Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • 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 polyamide resin composition in which a polyamide resin is blended with a polyamide resin has been reported for the purpose of improving the flexibility and impact resistance of the polyamide resin (see Patent Document 1).
• Magnetic resin composite materials are widely used in OA equipment, motors, actuators, sensors, etc.
• the magnetic material resin composite material is required to have excellent magnetic properties, and for that purpose, it is required that the magnetic powder is well dispersed even if a large amount of the magnetic powder is blended.
• the magnetic material resin composite material is required to have mechanical properties and other physical properties.
• a magnetic resin composite material containing a magnetic powder, a polyamide resin, and an epoxy compound is known in order to achieve both moldability and mechanical properties of the magnetic resin composite material (see Patent Document 3).
• a magnetic material resin composite material containing a magnetic powder and an aromatic polyamide resin is known (see Patent Document 4).
• the reaction between the amino group of the polyamide resin and the epoxy group of the epoxy resin may generate a rigid and inflexible composite resin, which may be combined with the terminal carboxyl group of the polyamide resin. It was necessary to set the ratio with the terminal amino group to a specific range.
• the magnetic material resin composite material of Patent Document 4 has poor flexibility. Further toughness was required for the polyamide resin composition of Patent Document 1 and the magnetic material resin composite material of Patent Document 2.
• An object of the present invention is to provide a polyamide resin composition which has good molding processability, is tough, has flexibility, and can obtain a molded product having excellent impact resistance.
• the present invention is, for example, the following [1] to [8].
• [1] In 100% by mass of the polyamide resin composition, 15 to 35% by mass of the polyamide-based elastomer (A) and 40 to 79% by mass of the aliphatic polyamide resin (B) having an average carbon atom number of more than 6 per amide group.
• [2] The polyamide resin composition of [1], wherein the polyamide-based elastomer (A) has a polyether structure.
• the polyamide-based elastomer (A) is 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), according to the following formula (3).
• 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. ] [However, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20. ] [However, R 3 represents a linking group containing a hydrocarbon chain, and m is 0 or 1.
• [6] A molded product of the polyamide resin composition according to any one of [1] to [5].
• [7] A magnetic resin composite material containing the polyamide resin composition according to any one of [1] to [5] and a magnetic powder.
• [8] A molded product of the magnetic resin composite material of [7].
• the polyamide resin composition of the present invention has good molding processability, and can obtain a molded product that is tough, flexible, and has excellent impact resistance.
• the polyamide resin composition in 100% by mass of the polyamide resin composition, 15 to 35% by mass of the polyamide-based elastomer (A) and 40 to 79% by mass of the aliphatic polyamide resin (B) having an average carbon atom number of more than 6 per amide group. %, 0.1 to 35% by mass of the aromatic polyamide resin (C), and 0 to 10% by mass of the aliphatic polyamide resin (D) having an average carbon atom number of 6 or less per amide group. ..
• the polyamide resin composition contains a polyamide-based elastomer (A). Since the polyamide resin composition contains the polyamide-based elastomer (A), the molded product exhibits excellent flexibility.
• the polyamide-based elastomer (A) has a hard segment and a soft segment, and the hard segment has a polyamide structure.
• the soft segment of the polyamide-based elastomer preferably has a polyether structure, and more preferably has a structural unit derived from a polyether diamine compound.
• Examples of the polyamide-based 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 by an ester bond, and a polyether polyamide elastomer in which a hard segment and a soft segment are bonded by an amide bond. From the viewpoint of exhibiting the effect of the present invention, excellent in hydrolysis resistance, and from the viewpoint of stability, a polyether polyamide elastomer in which a hard segment and a soft segment are bonded by an amide bond is preferable.
• the polyamide structure in the hard segment is at least one selected from the group consisting of a nylon salt composed of a diamine and a dicarboxylic acid, an aminocarboxylic acid compound represented by the following formula (1), and a lactam compound represented by the following formula (2).
• a polycondensate having a structural unit derived from the seed polyamide-forming monomer is preferred.
• R 1 represents a linking group containing a hydrocarbon chain.
• R 2 represents a linking group containing a hydrocarbon chain.
• R 1 is preferably a divalent hydrocarbon group containing an aliphatic group having 2 to 20 carbon atoms, an alicyclic group and / or an aromatic group, and more preferably a carbon number.
• aminocarboxylic acid compound (1) examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like having 5 to 20 carbon atoms.
• the aliphatic ⁇ -aminocarboxylic acid of the above can be mentioned.
• R 2 is preferably a divalent hydrocarbon group containing an aliphatic group having 3 to 20 carbon atoms, an alicyclic group and / or an aromatic group, and more preferably having 3 carbon atoms.
• lactam compound (2) examples include aliphatic lactams having 4 to 20 carbon atoms such as ⁇ -caprolactam, ⁇ -enantractam, ⁇ -undecalactam, ⁇ -lauryl lactam, and 2-pyrrolidone.
• ⁇ -lauric lactam, 11-aminoundecanoic acid or 12-aminododecanoic acid are preferable from the viewpoint of dimensional stability due to low water absorption, chemical resistance, and mechanical properties.
• diamines in the nylon salt examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2.
