[go: up one dir, main page]

WO2022149436A1 - Composition de polyamide, corps moulé, et procédé de suppression de la propagation d'une vibration ou d'un son de dispositif - Google Patents

Composition de polyamide, corps moulé, et procédé de suppression de la propagation d'une vibration ou d'un son de dispositif Download PDF

Info

Publication number
WO2022149436A1
WO2022149436A1 PCT/JP2021/046776 JP2021046776W WO2022149436A1 WO 2022149436 A1 WO2022149436 A1 WO 2022149436A1 JP 2021046776 W JP2021046776 W JP 2021046776W WO 2022149436 A1 WO2022149436 A1 WO 2022149436A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
less
polyamide composition
mass
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/046776
Other languages
English (en)
Japanese (ja)
Inventor
真次 家田
純 三上
巌生 加藤
圭 山内
裕輝 池田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp, Asahi Chemical Industry Co Ltd filed Critical Asahi Kasei Corp
Priority to JP2022573974A priority Critical patent/JP7524361B2/ja
Publication of WO2022149436A1 publication Critical patent/WO2022149436A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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 method of suppressing vibration or sound propagation of a polyamide composition, a molded body, and an apparatus.
  • resin materials have been developed as lightweight materials to replace metal materials in parts in various fields such as automobile parts.
  • the resin material when a resin material is applied to parts in an engine room such as an oil pan, a cylinder head cover, and a chain case among automobile parts, the resin material has heat resistance, high rigidity, impact resistance, and the like. Excellent vibration properties are required.
  • Patent Document 1 discloses a method for producing a nylon composite having good vibration damping properties by blending an elastomer with a fiber-blended nylon mixed with glass fiber.
  • the vibration suppressing effect is imparted by adding an elastomer to the resin material, but there is a concern that the strength and elastic modulus of the obtained molded body may decrease.
  • the present invention has been made in view of the above circumstances, is excellent in flexural modulus, tensile strength and appearance when formed into a molded body, and generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower.
  • a polyamide composition having an excellent vibration damping and noise suppressing effect of the device, and a method for suppressing vibration or sound propagation of a molded body obtained by molding the polyamide composition and a device using the molded body.
  • the tan ⁇ peak temperature of the polyamide composition is 90 ° C. or higher, and the temperature is 90 ° C. or higher.
  • the (B) amorphous polyamide is dispersed in the (A) crystalline polyamide to form a domain.
  • (B) A polyamide composition having an average particle size of 10 nm or more and 1.0 ⁇ m or less of the amorphous polyamide forming the domain.
  • (4) The polyamide composition according to any one of (1) to (3) above, wherein the (A) crystalline polyamide is polyamide 66 or polyamide 610 or polyamide 6.
  • the (B) amorphous polyamide contains a dicarboxylic acid unit containing at least 75 mol% of an isophthalic acid unit and a diamine unit containing at least 50 mol% of a diamine unit having 4 or more and 10 or less carbon atoms.
  • the polyamide composition according to. (9) The polyamide composition according to any one of (1) to (8) above, wherein the melting point Tm2 is 240 ° C. or higher and 260 ° C. or lower. (10) The terminal amount sealed with the sealant per 1 g of at least one polyamide selected from the group consisting of the (A) crystalline polyamide and the (B) amorphous polyamide is 30 ⁇ mol equivalent / g or more and 140 ⁇ mol.
  • (11) The polyamide composition according to any one of (1) to (10) above, wherein the polyamide composition has a weight average molecular weight Mw of 15,000 or more and 34,000 or less.
  • (12) The polyamide composition according to any one of (1) to (11) above, wherein the polyamide composition has a molecular weight distribution Mw / Mn of 2.4 or less.
  • the total amount of amino-terminal and carboxy-terminal amounts per 1 g of at least one polyamide selected from the group consisting of the (A) crystalline polyamide and the (B) amorphous polyamide is 70 ⁇ mol equivalent / g or more and 145 ⁇ mol.
  • the polyamide composition according to any one of (1) to (12) above which has an equivalent amount / g or less.
  • the bending elastic modulus of a dumbbell having a thickness of 4 mm conforming to ISO178, which is obtained by molding the polyamide composition, at 23 ° C. measured according to ISO178 is 10 GPa or more, and the above (1) to (13). ).
  • the apparatus which comprises using the molded product according to any one of (15) to (20) above, for an apparatus that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower. A method of suppressing vibration or sound propagation.
  • the bending elastic modulus, the tensile strength and the appearance of the molded product are excellent, and the vibration damping of the device that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower is achieved. It is possible to provide a polyamide composition having an excellent noise suppression effect.
  • the molded body of the above embodiment is formed by molding the polyamide composition, and is excellent in flexural modulus, tensile strength and appearance, and vibration damping of an apparatus that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower. And excellent noise suppression effect.
  • the method of the above aspect is a method using the molded body, and can attenuate the vibration of a device that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower, and suppress noise.
  • the present embodiment a mode for carrying out the present invention (hereinafter, abbreviated as “the present embodiment”) will be described in detail.
  • the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
  • polyamide means a polymer having an amide (-NHCO-) group in the backbone.
  • the polyamide composition of the present embodiment is used for a molded body for suppressing vibration or sound propagation of an apparatus that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower.
  • the polyamide composition of the present embodiment contains (A) crystalline polyamide and (B) amorphous polyamide.
  • the content of the (B) amorphous polyamide is 10.0% by mass or more and 50.0% by mass or less with respect to the mass of the total polyamide in the polyamide composition. It is preferably 10.0% by mass or more and 45.0% by mass or less, more preferably 12.5% by mass or more and 45.0% by mass or less, further preferably 15.0% by mass or more and 42.5% by mass or less, and 17.5% by mass. More preferably, it is more preferably mass% or more and 40.0 mass% or less, particularly preferably 20.0 mass% or more and 37.5 mass% or less, and most preferably 22.5 mass% or more and 35.0 mass% or less.
  • the lower limit of the tan ⁇ peak temperature of the polyamide composition of the present embodiment is 90 ° C., preferably 95 ° C., more preferably 100 ° C., and even more preferably 105 ° C.
  • the upper limit of the tan ⁇ peak temperature of the resin composition is preferably 150 ° C., more preferably 140 ° C., and even more preferably 130 ° C.
  • the tan ⁇ peak temperature of the resin composition is 90 ° C. or higher, preferably 95 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or higher and 140 ° C. or lower, and even more preferably 105 ° C. or higher and 130 ° C. or lower.
  • the polyamide composition of the present embodiment When the tan ⁇ peak temperature of the polyamide composition of the present embodiment is at least the above lower limit value, the polyamide composition tends to be more excellent in rigidity and strength in a high temperature environment when formed into a molded product. On the other hand, when the tan ⁇ peak temperature of the polyamide composition is not more than the above upper limit value, the molded product obtained from the polyamide composition containing a component typified by a filler tends to have a better surface appearance. be.
  • a method for controlling the tan ⁇ peak temperature of the polyamide composition within the above range for example, a method for controlling the contents of (A) crystalline polyamide and (B) amorphous polyamide within the range described later and the above range, respectively. And so on.
  • the ratio (E2 / E1) of the loss elastic modulus E2 to the storage elastic modulus E1 measured using a viscoelasticity measurement analyzer or the like is tan ⁇ , and the highest temperature is the tan ⁇ peak temperature. More specifically, it can be measured by the method described in Examples described later.
