same as the kneading temperature.
  • Molded products are usually further magnetized to improve their performance as permanent magnets. Magnetization is performed by a conventional method, such as an electromagnet that generates a static magnetic field or a capacitor magnetizer that generates a pulsed magnetic field.
  • the magnetic field strength at this time is preferably 15 kOe or more, more preferably 30 kOe or more.
  • Molded products made of magnetic resin composite materials are used for electromagnetic equipment, automotive electromagnetic equipment (motors, generators, etc.), toys, office equipment, audio equipment, etc., and their parts.
  • the relative viscosity of the polyamide resin is a value measured at 25° C. in accordance with JIS K 6920-2 by dissolving 1 g of the polyamide resin in 100 ml of 96% concentrated sulfuric acid.
  • the relative viscosity of the polyamide elastomer is a value measured at 25° C. in accordance with JIS K 6920-2 by dissolving 0.25 g of the polyamide elastomer in 50 ml of reagent grade m-cresol.
  • ⁇ MFR> The MFR (melt flow rate) of the polyamide resin composition was measured at 190° C. under a load of 1.00 kg in accordance with ISO 1133. From the obtained MFR measurement results, moldability was evaluated based on the following criteria. When the MFR is 12.0 g/10 minutes or more and less than 18.0 g/10 minutes, moldability is good. ⁇ : MFR is 12.0 g/10 minutes or more and less than 18.0 g/10 minutes. ⁇ : MFR is less than 12.0 g/10 minutes, or 18.0 g/10 minutes or more.
  • the polyamide elastomer had a relative viscosity of 1.94, a terminal amino group concentration of 22.8 ⁇ mol/g, and a Shore D hardness of 44.
  • Examples 1 to 4 Each component listed in Table 1 was blended in a blender for 10 minutes to obtain each blend composition. From each of the obtained blend compositions, test pieces used for the evaluation of the mechanical properties described above were prepared using a Sumitomo SG75 injection molding machine manufactured by Sumitomo Heavy Industries. The cylinder temperature of the injection molding machine was set at 230°C, and a test piece was produced. Table 1 shows the results of physical and mechanical property evaluation. In addition, the unit of the composition in Table 1 is mass %, and the whole polyamide resin composition is taken as 100 mass %.
  • the polyamide resin composition of the present invention has good moldability and impact resistance. From Comparative Example 1, impact resistance is poor if the aliphatic copolymerized polyamide resin (C) is not included. Comparative Examples 2 to 4 show that when an aromatic polyamide resin is included instead of the aliphatic copolymerized polyamide resin (C), the impact resistance is inferior, and as the amount of the aromatic polyamide resin increases, moldability also decreases. do. Comparative Example 5 shows that if the polyamide elastomer (A) and the aliphatic copolymer polyamide resin (C) are not included, the impact resistance is significantly inferior.
  • Comparative Example 6 moldability is poor if the aliphatic homopolyamide resin (B) and the aliphatic copolyamide resin (C) are not included. Comparative Examples 7 and 8 show that when the aliphatic homopolyamide resin (B) is not included and instead the aliphatic copolyamide resin (C) is included beyond the scope of the present invention, moldability is poor.
  • Example 5 Each polyamide resin and polyamide elastomer having the formulation shown in Table 2 were blended in a blender for 10 minutes to obtain each polyamide resin composition.
  • the polyamide resin composition and magnetic powder were stirred and mixed in a small Henschel mixer at the compounding ratio shown in Table 2, and then kneaded and extruded using a twin-screw extruder to produce pellets (magnetic material-resin composite material). The above evaluation was performed using the magnetic resin composite material.
  • the unit of composition in Table 2 is mass %
  • the content of the polyamide elastomer and polyamide resin is a value with the entire polyamide resin composition as 100 mass %
  • the content of the polyamide resin composition and magnetic powder is The amount is a value based on the total of the polyamide resin composition and magnetic powder as 100% by mass.
  • the magnetic resin composite material of the present invention has good strength and toughness. Comparative Example 9 shows that when the polyamide elastomer (A) and the aliphatic copolymer polyamide resin (C) are not included, the toughness is poor. Comparative Example 10 shows that the strength is poor when the aliphatic homopolyamide resin (B) is not included.
  • Polyamide elastomer (A) Polyamide elastomer produced in Production Example 1 (relative viscosity: 1.94, terminal amino group concentration: 22.8 ⁇ mol/g).
  • Aliphatic homopolyamide resin (B) Polyamide 12 (PA12): manufactured by UBE Corporation (relative viscosity: 1.63, terminal amino group concentration: 13.3 ⁇ mol/g).
  • Aliphatic copolymer polyamide resin (C) Polyamide 6/12 (PA6/12) PA6 25% by mass, PA12 75% by mass: manufactured by UBE Corporation (relative viscosity: 1.75, terminal amino group concentration: 13.6 ⁇ mol/g).
  • Aliphatic homopolyamide resin polyamide 6 (PA6) other than (B) manufactured by UBE Corporation (relative viscosity: 2.47).
  • Aromatic polyamide resin polyamide 6T/6I (PA6T/6I) manufactured by EMS-CHEMIE (Japan) Co., Ltd., product name "Grivory (registered trademark) G21").
  • Magnetic powder strontium ferrite manufactured by Kojundo Kagaku Kenkyusho Co., Ltd., density 5, average particle size 1 ⁇ m.