• Diamines such as aliphatic diamines having 2 to 20 carbon atoms such as 4-trimethylhexane-1,6-diamine, 2,4,4-trimethylhexane-1,6-diamine, 3-methylpentane-1,5-diamine Examples include compounds.
• dicarboxylic acid in the nylon salt at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or a derivative thereof can be used.
• dicarboxylic acid examples include linear aliphatic dicarboxylic acids having 2 to 25 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
• an aliphatic dicarboxylic acid such as a dimerized aliphatic dicarboxylic acid (dimeric acid) having 14 to 48 carbon atoms obtained by distilling an unsaturated fatty acid obtained by distilling triglyceride and a hydrogenated product thereof (hydrogenated dicarboxylic acid).
• the hard segment can also be derived from a polyamide having a carboxyl group at both terminal groups, in which case the hard segment is selected from the group consisting of a polyamide structure and an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid and an aromatic dicarboxylic acid. It is also a segment containing a structural unit derived from at least one dicarboxylic acid (4).
• R 3 represents a linking group containing a hydrocarbon chain, and m is 0 or 1.
• dicarboxylic acid compound (4) at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or a derivative thereof can be used.
• R 3 is preferably a divalent hydrocarbon group containing an aliphatic group having 1 to 20 carbon atoms, an alicyclic group group and / or an aromatic group, and more preferably 1 carbon atom.
• the hydrocarbon group having up to 15 carbon atoms more preferably the hydrocarbon group having 2 to 12 carbon atoms, still more preferably the hydrocarbon group having 4 to 10 carbon atoms, and particularly preferably 4 to 10 carbon atoms.
• It is an alkylene group of 10.
• Specific examples of the dicarboxylic acid compound represented by the above formula (4) include a compound exemplified as a dicarboxylic acid compound of a nylon salt composed of a diamine compound and a dicarboxylic acid compound.
• the above-mentioned polyamide-forming monomer can be obtained by ring-opening polymerization or polycondensation by a conventional method to obtain a polyamide having carboxyl groups at both ends.
• the hard segment dicarboxylic acid can be used as a molecular weight modifier.
• the number average molecular weight of the hard segment is preferably 300 to 15,000, and more preferably 300 to 6000 from the viewpoint of flexibility and moldability.
• the number average molecular weight is a value obtained by gel permeation chromatography.
• the soft segment preferably has a polyether structure, and the constituent unit of the polyether structure is preferably an 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, and is preferably an ethylene group, an n-propylene group, an i-propylene group, a 1-methylethylene group, or a 2-methylethylene group. , N-butylene group, 1-methylpropylene group, 2-methylpropylene group, dimethylethylene group, ethylethylene group and the like.
• the structural unit of the polyether structure may be one kind alone or two or more kinds, but two or more kinds are preferable.
• soft segment's polyether structure 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 have a structure represented by the following chemical formula. (In the formula, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and 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, further preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12.
• y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, further preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.
• a polyether diamine compound can be obtained by reacting the ends of these polyethers with ammonia or the like.
• the number average molecular weight of the soft segment is preferably 200 to 6000, more preferably 650 to 2000.
• the XYX type triblock polyether diamine compound is represented by, for example, the following 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, further preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12.
• y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, further preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.
• each combination of the hard segment and the soft segment mentioned above can be mentioned.
• the hard segment / soft segment (mass ratio) is more preferably 95/5 to 25/75.
• the ratio (mass ratio) between the hard segment and 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 and the soft segment of the obtained polyamide elastomer is equal to the value calculated based on the blending amount of the monomer components constituting each segment.
• the hard segment / soft segment (mass ratio) is smaller than the above range, the crystallinity of the polyamide component may be lowered, and the mechanical properties such as strength and elastic modulus may be lowered, which may not be preferable.
• the hard segment / soft segment (mass ratio) is larger than the above range, it may not be preferable because the function and performance as an elastomer such as rubber elasticity and flexibility are difficult to be exhibited.
• polyamide-based elastomers include, for example, the product name "Dyamide (registered trademark)” series manufactured by Daicel Ebonic, the product name “Pebax” series manufactured by ARKEMA, and the product name "Grill” manufactured by MSMEM Japan. Examples include “Flex (registered trademark) EBG”, “Grillflex (registered trademark) ELG”, “Grillon (registered trademark) ELX”, and Ube Kosan Co., Ltd. trade name "UBESTA XPA (registered trademark)” series.
• the product name "UBESTA XPA (registered trademark)" series manufactured by Ube Kosan Co., Ltd. is preferable from the viewpoint of exhibiting the effect of the present invention and excellent in hydrolysis resistance.
• the polyamide elastomer (A) may be used alone or in combination of two or more.
• the degree of polymerization of the polyamide-based elastomer (A) is not particularly limited, but in accordance with JIS K6920-2, 0.25 g of the polyamide-based elastomer was dissolved in 50 ml of m-cresol, which is a special reagent product, and measured at 25 ° C.
• the relative viscosity is preferably 1.10 to 5.00, more preferably 1.50 to 4.50, and particularly preferably 1.50 to 3.00.
• the hardness (shore D) of the polyamide-based 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 to 70.