  • the (B) amorphous polyamide is dispersed in the (A) crystalline polyamide to form a domain. That is, it can be said that the amorphous polyamide is finely dispersed in (A) crystalline polyamide and forms a phase-separated structure or a sea-island structure.
  • the amount of the interface forming the domains of (A) crystalline polyamide and (B) amorphous polyamide having different molecular motility is large, and therefore the domain size. Is desirable to be small. Further, in order to exert the vibration damping and noise suppressing effects at low frequencies, the domain size is preferably 10 nm or more.
  • the number average particle size of (A) the amorphous polyamide dispersed in the crystalline polyamide and forming a domain is 10 nm or more and 1.0 ⁇ m or less, preferably 10 nm or more and 500 nm or less. It is more preferably 10 nm or more and 300 nm or less, further preferably 20 nm or more and 100 nm or less, and particularly preferably 30 nm or more and 80 nm or less.
  • the number average particle size (50% cumulative value of the dispersed particle size distribution) of the (B) amorphous polyamide forming the domain can be measured, for example, by using the method described in Examples described later.
  • the polyamide composition of the present embodiment is excellent in flexural modulus, tensile strength and appearance, and vibration damping and vibration damping of an apparatus that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower.
  • a molded body having an excellent noise suppression effect can be obtained.
  • the crystalline polyamide is a polyamide having a heat of fusion of crystals of 4 J / g or more when measured at 20 ° C./min by a differential scanning calorimeter.
  • the (A) crystalline polyamide is not specifically limited to the following, but for example, (a) a polyamide obtained by ring-opening polymerization of lactam, (b) a polyamide obtained by self-condensation of ⁇ -aminocarboxylic acid, ( c) Polyamides obtained by condensing diamine and dicarboxylic acid, copolymers thereof and the like can be mentioned. These crystalline polyamides may be used alone or as a mixture of two or more.
  • the lactam of (a) is not limited to the following, and examples thereof include pyrrolidone, caprolactam, undecalactam, and dodecalactam.
  • the ⁇ -aminocarboxylic acid in (b) is not limited to the following, and examples thereof include ⁇ -amino fatty acid, which is a ring-opening compound of lactam with water.
  • lactam or ⁇ -aminocarboxylic acid two or more kinds of monomers may be used in combination and condensed.
  • the diamine (monomer) of (c) is not limited to the following, but for example, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, etc.
  • Examples thereof include linear saturated aliphatic diamines having 2 or more and 20 or less carbon atoms such as decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.
  • the diamine constituting the diamine unit having a substituent branched from the main chain is not limited to the following, but is also referred to as, for example, 2-methylpentamethylenediamine (2-methyl-1,5-diaminopentane). ), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), 2,4- Examples thereof include branched chain saturated aliphatic diamines having 3 or more carbon atoms and 20 or less carbon atoms such as dimethyloctamethylenediamine.
  • 2-methylpentamethylenediamine or 2-methyl-1,8-octanediamine is preferable, and 2-methylpentamethylenediamine is more preferable.
  • the polyamide composition tends to be excellent in heat resistance, rigidity and the like.
  • the number of carbon atoms in the diamine unit is preferably 4 or more and 12 or less, and more preferably 4 or more and 10 or less.
  • the number of carbon atoms is at least the above lower limit value, the heat resistance is excellent, while when the number of carbon atoms is at least the above upper limit value, the crystallinity and releasability are excellent.
  • the aliphatic diamine may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine, if necessary.
  • a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine, if necessary.
  • the diamine only one kind may be used alone, or two or more kinds may be used in combination.
  • the dicarboxylic acid (monomer) of (c) is not limited to the following, but is, for example, an aliphatic dicarboxylic acid such as succinic acid, adipic acid, pimelic acid, sebacic acid, dodecanedioic acid, or tetradecanedioic acid; isophthalic acid.
  • Aromatic dicarboxylic acids such as terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
  • the above-mentioned diamine and dicarboxylic acid as monomers may be condensed by one kind alone or two or more kinds in combination, respectively.
  • the crystalline polyamide may further contain a unit derived from a trivalent or higher valent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary.
  • a trivalent or higher valent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary.
  • the polyvalent carboxylic acid having a trivalent or higher value only one type may be used alone, or two or more types may be used in combination.
  • polyamide 4 poly ⁇ -pyrrolidone
  • polyamide 6 polycaproamide
  • polyamide 11 polyundecaneamide
  • polyamide 12 Polydodecaneamide
  • Polyamide 46 Polytetramethylene adipamide
  • Polyamide 56 Polypentamethylene adipamide
  • Polyamide 66 Polyhexamethylene adipamide
  • Polyamide 610 Polyhexamethylene sebacamide
  • Polyamide 612 polyhexamethylene dodecamide
  • polyamide 4T polytetramethylene terephthalamide
  • polyamide 6T polyhexamethylene terephthalamide
  • polyamide 9T polynonane methylene terephthalamide
  • Polyamide can be mentioned. Among them, polyamide 6, polyamide 46, polyamide 66, or polyamide 610 is preferable, and polyamide 6, polyamide 66, or polyamide 610 is more preferable.
  • Polyamide 66 is considered to be a suitable material for automobile parts because it is excellent in heat resistance, moldability and toughness. Further, a long-chain aliphatic polyamide such as polyamide 610 is preferable because of its excellent chemical resistance.
  • the melting point Tm2 of the crystalline polyamide (A) is preferably 200 ° C. or higher, more preferably 220 ° C. or higher and 295 ° C. or lower, further preferably 230 ° C. or higher and 265 ° C. or lower, particularly preferably 240 ° C. or higher and 260 ° C. or lower, and 250 ° C. or higher. Most preferably, it is 260 ° C. or lower.
  • the melting point Tm2 of the crystalline polyamide (A) is at least the above lower limit value, it tends to be possible to obtain a polyamide composition having better thermal rigidity and the like.
  • the melting point Tm2 of the crystalline polyamide (A) is not more than the above upper limit value, it tends to be possible to further suppress the thermal decomposition of the polyamide composition in the melt processing such as extrusion and molding.
  • the melting point Tm2 is measured using a differential scanning calorimeter (DSC) according to JIS-K7121 as described in the following examples.
  • the content of (A) crystalline polyamide shall be, for example, 50.0% by mass or more and 90.0% by mass or less with respect to the mass of the total polyamide in the polyamide composition. 52.5% by mass or more and 90.0% by mass or less is preferable, 54.0% by mass or more and 90.0% by mass or less is more preferable, and 55.0% by mass or more and 85.0% by mass or less is further preferable. It is more preferably 56.0% by mass or more and 80.0% by mass or less, particularly preferably 57.0% by mass or more and 77.5% by mass or less, and most preferably 57.5% by mass or more and 75.5% by mass or less.
  • Amorphous polyamide refers to a polyamide having a crystallization enthalpy ⁇ H of 15 J / g or less.
  • the crystallization enthalpy of the amorphous polyamide is preferably 10 J / g or less, more preferably 5 J / g or less, and further preferably 0 J / g.
  • the crystallization enthalpy ⁇ H can be measured using, for example, a measuring device such as Diamond-DSC manufactured by PERKIN-ELMER.
  • the amorphous polyamide (B) is not particularly limited as long as the crystallization enthalpy ⁇ H is not more than the above upper limit value, but may be a semi-aromatic polyamide.
  • the amorphous polyamide is a semi-aromatic polyamide, it is preferably a polyamide containing a diamine unit and a dicarboxylic acid unit.