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Abstract

La présente invention concerne une composition de résine polyamide qui contient, pour 100 % en masse de la composition de résine polyamide, 10 % en masse à 50 % en masse d'un élastomère de polyamide (A), 40 % en masse à 75 % en masse d'une résine homopolyamide aliphatique (B) qui contient en moyenne plus de 6 atomes de carbone pour un groupe amide, et 0,5 % en masse à 30 % en masse d'une résine polyamide copolymérisée aliphatique (C), tout en étant sensiblement dépourvue de résines polyamides aromatiques. La présente invention concerne également un matériau composite de résine de matériau magnétique qui contient une composition de résine polyamide (X) et une poudre magnétique (Y), dans lequel : 5,0 % en masse à 30,0 % en masse de la composition de résine polyamide (X), et 70,0 % en masse à 95,0 % en masse de la poudre magnétique (Y) sont présents dans un total de 100 % en masse de la composition de résine de polyamide (X) et de la poudre magnétique (Y) ; et 10 % en masse à 50 % en masse d'un élastomère de polyamide (A), 40 % en masse à 75 % en masse d'une résine d'homopolyamide aliphatique (B) qui contient en moyenne plus de 6 atomes de carbone pour un groupe amide, 0,5 % en masse à 30 % en masse d'une résine polyamide copolymérisée aliphatique (C), et aucune résine polyamide aromatique pour 100 % en masse de la composition de résine polyamide (X).
PCT/JP2023/004979 2022-03-23 2023-02-14 Composition de résine polyamide, matériau composite de résine de matériau magnétique et article moulé correspondant WO2023181711A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH115898A (ja) * 1997-06-19 1999-01-12 Toray Ind Inc 振動溶着用樹脂組成物
WO2008123450A1 (fr) * 2007-03-30 2008-10-16 Ube Industries, Ltd. Composition de résine et article moulé
JP2010222394A (ja) * 2009-03-19 2010-10-07 Ube Ind Ltd 磁性材樹脂複合体成形用ポリアミド樹脂組成物、磁性材樹脂複合材料、及び磁性材樹脂複合体
JP2020200555A (ja) * 2019-06-11 2020-12-17 住友精化株式会社 繊維加工用樹脂組成物
JP2021113274A (ja) * 2020-01-17 2021-08-05 ダイセル・エボニック株式会社 硬化性樹脂組成物およびその用途ならびにそれらの製造方法
WO2022075180A1 (fr) * 2020-10-05 2022-04-14 宇部興産株式会社 Composition de résine de polyamide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH115898A (ja) * 1997-06-19 1999-01-12 Toray Ind Inc 振動溶着用樹脂組成物
WO2008123450A1 (fr) * 2007-03-30 2008-10-16 Ube Industries, Ltd. Composition de résine et article moulé
JP2010222394A (ja) * 2009-03-19 2010-10-07 Ube Ind Ltd 磁性材樹脂複合体成形用ポリアミド樹脂組成物、磁性材樹脂複合材料、及び磁性材樹脂複合体
JP2020200555A (ja) * 2019-06-11 2020-12-17 住友精化株式会社 繊維加工用樹脂組成物
JP2021113274A (ja) * 2020-01-17 2021-08-05 ダイセル・エボニック株式会社 硬化性樹脂組成物およびその用途ならびにそれらの製造方法
WO2022075180A1 (fr) * 2020-10-05 2022-04-14 宇部興産株式会社 Composition de résine de polyamide

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