• a preferred embodiment of the polyamide-based elastomer (A) is a structural unit derived from an aminocarboxylic acid compound represented by the above formula (1) and / or a lactam compound represented by the above formula (2), represented by the above formula (3). It is a polymer containing the structural unit derived from the XYX type triblock polyether diamine compound and the structural unit derived from the dicarboxylic acid compound represented by the above formula (4).
• a method for producing the polyamide-based elastomer (A) in a preferred embodiment consisting of a step of melt-polymerizing a polyamide-forming monomer, an XYX-type triblock polyetherdiamine, and a dicarboxylic acid under pressure and / or normal pressure, and further melt-polymerizing under reduced pressure, if necessary, can be used.
• a method comprising the steps of simultaneously melt-polymerizing the three components of a polyamide-forming monomer, an XYX-type triblock polyetherdiamine, and a dicarboxylic acid under pressure and / or normal pressure, and further melt-polymerizing under reduced pressure as necessary. Can be used.
• a method of first polymerizing the two components of the polyamide-forming monomer and the dicarboxylic acid and then polymerizing the XYX-type triblock polyether diamine can also be used.
• a similar production method can be mentioned for a polyamide elastomer having a polyether structural unit derived from polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol or the like as a soft segment.
• the polyamide elastomer can be produced at a polymerization temperature of preferably 150 to 300 ° C, more preferably 160 to 280 ° C, and particularly preferably 180 to 250 ° C.
• a polymerization temperature preferably 150 to 300 ° C, more preferably 160 to 280 ° C, and particularly preferably 180 to 250 ° C.
• the polyamide elastomer can be produced by a method consisting of a normal pressure melt polymerization or a normal pressure melt polymerization followed by a vacuum melt polymerization step.
• a lactam compound or a compound synthesized from a diamine compound and a dicarboxylic acid compound and / or a salt thereof is used as the polyamide-forming monomer
• an appropriate amount of water is allowed to coexist and the pressure is 0.1 to 5 MPa. It can be produced by a method consisting of the melt polymerization of the above, followed by the atmospheric melt polymerization and / or the vacuum melt polymerization.
• the 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 long, coloring due to thermal decomposition or the like is likely to occur, and in either case, a polyetheramide elastomer having desired physical properties may not be obtained.
• the production of the polyamide elastomer can be carried out by a batch type or a continuous type, and a batch type reaction kettle, a single-tank or multi-tank continuous reaction device, a tubular continuous reaction device, or the like is used alone or in combination as appropriate. be able to.
• monoamines such as laurylamine, stearylamine, hexamethylenediamine, and methoxylylenediamine, and diamines, acetic acids, and benzoic acids are used to adjust the molecular weight and stabilize the melt viscosity during molding, if necessary.
• Monocarboxylic acid such as stearic acid, adipic acid, sebacic acid, dodecanedioic acid, dicarboxylic acid and the like can be added. It is preferable to appropriately add these amounts so that the relative viscosity of the finally obtained elastomer is in the range of 1.10 to 5.00.
• the amount of the above monoamine and diamine, monocarboxylic acid, dicarboxylic acid and the like added is preferably in a range that does not impair the characteristics of the obtained polyamide elastomer.
• phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are used as catalysts as necessary, and phosphorous acid, hypophosphorous acid, and these are used for the effects of both catalysts and heat resistant agents.
• Inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts can be added. The addition amount is usually 50 to 3000 ppm with respect to the charged raw material.
• the content of the polyamide-based elastomer (A) in 100% by mass of the polyamide resin composition is 15 to 35% by mass, preferably 15 to 30% by mass, and more preferably 20 to 30% by mass.
• the content of the polyamide-based elastomer (A) is within the above range, a molded product having both flexibility and toughness and excellent impact resistance can be obtained.
• the polyamide resin composition contains an aliphatic polyamide resin (B) having an average carbon atom number of more than 6 per amide group (hereinafter, also referred to as “aliphatic polyamide resin (B)”).
• aliphatic polyamide resin (B) When the polyamide resin composition contains the aliphatic polyamide resin (B) having an average carbon atom number of more than 6 per amide group, it becomes easy to improve the molding processability, and the flexibility and mechanical properties of the molded product are easily improved. It becomes easy to improve. Further, since the polyamide resin has low water absorption, it is superior in hydrolysis resistance to other thermoplastic resins.
• the aliphatic polyamide resin examples include an aliphatic homopolyamide resin and an aliphatic copolymerized polyamide resin.
• the aliphatic homopolyamide resin is a polyamide resin composed of one kind of constituent unit derived from an aliphatic monomer.
• the aliphatic homopolyamide resin may be composed of at least one of one kind of lactam and aminocarboxylic acid which is a hydrolyzate of the lactam, and is composed of a combination of one kind of diamine and one kind of dicarboxylic acid. It may be a thing.
• the aliphatic copolymerized polyamide resin is a polyamide resin composed of two or more kinds of constituent units derived from an aliphatic monomer.
• the aliphatic copolymerized polyamide resin is two or more copolymers selected from the group consisting of a combination of diamine and dicarboxylic acid, lactam and aminocarboxylic acid.
• the combination of diamine and dicarboxylic acid is regarded as one kind of monomer by the combination of one kind of diamine and one kind of dicarboxylic acid.