  • the amorphous polyamide contains at least 75 mol% of (BA) dicarboxylic acid units containing at least 75 mol% of isophthalic acid units and at least 50 mol% of diamine units having 4 or more and 10 or less carbon atoms (B) diamine units. It is preferable that the polyamide contains and.
  • the total amount of the isophthalic acid unit and the diamine unit having 4 or more and 10 or less carbon atoms is preferably 75 mol% or more and 100 mol% or less, preferably 90 mol% or less, based on the total amount of all the constituent units of (B) the amorphous polyamide. More than 100 mol% is more preferable, and 100 mol% is further preferable.
  • (B) the ratio of a predetermined monomer unit constituting the amorphous polyamide can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.
  • the content of the isophthalic acid unit with respect to the total amount of the dicarboxylic acid is preferably 75 mol% or more, more preferably 75 mol% or more and 100 mol% or less, and 90 mol% or more and 100 mol% or less. Is more preferable, and 100 mol% is particularly preferable.
  • a polyamide that simultaneously satisfies mechanical properties, thermal rigidity, fluidity, surface appearance, vibration damping, and noise suppression effect when the content of isophthalic acid unit with respect to the total number of moles of dicarboxylic acid is equal to or higher than the above lower limit.
  • the composition can be obtained.
  • the (BA) dicarboxylic acid unit may contain an aromatic dicarboxylic acid unit, an aliphatic dicarboxylic acid unit, and an alicyclic dicarboxylic acid unit other than the isophthalic acid unit.
  • aromatic dicarboxylic acid unit examples include, but are not limited to, a dicarboxylic acid having a phenyl group and a naphthyl group.
  • the aromatic group of the aromatic dicarboxylic acid may be unsubstituted or have a substituent.
  • the substituent is not particularly limited, and is, for example, an alkyl group having 1 or more and 4 or less carbon atoms, an aryl group having 6 or more and 10 or less carbon atoms, an arylalkyl group having 7 or more and 10 or less carbon atoms, a chloro group, a bromo group and the like.
  • Examples thereof include a halogen group of the above, a silyl group having 1 or more and 6 or less carbon atoms, a sulfonic acid group and a salt thereof (sodium salt, etc.). Specifically, it is not limited to the following, but is not substituted with terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid and the like. Alternatively, an aromatic dicarboxylic acid having 8 or more and 20 or less carbon atoms substituted with a predetermined substituent can be mentioned. Of these, terephthalic acid is preferable. As the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.
  • the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, and is, for example, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethyl.
  • Glutalic acid 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azeline Linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acids, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid, diglycolic acid, etc. Can be mentioned.
  • alicyclic dicarboxylic acid unit The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit (hereinafter, also referred to as “alicyclic dicarboxylic acid unit”) is not limited to the following, but for example, the number of carbon atoms in the alicyclic structure is limited. Examples thereof include alicyclic dicarboxylic acids having 3 or more and 10 or less, and alicyclic dicarboxylic acids having an alicyclic structure having 5 or more and 10 or less carbon atoms are preferable.
  • the alicyclic dicarboxylic acid is not limited to the following, and examples thereof include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Can be mentioned. Of these, 1,4-cyclohexanedicarboxylic acid is preferable.
  • the alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit only one kind may be used alone, or two or more kinds may be used in combination.
  • the alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or have a substituent.
  • the substituent is not limited to the following, but for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like having 1 or more carbon atoms 4
  • the following alkyl groups and the like can be mentioned.
  • the dicarboxylic acid unit other than the isophthalic acid unit preferably contains an aromatic dicarboxylic acid unit, and more preferably contains an aromatic dicarboxylic acid having 6 or more and 12 or less carbon atoms.
  • an aromatic dicarboxylic acid unit preferably contains an aromatic dicarboxylic acid having 6 or more and 12 or less carbon atoms.
  • the dicarboxylic acid constituting the (BA) dicarboxylic acid unit is not limited to the compound described as the dicarboxylic acid, but is a compound equivalent to the dicarboxylic acid. May be good.
  • the "compound equivalent to a dicarboxylic acid” refers to a compound having a dicarboxylic acid structure similar to that of the dicarboxylic acid derived from the dicarboxylic acid. Examples of such compounds include, but are not limited to, anhydrides and halides of dicarboxylic acids.
  • the (B) amorphous polyamide may further contain a unit derived from a trivalent or higher valent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary.
  • a trivalent or higher valent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary.
  • the polyvalent carboxylic acid having a trivalent or higher value only one type may be used alone, or two or more types may be used in combination.
  • the (B) diamine unit constituting the (B) amorphous polyamide preferably contains at least 50 mol% of the diamine unit having 4 or more and 10 or less carbon atoms. Examples thereof include, but are not limited to, an aliphatic diamine unit, an alicyclic diamine unit, and an aromatic diamine unit.
  • the aliphatic diamine constituting the aliphatic diamine unit is not limited to the following, and for example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, etc.
  • Examples thereof include linear saturated aliphatic diamines having 2 or more and 20 or less carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.
  • alicyclic diamine unit The alicyclic diamine constituting the alicyclic diamine unit (hereinafter, also referred to as “alicyclic diamine”) is not limited to the following, and is, for example, 1,4-cyclohexanediamine, 1,3-. Cyclohexanediamine, 1,3-cyclopentanediamine and the like can be mentioned.
  • aromatic diamine unit The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it is a diamine containing an aromatic, and examples thereof include metaxylylenediamine.
  • an aliphatic diamine unit is preferable, a diamine unit having a linear saturated aliphatic group having 4 or more and 10 or less carbon atoms is more preferable, and a diamine unit having a linear saturated aliphatic group having 6 or more and 10 or less carbon atoms is preferable. Further preferred, hexamethylenediamine units are particularly preferred.
  • the polyamide composition tends to be excellent in mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, surface appearance, corrosiveness and the like.
  • the diamine only one kind may be used alone, or two or more kinds may be used in combination.
  • polyamide 6I, 6I / 6T, 9I and 10I are preferable, and polyamide 6I is particularly preferable.
  • the amorphous polyamide may further contain a trivalent or higher valent aliphatic amine such as bishexamethylenetriamine, if necessary.
  • the trivalent or higher polyvalent aliphatic amine may be used alone or in combination of two or more.
  • the amorphous polyamide can further contain at least one unit selected from the group consisting of lactam units and aminocarboxylic acid units. By including such a unit, a polyamide having better toughness tends to be obtained.
  • the lactam and the aminocarboxylic acid constituting the lactam unit and the aminocarboxylic acid unit refer to the lactam and the aminocarboxylic acid that can be combined (reduced).
  • lactam and aminocarboxylic acid constituting the lactam unit and the aminocarboxylic acid unit are not limited to the following, but for example, lactam and aminocarboxylic acid having 4 or more and 14 or less carbon atoms are preferable, and 6 or more and 12 carbon atoms are preferable.
  • lactams and aminocarboxylic acids are more preferred.
  • the lactam constituting the lactam unit is not limited to the following, and examples thereof include butyloractam, pivalolactam, ⁇ -caprolactam, caprolactam, enantractam, undecanolactam, laurolactam (dodecanolactam) and the like. Will be. Among them, as the lactam, ⁇ -caprolactam or laurolactam is preferable, and ⁇ -caprolactam is more preferable. The inclusion of such lactam tends to result in a polyamide composition having better toughness.
  • the aminocarboxylic acid constituting the aminocarboxylic acid unit is not limited to the following, and examples thereof include ⁇ -aminocarboxylic acid and ⁇ , ⁇ -amino acids, which are compounds in which lactam is opened.
  • ⁇ -aminocarboxylic acid a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms in which the ⁇ position is substituted with an amino group is preferable.
  • Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like.
  • examples of the aminocarboxylic acid include paraaminomethylbenzoic acid and the like.
  • lactam and aminocarboxylic acid constituting the lactam unit and the aminocarboxylic acid unit may be used alone or in combination of two or more.
  • the total ratio (mol%) of the lactam unit and the aminocarboxylic acid unit is preferably 0 mol% or more and 20 mol% or less, more preferably 0 mol% or more and 10 mol% or less, and 0 mol% or more and 5 of the total polyamide. More preferably, it is mol% or less.
  • the total ratio of the lactam unit and the aminocarboxylic acid unit is within the above range, the effect of improving the fluidity or the like tends to be obtained.
  • At least one polyamide selected from the group consisting of (A) crystalline polyamide and (B) amorphous polyamide contained in the polyamide composition of the present embodiment has an end sealed with an end sealant. May be.
  • Such a terminal encapsulant is used when producing a polyamide from the above-mentioned dicarboxylic acid and diamine, and at least one compound selected from the group consisting of lactam and aminocarboxylic acid, which is used as necessary. It can also be added as a molecular weight modifier.
  • terminal encapsulant examples include, but are not limited to, acid anhydrides, monoisocyanates, monoacid halides, monoesters, and monoalcohols.
  • acid anhydride examples include monocarboxylic acid, monoamine, phthalic anhydride and the like. Of these, monocarboxylic acids or monoamines are preferred. Since the ends of the polyamide are sealed with an end sealant, the polyamide composition tends to have better thermal stability. As the end sealant, only one type may be used alone, or two or more types may be used in combination.
  • the monocarboxylic acid that can be used as the terminal encapsulant may be any acid that has reactivity with an amino group that can be present at the terminal of the polyamide.
  • Specific examples of the monocarboxylic acid include, but are not limited to, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids.
  • the aliphatic monocarboxylic acid is not limited to, but is not limited to, for example, formic acid, acetic acid, propionic acid, fatty acid, valeric acid, caproic acid, capric acid, lauric acid, tridecylic acid, myristyl acid, palmitic acid, and the like.
  • Examples thereof include stearic acid, pivalic acid, isobutyl acid and the like.
  • Examples of the alicyclic monocarboxylic acid include, but are not limited to, cyclohexanecarboxylic acid.
  • Examples of the aromatic monocarboxylic acid include, but are not limited to, benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and the like. These monocarboxylic acids may be used alone or in combination of two or more.
  • the monoamine that can be used as the terminal encapsulant may be any monoamine that has reactivity with a carboxy group that may be present at the terminal of the polyamide.
  • Specific examples of the monoamine include, but are not limited to, aliphatic monoamines, alicyclic monoamines, aromatic monoamines, and the like.
  • the aliphatic amine is not limited to, but is not limited to, for example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. And so on.
  • alicyclic amine examples include, but are not limited to, cyclohexylamine and dicyclohexylamine.
  • the aromatic amine is not limited to the following, and examples thereof include aniline, toluidine, diphenylamine, and naphthylamine. These monoamines may be used alone or in combination of two or more.
  • Polyamide compositions containing polyamides terminally sealed with an end sealant tend to be excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, corrosion resistance, vibration damping and noise suppression effects. ..
  • the amount of the dicarboxylic acid added and the amount of the diamine added are preferably close to the same molar amount.
  • the molar amount of the entire diamine is preferably 0.9 or more and 1.2 or less with respect to the molar amount of 1 of the total dicarboxylic acid. , 0.95 or more and 1.1 or less are more preferable, and 0.98 or more and 1.05 or less are further preferable.
  • the method for producing a polyamide is not limited to the following, but includes, for example, the following polymerization step (1) or (2).
  • (1) A step of polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit to obtain a polymer.
  • (2) A step of polymerizing one or more selected from the group consisting of lactam constituting a lactam unit and aminocarboxylic acid constituting an aminocarboxylic acid unit to obtain a polymer.
  • a method for producing a polyamide it is preferable to further include an increasing step of increasing the degree of polymerization of the polyamide after the polymerization step. Further, if necessary, after the polymerization step and the ascending step, a sealing step of sealing the ends of the obtained polymer with an end-sealing agent may be included.
  • aqueous solutions or aqueous suspensions selected from the group consisting of a dicarboxylic acid-diamine salt, a mixture of a dicarboxylic acid and a diamine, lactam, and an aminocarboxylic acid are heated and polymerized while maintaining a molten state. (Hereinafter, it may be referred to as "heat melt polymerization method").
  • Hot melt polymerization / solid phase polymerization method A method of increasing the degree of polymerization of a polyamide obtained by a hot melt polymerization method while maintaining a solid state at a temperature below the melting point.
  • a method of polymerizing using a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component hereinafter, may be referred to as "solution method”).
  • a production method including a hot melt polymerization method is preferable. Further, when producing a polyamide by the hot melt polymerization method, it is preferable to maintain the molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to produce the product under polymerization conditions suitable for polyamide. Examples of the polymerization conditions include the following conditions. First, the polymerization pressure in the hot melt polymerization method is controlled to 14 kg / cm 2 or more and 25 kg / cm 2 or less (gauge pressure), and heating is continued. Next, the pressure is lowered while applying 30 minutes or more until the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm 2 ).
  • the polymerization form is not particularly limited, and may be a batch type or a continuous type.
  • the polymerization apparatus used for producing the polyamide is not particularly limited, and a known apparatus can be used. Specific examples of the polymerization apparatus include an autoclave type reactor, a tumbler type reactor, an extruder type reactor (kneader and the like) and the like.
  • a method for producing a polyamide a method for producing a polyamide by a batch-type hot melt polymerization method will be specifically shown, but the method for producing a polyamide is not limited to this.
  • a raw material component of polyamide a combination of a dicarboxylic acid and a diamine, and, if necessary, at least one selected from the group consisting of lactam and aminocarboxylic acid.
  • a aqueous solution is concentrated to about 65% by mass or more and 90% by mass or less in a concentration tank operated at a temperature of 110 ° C. or more and 180 ° C.
  • the pressure is maintained at about 1.2 MPa or more and 2.2 MPa or less (gauge pressure) while removing at least one of the water and gas components. Then, when the temperature reaches about 220 ° C. or higher and 260 ° C. or lower, the pressure is lowered to atmospheric pressure (gauge pressure is 0 MPa).
  • the autoclave is then pressurized with an inert gas such as nitrogen to extrude the polyamide melt from the autoclave as strands.
  • the extruded strands are cooled and cut to obtain polyamide pellets.
  • the polymer terminal of the polyamide ((A) crystalline polyamide and (B) amorphous polyamide) contained in the polyamide composition of the present embodiment is not particularly limited, but is classified into the following 1) to 4) and defined. can do. That is, 1) amino terminal, 2) carboxy terminal, 3) terminal by encapsulant, and 4) other terminal.
  • the amino terminus is a polymer terminus having an amino group (-NH 2 groups) and is derived from a diamine unit.
  • the carboxy terminal is a polymer terminal having a carboxy group (-COOH group) and is derived from a dicarboxylic acid.
  • the end by the encapsulant is the end formed when the encapsulant is added at the time of polymerization.
  • Examples of the encapsulant include end encapsulants described later.
  • the other terminals are polymer ends that are not classified into 1) to 3) described above. Specific examples of the other terminal include a terminal produced by a decarboxylation reaction of an amino terminal, a terminal produced by a decarboxylation reaction from a carboxy terminal, and the like.