• An aliphatic homopolyamide resin having an average number of carbon atoms per amide group of more than 6 means that when the constituent units are lactam and aminocarboxylic acid, the number of carbon atoms in the hydrocarbon chain of the constituent units exceeds 6. To say.
• the constituent unit is a combination of diamine and dicarboxylic acid, the value obtained by multiplying the number of carbon atoms of the diamine hydrocarbon chain by the molar concentration of diamine in the polyamide and the number of carbon atoms of the diamine hydrocarbon chain in the polyamide It means that the sum with the value obtained by multiplying the molar concentration of the dicarboxylic acid of is more than 6.
• polytetramethylene sebacamide (polyamide 410) is an aliphatic homopolyamide resin having an average carbon atom number of more than 6 per amide group when tetramethylenediamine is less than 67 mol% in polyamide. Further, if it is 67 mol% or more, it is an aliphatic homopolyamide resin having an average carbon atom number of 6 or less with respect to one amide group described later.
• the number of carbon atoms per amide group of each constituent unit constituting the copolymer is obtained as described above, and the copolymer weight is obtained. It means that the average number of carbon atoms in the copolymer, which is the product of the molar concentration of each structural unit in the coalescence and the number of carbon atoms for one amide group of each structural unit, exceeds 6.
• Polyundecane lactam (polyamide 11), polylauryl lactam (polyamide 12), polytetramethylene dodecamide (polyamide 412), and polypentamethylene are examples of aliphatic homopolyamide resins having an average carbon atom number of more than 6 per amide group.
• Azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene sveramide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexa Methylene sebacamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), polyhexamethylene dodecamide (polyamide 612), polyhexamethylenetetradecamide (polyamide 614), polyhexamethylene hexadecamide (polyamide 616).
• Polyhexamethylene octadecamide polyamide 618
• polynonamethylene adipamide polyamide 96
• polynonamethylene sveramide polyamide 98
• polynonamethylene azelamide polyamide 99
• polynonamethylene sebacamide Polyamide 910
• Polynonamethylene dodecamide Polyamide 912
• Polydecamethylene adipamide Polyamide 106
• Polydecamethylene sveramide Polyamide 108
• Polydecamethylene azelamide Polyamide 109
• Polydecamethylene se Polydecamethylene se.
• aliphatic copolymerized polyamide resin having an average carbon atom number of more than 6 for one amide group a raw material monomer for forming an aliphatic homopolypolymer resin having an average carbon atom number of more than 6 for one amide group is used.
• a raw material monomer for forming an aliphatic homopolypolymer resin having an average carbon atom number of more than 6 for one amide group is used.
• caprolactam / hexamethylene diaminoazeline acid copolymer polyamide 6/69
• caprolactam / hexamethylene diaminosevacinic acid copolymer polyamide 6/610
• caprolactam / hexamethylene diaminoundecane caprolactam / hexamethylene diaminoundecane.
• Dicarboxylic acid copolymer (polyamide 6/611), caprolactam / hexamethylene diaminododecanedicarboxylic acid copolymer (polyamide 6/612), caprolactam / aminoundecanoic acid copolymer (polyamide 6/11), caprolactam / lauryllactam Polymer (Polymer 6/12), Caprolactam / Hexamethylene diaminoadipic acid / Lauryl lactam copolymer (Polymer 6/66/12), Caprolactum / Hexamethylene diaminoadipic acid / Hexamethylene diaminosevacinic acid copolymer (Polymer 6) / 66/610), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminododecanedicanoic acid copolymer (polyamide 6/66/612) and the like can be mentioned.
• the aliphatic polyamide resin (B) preferably has an average carbon atom number of 8 to 12 per amide group, and more preferably 10 to 12. It is particularly preferably at least one selected from the group consisting of polyamide 11, polyamide 12, polyamide 612, polyamide 611, polyamide 610, polyamide 6/12 copolymer and polyamide 6/66/12 copolymer.
• the degree of polymerization of the aliphatic polyamide resin (B) is not particularly limited, but in accordance with JIS K6933, 1 g of the polyamide resin is dissolved in 100 ml of 96% concentrated sulfuric acid, and the relative viscosity measured at 25 ° C. is 1.10. It is preferably ⁇ 5.00, more preferably 1.50 to 4.50, and particularly preferably 1.50 to 3.00.
• the content of the aliphatic polyamide resin (B) having an average carbon atom number of more than 6 per amide group in 100% by mass of the polyamide resin composition is 40 to 79% by mass, preferably 45 to 77% by mass. , 50-75% by mass is more preferable.
• the content of the aliphatic polyamide resin (B) is within the above range, a molded product having both flexibility and toughness and excellent impact resistance can be obtained.
• the polyamide resin composition contains an aromatic polyamide resin (C).
• the aromatic polyamide resin is an aromatic polyamide resin containing at least one aromatic monomer component, and is, for example, an aliphatic dicarboxylic acid and an aromatic diamine, an aromatic dicarboxylic acid and an aliphatic diamine, or an aromatic diamine and an aromatic. It is a polyamide resin obtained by polycondensation of dicarboxylic acid as a raw material.