  • (A) Weight average molecular weight Mw (A) of crystalline polyamide) (A) A weight average molecular weight can be used as an index of the molecular weight of the crystalline polyamide.
  • the weight average molecular weight (Mw (A)) of the crystalline polyamide is preferably 10,000 or more and 50,000 or less, more preferably 15,000 or more and 45,000 or less, further preferably 20,000 or more and 43,000 or less, and particularly preferably 25,000 or more and 40,000 or less.
  • Mw (A) is in the above range, there is a tendency to obtain a polyamide composition that can simultaneously satisfy mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, corrosion resistance and the like.
  • the molded product obtained from the polyamide composition containing a component typified by an inorganic filler has a more excellent surface appearance.
  • Mw (A) The weight average molecular weight (Mw (A)) of the crystalline polyamide can be measured by using GPC.
  • the molecular weight distribution of (A) crystalline polyamide is based on (A) weight average molecular weight of (A) crystalline polyamide (Mw (A)) / (A) number average molecular weight of (A) crystalline polyamide (Mn (A)) as an index.
  • Mw (A) / Mn (A) is preferably 1.0 or more, more preferably 1.8 or more and 2.2 or less, and further preferably 1.9 or more and 2.1 or less.
  • Mw (A) / Mn (A) is in the above range, a polyamide composition having excellent fluidity and the like can be obtained. Further, the molded product obtained from the polyamide composition containing a component typified by an inorganic filler has a more excellent surface appearance.
  • Examples of the method for controlling Mw (A) / Mn (A) within the above range include the methods shown in 1) or 2) below. 1) A method of adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive during thermal melt polymerization of polyamide. 2) In addition to the method of 1) above, a method of controlling polymerization conditions such as heating conditions and depressurizing conditions.
  • a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite
  • Mw (A) / Mn (A) can be calculated using Mw (A) and Mn (A) obtained by using GPC.
  • the sealed terminal amount of (A) crystalline polyamide is preferably 5 ⁇ mol equivalent / g or more and 180 ⁇ mol equivalent / g or less, more preferably 5 ⁇ mol equivalent / g or more and 150 ⁇ mol equivalent / g or less, per 1 g of (A) crystalline polyamide. It is more preferably 10 ⁇ mol equivalent / g or more and 100 ⁇ mol equivalent / g or less, particularly preferably 15 ⁇ mol equivalent / g or more and 80 ⁇ mol equivalent / g or less, and most preferably 20 ⁇ mol equivalent / g or more and 60 ⁇ mol equivalent / g or less.
  • the amount of the sealed end is in the above range, the generation of mold deposit (MD) during molding is suppressed, and the surface appearance, thermal strength, vibration damping and noise suppression effect of the molded product are excellent. It can be a composition.
  • the amount of sealed ends can be measured, for example, by NMR.
  • the lower limit of the melting point Tm2 of the crystalline polyamide (A) is preferably 220 ° C., more preferably 230 ° C., and even more preferably 240 ° C.
  • the upper limit of the melting point Tm2 of the crystalline polyamide (A) is preferably 300 ° C., more preferably 290 ° C., still more preferably 280 ° C., and particularly preferably 270 ° C.
  • the melting point Tm2 of the crystalline polyamide (A) is preferably 220 ° C. or higher and 300 ° C. or lower, more preferably 230 ° C. or higher and 290 ° C.
  • the lower limit of the crystallization enthalpy ⁇ H of the crystalline polyamide is preferably 30 J / g, more preferably 40 J / g, still more preferably 50 J / g, from the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity. , 60 J / g is particularly preferable.
  • the tan ⁇ peak temperature of the crystalline polyamide is preferably 40 ° C. or higher, more preferably 50 ° C. or higher and 110 ° C. or lower, further preferably 60 ° C. or higher and 100 ° C. or lower, particularly preferably 70 ° C. or higher and 95 ° C. or lower, and particularly preferably 80 ° C. Most preferably, it is 90 ° C. or higher and 90 ° C. or lower.
  • the tan ⁇ peak temperature of the crystalline polyamide can be measured by using a viscoelasticity measuring and analyzing device (manufactured by Rheology: DVE-V4) in the same manner as the polyamide composition.
  • (B) Weight average molecular weight Mw (B) of amorphous polyamide) As an index of the molecular weight of (B) amorphous polyamide, (B) weight average molecular weight (Mw (B)) of (B) amorphous polyamide can be used.
  • the weight average molecular weight (Mw (B)) of the amorphous polyamide is preferably 10,000 or more and 50,000 or less, more preferably 10,000 or more and 45,000 or less, further preferably 13,000 or more and 40,000 or less, and further preferably 15,000 or more and 35,000 or less. , 18,000 or more and 30,000 or less are particularly preferable, and 19000 or more and 25,000 or less are most preferable.
  • the weight average molecular weight (Mw (B)) of the (B) amorphous polyamide when the weight average molecular weight (Mw (B)) of the (B) amorphous polyamide is in the above range, the molecular weight can be made smaller than that of the (A) crystalline polyamide, and the molded product is mechanically formed.
  • a polyamide composition excellent in properties, particularly water absorption rigidity, thermal rigidity, fluidity, vibration damping and noise suppression effects can be obtained. Further, the molded product obtained from the polyamide composition containing a component typified by an inorganic filler has a more excellent surface appearance.
  • the weight average molecular weight (Mw (B)) of the amorphous polyamide can be measured by using GPC.
  • Mw (B) / Mn (B) is preferably 1.0 or more and 3.5 or less, more preferably 1.0 or more and 3.0 or less, further preferably 1.7 or more and 2.5 or less, and 1.8 or more and 2 It is more preferably 0.3 or less, particularly preferably 1.9 or more and 2.2 or less, and most preferably 1.9 or more and 2.1 or less.
  • Examples of the method for controlling Mw (B) / Mn (B) within the above range include the methods shown in 1) or 2) below.
  • Mw / Mn molecular weight distribution
  • a high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional structure of the molecule.
  • An excellent polyamide composition can be obtained due to the noise suppression effect.
  • the surface appearance of the molded product obtained from the polyamide composition containing a component typified by an inorganic filler becomes more excellent.
  • the measurement of Mw (B) / Mn (B) can be calculated using Mw (B) and Mn (B) obtained by using GPC.
  • the crystallization enthalpy ⁇ H of the amorphous polyamide is preferably 15 J / g or less, more preferably 10 J / g or less, further preferably 5 J / g or less, and 0 J / g from the viewpoint of vibration attenuation and noise suppression effect. Is particularly preferable.
  • a known method for reducing the crystallinity of the polyamide can be taken and is not particularly limited.
  • the (B) amorphous polyamide may contain 75 mol% or more of the isophthalic acid unit as the (BA) dicarboxylic acid unit in the total dicarboxylic acid units constituting the (B) amorphous polyamide. It is preferable, and it is particularly preferable to contain 100 mol%.
  • the device for measuring the crystallization enthalpy ⁇ H of the amorphous polyamide include Diamond-DSC manufactured by PERKIN-ELMER.
  • the tan ⁇ peak temperature of the amorphous polyamide is preferably 90 ° C. or higher, more preferably 100 ° C. or higher and 160 ° C. or lower, further preferably 110 ° C. or higher and 150 ° C. or lower, particularly preferably 120 ° C. or higher and 145 ° C. or lower, and 130 ° C. or higher. Most preferably, it is °C or more and 140 °C or less.
  • the (B) amorphous polyamide may contain 75 mol% or more of the isophthalic acid unit as the (BA) dicarboxylic acid unit in the total dicarboxylic acid units constituting the (B) amorphous polyamide. It is important and is particularly preferred to contain 100 mol%.
  • the tan ⁇ peak temperature of the amorphous polyamide can be measured by using, for example, a viscoelasticity measuring and analyzing device (manufactured by Rheology: DVE-V4) in the same manner as the polyamide composition.
  • the terminal amount sealed with the sealant of the amorphous polyamide is preferably 5 ⁇ mol equivalent / g or more and 180 ⁇ mol equivalent / g or less, and 10 ⁇ mol equivalent / g or more and 170 ⁇ mol equivalent per 1 g of the (B) amorphous polyamide.
  • / G or less is more preferable, 30 ⁇ mol equivalent / g or more and 160 ⁇ mol equivalent / g or less is further preferable, 50 ⁇ mol equivalent / g or more and 160 ⁇ mol equivalent / g or less is particularly preferable, and 60 ⁇ mol equivalent / g or more and 160 ⁇ mol equivalent / g or less is most preferable.
  • the amount of the sealed end is in the above range, the generation of mold deposit (MD) during molding is suppressed, and the surface appearance, thermal strength, vibration damping and noise suppression effect of the molded product are excellent. It can be a composition. Further, it is particularly preferable that the amount of terminals sealed with acetic acid is in the above range. The amount of sealed ends can be measured by NMR.
  • the amino terminal amount of (B) amorphous polyamide is preferably 5 ⁇ mol equivalent / g or more and 90 ⁇ mol equivalent / g or less, more preferably 10 ⁇ mol equivalent / g or more and 80 ⁇ mol equivalent / g or less, per 1 g of (B) amorphous polyamide. It is more preferably 10 ⁇ mol equivalent / g or more and 70 ⁇ mol equivalent / g or less, particularly preferably 20 ⁇ mol equivalent / g or more and 60 ⁇ mol equivalent / g or less, and most preferably 30 ⁇ mol equivalent / g or more and 50 ⁇ mol equivalent / g or less.
  • the amount of the amino terminal of the (B) amorphous polyamide is in the above range, the compatibility with the (A) crystalline polyamide can be further improved, and the number average particle size of the domain can be further reduced. .. As a result, it is possible to obtain an excellent polyamide composition due to the effects of discoloration, vibration damping and noise suppression on heat and light when the molded product is formed.
  • the amount of amino terminal can be measured by NMR.
  • the carboxy terminal amount of (B) amorphous polyamide is preferably 20 ⁇ mol equivalent / g or more and 150 ⁇ mol equivalent / g or less, more preferably 30 ⁇ mol equivalent / g or more and 120 ⁇ mol equivalent / g or less, per 1 g of (B) amorphous polyamide. It is more preferably 30 ⁇ mol equivalent / g or more and 100 ⁇ mol equivalent / g or less, particularly preferably 40 ⁇ mol equivalent / g or more and 90 ⁇ mol equivalent / g or less, and most preferably 50 ⁇ mol equivalent / g or more and 80 ⁇ mol equivalent / g or less.
  • the amount of the carboxy terminal of the (B) amorphous polyamide is in the above range, the compatibility with the (A) crystalline polyamide can be further improved, and the number average particle size of the domain can be further reduced. .. As a result, a polyamide composition having excellent fluidity, vibration damping and noise suppressing effects when formed into a molded product can be obtained. In addition, the surface appearance of the molded product obtained from the polyamide composition containing a component typified by an inorganic filler becomes more excellent.
  • the amount of carboxy terminal can be measured by NMR.
  • the total amount of (B) amino-terminal amount and carboxy-terminal amount of (B) amorphous polyamide is preferably 50 ⁇ mol equivalent / g or more and 300 ⁇ mol equivalent / g or less, and 60 ⁇ mol equivalent / g or more and 270 ⁇ mol equivalent per 1 g of (B) amorphous polyamide.
  • / G or less is more preferable, 70 ⁇ mol equivalent / g or more and 250 ⁇ mol equivalent / g or less is further preferable, 80 ⁇ mol equivalent / g or more and 200 ⁇ mol equivalent / g or less is particularly preferable, and 90 ⁇ mol equivalent / g or more and 150 ⁇ mol equivalent / g or less is most preferable.
  • the compatibility with the (A) crystalline polyamide can be further improved, and the number average particle diameter of the domain can be improved. Can be made smaller.
  • the polyamide composition of the present embodiment includes (C) an elastomer, (D) an inorganic filler, (E) carbon black, and (F).
  • lubricants include lubricants, (G) phosphorus-based flame retardants, (H) nucleating agents, (I) heat stabilizers, (J) other polymers, and (K) other additives. Ingredients may be further included.
  • the polyamide composition of the present embodiment may contain (C) an elastomer in addition to (A) crystalline polyamide and (B) amorphous polyamide described above.
  • Examples of the elastomer include polymers showing elastic behavior such as hydrogenated styrene-based thermoplastic elastomers, olefin elastomers, urethane elastomers, and polyester elastomers.
  • Examples of the hydrogenated styrene-based thermoplastic elastomer include hydrogenated block copolymers having a styrene block.
  • the hydrogenated block copolymer is not particularly limited, and examples thereof include an unmodified hydrogenated block copolymer, a modified hydrogenated block copolymer, and a mixture thereof.
  • the hydrogenated block copolymer may be used alone or in combination of two or more.
  • Examples of the olefin elastomer include ethylene propylene elastomer.
  • the molded product obtained by molding the polyamide composition of the present embodiment can exhibit vibration damping and noise suppression effects even if it does not contain an elastomer. Further, as the content of the elastomer increases, the strength and elastic modulus of the molded product may decrease. Therefore, the content of the elastomer is preferably 12% by mass or less, preferably 5% by mass or less, based on the total mass of (A) crystalline polyamide and (B) amorphous polyamide in the polyamide composition. More preferably, it is more preferably mass% or less, further preferably 1 mass% or less, particularly preferably 0.1 mass% or less, and most preferably 0 mass%.
  • the inorganic filler (D) is not limited to the following, but is not limited to, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, clay, flake-shaped glass, talc, and the like.
  • Kaolin mica, hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide , Calcium silicate, sodium aluminosilicate, magnesium silicate, Ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling fluorine mica , Apatite and the like.
  • One type of these inorganic fillers may be used alone, or two or more types may be used in combination.
  • glass fiber from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber and clay.
  • one or more selected are preferred.
  • one or more selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate and clay is more preferable.
  • the number average fiber diameter (d) is preferably 3 ⁇ m or more and 30 ⁇ m or less, more preferably 3 ⁇ m or more and 20 ⁇ m or less, further preferably 3 ⁇ m or more and 12 ⁇ m or less, and particularly preferably 3 ⁇ m or more and 9 ⁇ m or less. It is preferably 4 ⁇ m or more and 6 ⁇ m or less, most preferably.
  • the cross section may be round or flat.
  • a flat cross section include, but are not limited to, a rectangle, an oval shape close to a rectangle, an ellipse shape, and a cocoon shape having a central portion in the longitudinal direction.
  • the "flattening ratio" in the present specification means a value represented by d2 / d1 when the major axis of the fiber cross section is d2 and the minor axis of the fiber cross section is d1 (a perfect circle is flat). The rate will be about 1).
  • the number average fiber diameter (d) is 3 ⁇ m or more and 30 ⁇ m or less, and the weight average fiber length (d) is particularly high from the viewpoint of imparting excellent mechanical strength to the polyamide composition. It is preferable that l) is 100 ⁇ m or more and 750 ⁇ m or less, and the ratio of the weight average fiber length (l) to the number average fiber diameter (d), that is, the aspect ratio (l / d) is 10 or more and 100 or less. be.