• Examples of the aliphatic diamine and the aliphatic dicarboxylic acid as raw materials include those similar to those exemplified in the above description of the aliphatic copolymerized polyamide resin.
• Examples of the aromatic diamine include methoxylylenediamine and paraxylylenediamine
• examples of the aromatic dicarboxylic acid include naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and phthalic acid. These aromatic diamines and aromatic dicarboxylic acids may be used alone or in combination of two or more.
• polyamide 9T polynonane methylene terephthalamide
• polyoxide 6T polyhexamethylene terephthalamide
• polyhexamethylene isophthalamide polyamide 6I
• polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer examples include polynonane methylene terephthalamide (polyamide 9T), polyhexamethylene terephthalamide (polyoxide 6T), polyhexamethylene isophthalamide (polyamide 6I), and polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer.
• an aromatic copolymerized polyamide containing at least two monomer components is preferable, and a semi-aromatic polyamide obtained by copolymerizing one or more aromatic monomer components and one or more aliphatic monomer components.
• Polyamide is more preferable, and polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I) and polyxylylene adipamide (polyamide MXD6) are further preferable.
• aromatic polyamide resin (C) particularly useful ones include an amorphous partially aromatic copolymerized polyamide resin containing at least two aromatic monomer components.
• the amorphous partially aromatic copolymerized polyamide resin an amorphous polyamide having a glass transition temperature of 100 ° C. or higher obtained by the peak temperature of the loss elastic modulus at the time of absolute drying obtained by measuring the dynamic viscoelasticity is used. preferable.
• the amorphous partially aromatic copolymerized polyamide resin include polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I).
• amorphous means that the amount of heat of crystal melting measured by a differential scanning calorimeter (DSC) is 1 cal / g or less.
• the degree of polymerization of the aromatic polyamide resin (C) is not particularly limited, but in accordance with JIS K6933, 1 g of the polyamide resin is dissolved in 100 ml of m-cresol, which is a special reagent product, and the relative viscosity measured at 25 ° C. is determined. It is preferably 1.50 to 4.00, more preferably 1.80 to 2.50.
• the content of the aromatic polyamide resin (C) in 100% by mass of the polyamide resin composition is 0.1 to 35% by mass, preferably 0.1 to 33% by mass, and more preferably 0.2 to 30% by mass. ..
• the content of the aromatic polyamide resin (C) is in the above range, the flexibility is not impaired and the impact resistance is excellent.
• the polyamide resin composition may optionally contain an aliphatic polyamide resin (D) having an average carbon atom number of 6 or less per amide group (hereinafter, also referred to as “aliphatic polyamide resin (D)”). preferable.
• the aromatic polyamide (C) can be easily blended, and molding processability is possible. It is preferable from the viewpoint of.
• Examples of the aliphatic polyamide resin (D) having an average carbon atom number of 6 or less per amide group include polycaprolactum (polyamide 6), polyethylene adipamide (polyamide 26), and polytetramethylene succinamide (polyamide 44). , Polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene sveramide (polyamide 48), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 54).
• polyamide 55 polypentamethylene adipamide (polyamide 56), polyhexamethylene adipamide (polyamide 66), caprolactam / hexamethylene diaminoadipic acid copolymer (polyamide 6/66).
• polyamide 6 is preferable from the viewpoint of compatibility with the aromatic polyamide resin (C).
• the degree of polymerization of the aliphatic polyamide resin (D) is not particularly limited, but in accordance with JIS K6933, 1 g of the polyamide resin is dissolved in 100 ml of 96% concentrated sulfuric acid, and the relative viscosity measured at 25 ° C. is 1.10. It is preferably 5.00 to 5.00, and more preferably 1.50 to 4.20.
• the content of the aliphatic polyamide resin (D) having an average carbon atom number of 6 or less per amide group in 100% by mass of the polyamide resin composition is 0 to 10% by mass.
• the content of the aliphatic polyamide resin (D) is in the above range, the flexibility is good and the aromatic polyamide resin (C) can be easily blended.
• Polyamide resin manufacturing equipment includes batch type reaction kettles, single-tank or multi-tank continuous reaction equipment, tubular continuous reaction equipment, uniaxial kneading extruders, kneading reaction extruders such as twin-screw kneading extruders, etc.
• a known polyamide production apparatus can be mentioned.
• As a polymerization method a known method such as melt polymerization, solution polymerization or 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 is preferably 30 ⁇ mol / g or more, and is in the range of 30 ⁇ mol / g or more and 110 ⁇ mol / g or less, as the terminal amino group concentration obtained by neutralization titration by dissolving in a mixed solvent of phenol and methanol. Is more preferable, and a range of 30 ⁇ mol / g or more and 70 ⁇ mol / g or less is further preferable. Within the above range, the molding processability of the polyamide resin composition is good.
• the terminal amino group concentration in the polyamide resin is preferably measured by the above neutralization pruning, but the terminal amino of each polyamide resin is preferable.
• the base concentration and the mixing ratio thereof are known, the average value calculated by multiplying the respective terminal amino group concentrations by the mixing ratio may be used as the terminal amino group concentration of the polyamide resin.
• the polyamide resin composition may contain a thermoplastic resin other than the polyamide elastomer and the polyamide resin as long as the object of the present invention is not impaired.
• the thermoplastic resin other than the polyamide-based elastomer and the 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 is a dye, a pigment, a fibrous reinforcing material, a particulate reinforcing material, a plasticizer, an antioxidant, a heat resistant agent, a foaming agent, and a weather resistant agent other than the above-mentioned components, as long as the object of the present invention is not impaired.
• a crystal nucleating agent, a crystallization accelerator, a mold release agent, a lubricant, an antistatic agent, a flame retardant, a flame retardant aid, a functionalizing agent such as a colorant, and the like may be appropriately contained.
• the content of the arbitrary component is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass in 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 for mixing the raw materials of each component.
• a method of simply mixing the raw materials of each component with a commonly known mixer such as a tumbler mixer or a blender can also be applied.
• a method of blending all raw materials and then melt-kneading a method of blending some raw materials, then melt-kneading, and then blending the remaining raw materials and melt-kneading, or one. Any method may be used, such as a method of mixing the remaining raw materials using a side feeder after blending the raw materials of the portion, but a method of blending all the raw materials and then melt-kneading is preferable.
• the MFR Melt flow rate measured at a temperature of 190 ° C. and a load of 1.00 kg is preferably less than 15 g / 10 minutes, preferably 4 g / 10 minutes or more and less than 15 g / 10 minutes. More preferably, it is 7 g / 10 minutes or more and less than 15 g / 10 minutes.
• the MFR is in this range, the moldability of the polyamide resin is good, but the toughness of the obtained molded product is not impaired.
• the density of the polyamide resin composition is preferably 1.02 g / cm 3 or more, more preferably 1.03 to 1.10 g / cm 3 , and even more preferably 1.03 to 1.06 g / cm 3 . When the density is in this range, various inorganic additives such as magnetic powder tend to be easily uniformly dispersed.
• the density of the polyamide resin composition is obtained by multiplying the density of each component by the content (% by mass) to obtain the sum of them. The density of each component was measured according to ISO1183-3.
• the polyamide resin composition can maintain flexibility in a wide temperature range. It is expected that the generation of cracks due to stress concentration due to dimensional changes can be suppressed.
• the polyamide resin composition can be suitably used for manufacturing an injection molded product by injection molding, an extrusion molded product by extrusion molding, a blow molded product by blow molding, and a rotation molded product by rotation molding. Since the polyamide resin composition has good injection moldability, it can be more preferably used as an injection molded product by injection molding.
• the method for producing an injection-molded product by injection molding from the polyamide resin composition is not particularly limited, and a known method can be used.
• the method for producing an extruded product from the polyamide resin composition by extrusion molding is not particularly limited, and a known method can be used.
• the method for producing a blow-molded product from the polyamide resin composition by blow molding is not particularly limited, and a known method can be used.
• the method for producing a rotary molded product by rotary molding from the polyamide resin composition is not particularly limited, and a known method can be used.
• a known method can be used.
• the method described in International Publication No. 2019/054109 is referred to.
• the injection molded product by injection molding, the extrusion molded product by extrusion molding, the blow molded product by blow molding, and the rotary molded product by rotary molding are not particularly limited, but are not particularly limited, but are spoilers, air intake ducts, intake manifolds, resonators, fuel tanks, and the like.
• Electric parts such as gas tanks, hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, other automobile parts such as hoses, tubes and tanks, electric tool housings, mechanical parts such as pipes, tanks, tubes, hoses, films, etc. -Various uses such as electronic parts, household / office supplies, building material-related parts, furniture parts, etc. are preferably mentioned. It was
• the polyamide resin composition has excellent gas barrier properties, it is suitably used for molded products that come into contact with high-pressure gas, for example, tanks, tubes, hoses, films, etc. that come into contact with high-pressure gas.
• the type of the gas is not particularly limited, and examples thereof include hydrogen, nitrogen, oxygen, helium, methane, butane, and propane. Gases having a small polarity are preferable, and hydrogen, nitrogen, and methane are particularly preferable.
• the polyamide resin composition can be used as a magnetic material resin composite material by blending with the magnetic powder.
• the magnetic powder is not particularly limited as long as it is a known magnetic powder that has a function of imparting magnetism and can be used for plastic magnets.
• ferrite-based magnetic powder alnico-based magnetic powder, rare earth magnetic powder, etc.
• examples of the ferrite-based magnetic powder include barium-ferrium-based magnetic powder such as iron oxide and barium carbonate, and strontium-based magnetic powder such as iron oxide and strontium carbonate.
• alnico-based magnetic powder examples include alnico made of nickel, aluminum, cobalt, and copper, 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 and the like, neodium-iron-boron magnets and the like. These can be used alone or in combination of two or more.
• the average particle size of the magnetic powder is 0. It is preferably 1 to 300 ⁇ m, more preferably 0.1 to 200 ⁇ m, and 0. It is more preferably 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 body may decrease.
• the blending amount of the magnetic powder is preferably 50 to 98% by mass, more preferably 65 to 97% by mass, and further preferably 70 to 95% by mass with respect to the entire magnetic material resin composite material. preferable.