  • the "number average fiber diameter (d)" referred to here is an average value of the major axis (d2) of the fiber cross section, and is obtained by using the calculation method described later.
  • the flatness is preferably 1.5 or more, and 1.5 or more is 10.0.
  • the following is more preferable, 2.5 or more and 10.0 or less are further preferable, more than 3.0 and 6.0 or less are particularly preferable, and 3.1 or more and 6.0 or less are most preferable.
  • the flatness is within the above range, crushing can be more effectively prevented during mixing with other components, kneading, molding, etc., so that the desired effect for the molded body can be more sufficiently obtained. become.
  • the thickness of the glass fiber or carbon fiber having a flatness of 1.5 or more is not limited to the following, but the minor axis d1 of the fiber cross section is 0.5 ⁇ m or more and 25 ⁇ m or less and the major axis d2 of the fiber cross section is 1.25 ⁇ m or more. It is preferably 250 ⁇ m or less. It is more preferable that the minor axis d1 of the fiber cross section is 3.0 ⁇ m or more and 25 ⁇ m or less and the major axis d2 of the fiber cross section is 1.25 ⁇ m or more and 250 ⁇ m or less.
  • the difficulty of spinning the fiber can be more effectively avoided, and the strength of the molded body is not reduced without reducing the contact area with the resin (polyamide). Can be further improved.
  • Glass fiber or carbon fiber having a flatness of 1.5 or more is an orifice plate having a large number of orifices on the bottom surface, which surrounds a plurality of orifice outlets and has a convex edge extending downward from the bottom surface, or an orifice plate.
  • the fiber strands may be used as they are as roving, or may be further obtained in a cutting step and used as chopped glass strands.
  • the "number average fiber diameter (d)" and the “weight average fiber length (l)" in the present specification can be obtained by the following methods.
  • the polyamide composition is placed in an electric furnace to incinerate the contained organic matter.
  • 100 or more glass fibers (or carbon fibers) are arbitrarily selected and observed with a scanning electron microscope (SEM), and the fiber diameter (major axis) of these glass fibers (or carbon fibers) is observed.
  • the number average fiber diameter can be obtained.
  • the weight average fiber length can be obtained by measuring the fiber length using SEM photographs of the above 100 or more glass fibers (or carbon fibers) taken at a magnification of 1000 times.
  • the glass fiber or the carbon fiber may be surface-treated with a silane coupling agent or the like.
  • silane coupling agent include, but are not limited to, aminosilanes, mercaptosilanes, epoxysilanes, vinylsilanes and the like.
  • aminosilanes include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane and the like.
  • Examples of the mercaptosilanes include ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane.
  • These silane coupling agents may be used alone or in combination of two or more. Among them, aminosilanes are preferable as the silane coupling agent.
  • the glass fiber or the carbon fiber may further contain a sizing agent.
  • a sizing agent for example, a copolymer or an epoxy compound containing an unsaturated vinyl monomer containing a carboxylic acid anhydride and an unsaturated vinyl monomer excluding the unsaturated vinyl monomer containing a carboxylic acid anhydride as a constituent unit.
  • These sizing agents may be used alone or in combination of two or more.
  • the sizing agent is a single amount of unsaturated vinyl excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer.
  • One or more selected from the group consisting of a copolymer containing a body as a constituent unit, an epoxy compound, and a polyurethane resin is preferable. Further, it is selected from the group consisting of a copolymer and a polyurethane resin containing an unsaturated vinyl monomer containing a carboxylic acid anhydride and an unsaturated vinyl monomer excluding the unsaturated vinyl monomer containing a carboxylic acid anhydride as a constituent unit. More than one kind is more preferable.
  • the glass fiber or carbon fiber is continuously produced by applying the above-mentioned sizing agent to the fiber and drying the fiber strand produced by using a known method such as a roller type applicator in the known manufacturing process of the fiber. It is obtained by reacting specifically.
  • the fiber strand may be used as it is as a roving, or may be further obtained in a cutting step and used as a chopped glass strand.
  • the sizing agent preferably imparts (adds) about 0.2% by mass or more and 3% by mass or less as a solid content to the total mass of the glass fiber or carbon fiber, and is 0.3% by mass or more and 2% by mass or less. It is more preferable to add (add) the following degree.
  • the sizing of the fibers can be maintained more effectively.
  • the thermal stability of the obtained polyamide composition is further improved.
  • the strands may be dried after the cutting step or after the strands have been dried.
  • inorganic fillers other than glass fiber and carbon fiber from the viewpoint of improving the strength, rigidity and surface appearance of the molded body, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, hoe Aluminum acid acid fiber or clay is preferred. Wollastonite, kaolin, mica, talc, calcium carbonate or clay are more preferred. Wollastonite, kaolin, mica or talc are more preferred. Wollastonite, mica or talc are particularly preferred. These inorganic fillers may be used alone or in combination of two or more.
  • the average particle size of the inorganic filler other than the glass fiber and the carbon fiber is preferably 0.01 ⁇ m or more and 38 ⁇ m or less, more preferably 0.03 ⁇ m or more and 30 ⁇ m or less, and 0 It is more preferably 0.05 ⁇ m or more and 25 ⁇ m or less, further preferably 0.10 ⁇ m or more and 20 ⁇ m or less, and particularly preferably 0.15 ⁇ m or more and 15 ⁇ m or less.
  • a polyamide composition having better toughness and surface appearance of the molded product can be obtained.
  • an excellent polyamide composition can be obtained in terms of cost, handling surface of powder, and physical properties (fluidity, etc.).
  • the number average particle size (hereinafter, may be simply referred to as "average particle size") is used as the average particle size. If the cross section is not a circle, the maximum value of the length is the (number average) fiber diameter.
  • the above-mentioned preferable range of the number average particle diameter and the following number average particle diameter (d) A numerical range calculated from a preferable range of the aspect ratio (l / d) of the number average particle length (l) with respect to is preferable.
  • the aspect ratio (l / d) of the number average particle length (l) to the number average particle diameter (d) improves the surface appearance of the molded product and is used in injection molding machines and the like. From the viewpoint of preventing wear of the metallic parts, 1.5 or more and 10 or less are preferable, 2.0 or more and 5 or less are more preferable, and 2.5 or more and 4 or less are further preferable.
  • the inorganic filler other than the glass fiber and the carbon fiber may be surface-treated with a silane coupling agent, a titanate-based coupling agent, or the like.
  • a silane coupling agent examples include those similar to those exemplified for the above-mentioned glass fibers and carbon fibers. Among them, aminosilanes are preferable as the silane coupling agent.
  • Such a surface treatment agent may be treated in advance on the surface of the inorganic filler, or may be added when the polyamide and the inorganic filler are mixed. The amount of the surface treatment agent added is preferably 0.05% by mass or more and 1.5% by mass or less with respect to the total mass of the inorganic filler.
  • the content of the inorganic filler is preferably 5% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and 20% by mass or more and 65% by mass or less with respect to the total mass of the polyamide composition. More preferably, it is particularly preferably 20% by mass or more and 60% by mass or less, and most preferably 20% by mass or more and 50% by mass or less.
  • (E) Carbon Black is classified into furnace black, channel black, thermal black, etc. according to its manufacturing method, and is classified into acetylene black, ketjen black, oil black, gas black, etc., depending on the difference in raw materials.