• the blending amount is less than the above value, the residual magnetic flux density is low, the practicality as a permanent magnet application is small, and the effect on the flow characteristics of the resin may be small.
• the magnetic field orientation is inferior, the residual magnetic flux density is not improved due to the decrease in the resin component, and the amount of resin is small, so that the fluidity is inferior. It may cause troubles such as defects and lack practicality.
• the magnetic powder may be treated in advance with a coupling agent or a surface modifier in order to improve the dispersibility or adhesion when blended in the polyamide resin composition.
• a coupling agent or surface modifier conventional coupling agents or surface modifiers such as silane-based, titanate-based, aluminum-based, phosphite ester and other organic phosphorus compound-based, chromium-based, and methacrylate-based agents can be used. ..
• the optimum type of these is appropriately selected depending on the type of resin used as the binder. Among these, amino group-containing silane-based compounds and titanate-based compounds are more preferable in order to enhance compatibility with polyamide resins.
• a lubricant, a stabilizer, or the like as an additive to improve the fluidity, molding processability, and magnetic properties of the magnetic resin composite material.
• the magnetic resin composite material is a dye, a pigment, a fibrous reinforcing material, a particulate reinforcing material, a plasticizer, an antioxidant, a heat resistant agent, a foaming agent, and a weather resistant material other than the above-mentioned components, as long as the object of the present invention is not impaired. It may appropriately contain a functionalizing agent such as an agent, 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, and a coloring agent.
• a functionalizing agent such as an agent, 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, and a coloring agent.
• the magnetic material resin composite material is produced by mixing a polyamide resin composition and a magnetic powder in a mixing step, and further through a kneading step. Further, each component of the polyamide resin composition and the magnetic powder are directly mixed by a mixing step, and further manufactured through a kneading step. In the mixing step, the magnetic powder, each component of the polyamide resin composition or the polyamide resin composition, and various additives, if necessary, are mixed and mixed by a known method. The mixing step is preferably performed before the kneading step described later.
• 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, and a tumbler. Further, it is also effective to add and grind and mix using a rotary ball mill, a vibrating ball mill, a planetary ball mill, a wet mill, a jet mill, a hammer mill, a cutter mill and the like.
• the shape of the polyamide resin composition for molding the magnetic resin composite may be any of pellets, beads, powder, paste, etc., but a fine particle size is desirable in order to improve the homogeneity of the mixture.
• a mixed magnetic powder, a polyamide resin composition and any various additives are used, or a mixed magnetic powder, each component of the polyamide resin composition and any various additives are used in a batch kneader such as a brabender.
• This is a step of kneading in a temperature range of 50 to 400 ° C. using a Banbury mixer, a Henshell mixer, a helical rotor, a roll, a single-screw extruder, a twin-screw extruder, or the like.
• the kneading temperature is generally selected from a temperature range in which the polyamide resin melts and does not decompose.
• the kneaded product is extruded into a strand or sheet and then cut, hot-cut, underwater-cut, or a block-shaped material that has been cooled and solidified is crushed into pellets or powder. To. In this way, a magnetic material resin composite material can be obtained.
• a molding process of further performing a molding process is performed.
• a one-step molding method in which the mixture is melt-kneaded and molded into a desired shape as it is, and a two-step molding in which a molding step is performed by a conventional method such as injection molding, extrusion molding, or compression molding while applying a magnetic field after the kneading step. It can be manufactured by either method.
• a pellet or powdery magnetic material resin composite material is heated and melted, and injection molding, extrusion molding, and compression are performed while applying a magnetic field as necessary.
• a method of molding can be mentioned.
• extrusion molding it can also be performed together with kneading.
• the injection molding method is particularly useful because it can obtain a magnetic material resin composite having 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 method usually performed, for example, an electromagnet that generates a static magnetic field, a condenser magnetizer that generates a pulse magnetic field, or the like.
• the magnetic field strength at this time is preferably 15 kOe or more, and more preferably 30 kOe or more.
• Molded products of magnetic resin composite materials are used for electromagnetic equipment, in-vehicle electromagnetic equipment (motors, generators, etc.), toys, office equipment, audio equipment, etc.
• the measured values of the examples are the values measured by the following measuring methods. ⁇ Density> The density of each component is multiplied by the content (% by mass) to obtain the sum of them. The density of each component was measured according to ISO1183-3.
• ⁇ MFR> The MFR (melt flow rate) of the polyamide resin composition was measured at 190 ° C. with a load of 1.00 kg in accordance with ISO 1133. From the obtained MFR measurement results, the molding processability was evaluated according to the following criteria. ⁇ : MFR is 7 g / 10 minutes or more and less than 15 g / 10 minutes. ⁇ : MFR is 4 g / 10 minutes or more and less than 7 g / 10 minutes. X: MFR is less than 4 g / 10 minutes or 15 g / 10 minutes or more.
• Toughness ⁇ Tensile yield stress, tensile yield strain, tensile fracture nominal strain and tensile modulus> Tensile yield stress and tensile of test piece (test piece size: 10 x 170 x 4 mm) using Shimadzu automatic extensometer AGX-AT / SIE-560SA according to ISO527-2 / 1A / 50. Yield strain was measured at 23 ° C., relative humidity 50% RH, and test speed 50 mm / min. From the measurement results of the obtained tensile yield stress, the toughness was evaluated according to the following criteria. ⁇ : Tension yield stress is 35 MPa or more. ⁇ : The tensile yield stress is 32 MPa or more and less than 35 MPa.
• X The tensile yield stress is less than 32 MPa. From the measurement results of the obtained tensile yield strain, the toughness was evaluated according to the following criteria. ⁇ : Tension yield strain is 9% or more. ⁇ : Tensile yield strain is 7% or more and less than 9%. X: The tensile yield strain is less than 7%. From the obtained measurement results of tensile fracture nominal strain, toughness was evaluated according to the following criteria. ⁇ : Tensile fracture nominal strain is 20% or more. ⁇ : Tensile fracture nominal strain is 14% or more and less than 20%. X: Tensile fracture nominal strain is less than 14%. From the obtained measurement results of tensile elastic modulus, toughness was evaluated according to the following criteria. ⁇ : The tensile elastic modulus is 1100 MPa or more. ⁇ : The tensile elastic modulus is 1000 MPa or more and less than 1100 MPa. X: The tensile elastic modulus is less than 1000 MPa.
• ⁇ Bending elastic modulus is 1100 MPa or more.
• ⁇ The flexural modulus is 1000 MPa or more and less than 1100 MPa.
• X The flexural modulus is less than 1000 MPa.
• Charpy impact strength is less than 4 kJ / m 2 . From the obtained measurement results of Charpy impact strength at ⁇ 40 ° C., the impact resistance was evaluated according to the following criteria. ⁇ : Charpy impact strength is 3 kJ / m 2 or more. ⁇ : Charpy impact strength is 2 kJ / m 2 or more and less than 3 kJ / m 2 . X: Charpy impact strength is less than 2 kJ / m 2 .
• ELASTAMINE RT-1000 10.51 kg, hindered phenolic antioxidant (manufactured by BASF Japan, trade name: Irganox (registered trademark) 245) 0.06 kg, and sodium hypophosphite (Taipei Chemical Industry Co., Ltd.) (Made) 0.03 kg was charged. After sufficiently replacing the inside of the container with nitrogen, the temperature was raised from room temperature to 230 ° C. over 1 hour to carry out polymerization.
• Examples 1 to 11, Comparative Examples 1 to 6 Each component listed in Table 1 was blended with a blender for 10 minutes to obtain each blend composition. From each of the obtained blend compositions, a test piece used for evaluating the above mechanical properties was prepared using a Sumitomo SG75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. The test pieces of Examples 1 and 4 to 11 are tested by setting the cylinder temperature of the injection molding machine to 250 ° C., and the test pieces of Examples 2 and 3 are tested by setting the cylinder temperature to 270 ° C. Pieces were made. For Comparative Example 1, the cylinder temperature was set to 210 ° C., and for Comparative Examples 2 to 6, the cylinder temperature was set to 250 ° C. Table 1 shows the results of evaluation of physical properties and mechanical properties. The unit of the composition in the table is mass%, and the entire polyamide resin composition is 100% by mass.
• the relative viscosities of the polyamide resins (B) and (D) are based on JIS K 6933, and are values measured at 25 ° C. with 1 g of the polyamide resin dissolved in 100 ml of 96% concentrated sulfuric acid.
• the relative viscosity of the above-mentioned polyamide-based elastomer (A) is a value measured at 25 ° C. in accordance with JIS K 6920-2 by dissolving 0.25 g of the polyamide-based elastomer in 50 ml of m-cresol, which is a special grade reagent.
• the polyamide resin compositions of Examples 1 to 11 have molding processability, toughness, flexibility and impact resistance. Since Comparative Example 1 does not contain the polyamide-based elastomer (A) and the aromatic polyamide (C), the tensile yield stress, the tensile fracture nominal strain and the tensile elastic modulus are high, but the tensile yield strain and the Charpy impact strength at 23 ° C. Since it is low, it is easily broken and lacks toughness. In addition, the molding processability is also inferior.
• Comparative Example 2 since the amount of the polyamide-based elastomer (A) is smaller than the range of the present invention, it can be seen that the values of tensile fracture nominal strain and Charpy impact strength are poor and the impact resistance is poor. In Comparative Example 3, since the amount of the aliphatic polyamide resin (B) is smaller than the range of the present invention, the value of the tensile yield stress is low and the toughness is lacking. In Comparative Example 4, since the amount of the polyamide-based elastomer (A) is larger than the range of the present invention, the tensile yield stress, the tensile elastic modulus, the bending strength and the bending elastic modulus are low, and the toughness is lacking and the flexibility is obtained. Lacking.
• Comparative Example 5 since the amount of the aliphatic polyamide resin (B) is larger than the range of the present invention, it can be seen that the value of Charpy impact strength at 23 ° C. is poor and the impact resistance is lacking.
• Comparative Example 6 since the amount of the polyamide-based elastomer (A) is smaller than the range of the present invention and the amount of the aromatic polyamide (C) is large, MFR, tensile yield strain, tensile fracture nominal strain, and Charpy impact strength. It can be seen that the value of is poor and the molding processability, toughness, and impact resistance are lacking.

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