  • the polyamide composition of the present embodiment can be used without particular limitation.
  • the average primary particle size of carbon black is preferably close to the number average particle size of the domains of (A) amorphous polyamide dispersed in (A) crystalline polyamide, and specifically, 10 nm or more. It is more preferably 10 nm or more and 100 nm or less, further preferably 15 nm or more and 60 nm or less, further preferably 15 nm or more and 50 nm or less, and even more preferably 15 nm or more and 40 nm or less. It is particularly preferably 15 nm or more and 30 nm or less. When the average primary particle size is within the above range, the weather resistance, vibration damping, and noise suppression effect of the molded product can be further improved.
  • an image in which carbon black particles are dispersed is obtained by the procedure described in the ATM D3849 standard (standard test method for carbon black-morphological characterization by electron microscopy), and 3 as unit constituent particles from this image. It is a value obtained by measuring the diameters of 000 particles and as the average value of these measured values.
  • the specific surface area of carbon black is preferably in the range of 50 m 2 / g or more and 300 m 2 / g or less (BET adsorption method). When the specific surface area is within the above range, the low warpage property, surface appearance, weather resistance, and gloss retention rate of the molded product can be further improved.
  • the specific surface area of carbon black is a value measured from the amount of nitrogen adsorbed according to JIS K6217.
  • the amount of DBP oil absorbed by carbon black (the amount of dibutyl phthalate absorbed by 100 g of carbon black) is preferably 50 mL / 100 g or more and 150 mL / 100 g or less.
  • the DBP oil absorption amount of carbon black is a value measured according to JIS K6221.
  • the content of carbon black is preferably 0.02% by mass or more and 3.0% by mass or less, more preferably 0.02% by mass or more and 1.0% by mass or less, and 0. It is more preferably 02% by mass or more and 0.8% by mass or less, particularly preferably 0.03% by mass or more and 0.1% by mass or less, and most preferably 0.03% by mass or more and 0.06% by mass or less.
  • the content of carbon black is within the above range, the weather resistance, vibration damping, and noise suppression effect can be further improved without impairing the appearance of the molded product.
  • the (F) lubricant is not particularly limited, and examples thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like.
  • the lubricant can also be used as a molding improver.
  • Examples of the higher fatty acid include linear or branched linear or branched saturated or unsaturated aliphatic monocarboxylic acids having 8 or more and 40 or less carbon atoms.
  • Examples of the saturated or unsaturated aliphatic monocarboxylic acid having 8 or more carbon atoms and 40 or less carbon atoms include lauric acid, palmitic acid, stearic acid, behenic acid, and montanic acid.
  • Examples of the branched chain saturated aliphatic monocarboxylic acid having 8 or more carbon atoms and 40 or less carbon atoms include isopalmitic acid and isostearic acid.
  • Examples of the linear unsaturated aliphatic monocarboxylic acid having 8 or more carbon atoms and 40 or less carbon atoms include oleic acid and erucic acid.
  • Examples of the branched chain unsaturated aliphatic monocarboxylic acid having 8 or more carbon atoms and 40 or less carbon atoms include isooleic acid and the like. Among them, stearic acid or montanic acid is preferable as the higher fatty acid.
  • the higher fatty acid metal salt is a metal salt of higher fatty acid.
  • the metal element of the metal salt include Group 1 element, Group 2 element and Group 3 element, zinc, aluminum and the like in the Periodic Table of the Elements.
  • Examples of Group 1 elements in the Periodic Table of the Elements include sodium, potassium and the like.
  • Examples of Group 2 elements in the Periodic Table of the Elements include calcium and magnesium.
  • Examples of Group 3 elements in the Periodic Table of the Elements include scandium and yttrium. Among them, Group 1 and Group 2 elements of the Periodic Table of the Elements, or aluminum is preferable, and sodium, potassium, calcium, magnesium, or aluminum is more preferable.
  • the higher fatty acid metal salt examples include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate and the like.
  • a metal salt of montanic acid or a metal salt of stearic acid is preferable.
  • the higher fatty acid ester is an esterified product of a higher fatty acid and an alcohol.
  • an ester of an aliphatic carboxylic acid having 8 or more and 40 or less carbon atoms and an aliphatic alcohol having 8 or more and 40 carbon atoms or less is preferable.
  • the aliphatic alcohol having 8 or more carbon atoms and 40 or less carbon atoms include stearyl alcohol, behenyl alcohol, and lauryl alcohol.
  • Specific examples of the higher fatty acid ester include stearyl stearate and behenic behenate.
  • the higher fatty acid amide is an amide compound of a higher fatty acid.
  • the higher fatty acid amide include stearate amide, oleic acid amide, erucate amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl steayl amide, N-stearyl erucate amide and the like.
  • Each of these higher fatty acids, higher fatty acid metal salts, higher fatty acid esters and higher fatty acid amides may be used alone or in combination of two or more.
  • the phosphorus-based flame retardant is not particularly limited as long as it is a flame retardant that does not contain a halogen element but contains a phosphorus element.
  • Examples of the phosphorus-based flame retardant include a phosphoric acid ester-based flame retardant, a polyphosphate melamine-based flame retardant, a phosphazen-based flame retardant, a phosphinic acid-based flame retardant, and a red phosphorus-based flame retardant.
  • the phosphorus-based flame retardant is preferably a phosphoric acid ester-based flame retardant, a polyphosphate melamine-based flame retardant, a phosphazen-based flame retardant or a phosphinic acid-based flame retardant, and a phosphinic acid-based flame retardant is particularly preferable. ..
  • phosphinic acid-based flame retardant examples include a phosphinate represented by the following general formula (1) (hereinafter, may be abbreviated as “phosphinate (1)”) and the following general formula (2). ) (Hereinafter, may be abbreviated as “diphosphinate (2)”) and at least one phosphinate selected from the group consisting of condensates thereof may be contained.
  • R 11 and R 12 are independently an alkyl group having 1 or more and 6 or less carbon atoms or an aryl group having 6 or more and 10 or less carbon atoms.
  • M n11 + is an n11-valent metal ion.
  • M is an element belonging to Group 2 or Group 15 of the Periodic Table of the Elements, a transition element, zinc or aluminum.
  • n11 is 2 or 3.
  • a plurality of R 11 and R 12 may be the same or different from each other.
  • R 21 and R 22 are independently alkyl groups having 1 or more and 6 or less carbon atoms or aryl groups having 6 or more and 10 or less carbon atoms.
  • Y 21 is an alkylene group having 1 or more and 10 or less carbon atoms or an arylene group having 6 or more and 10 or less carbon atoms.
  • M'm21 + is an m21-valent metal ion.
  • M' is an element belonging to Group 2 or Group 15 of the Periodic Table of the Elements, a transition element, zinc or aluminum.
  • n21 is an integer of 1 or more and 3 or less. When n21 is 2 or 3, a plurality of R 21 , R 22 and Y 21 may be the same or different from each other.
  • m21 is 2 or 3.
  • x is 1 or 2. When x is 2, a plurality of existing M's may be the same or different.
  • R 11 , R 12 , R 21 and R 22 are independently alkyl groups having 1 or more and 6 or less carbon atoms and aryl groups having 6 or more and 10 or less carbon atoms.
  • a plurality of R 11 and R 12 may be the same or different from each other, but they are preferably the same because they are easy to manufacture.
  • n21 is 2 or 3
  • the plurality of R 21 and R 22 may be the same or different, but they are preferably the same because they are easy to manufacture.
  • the alkyl group may be chain-like or cyclic, but is preferably chain-like.
  • the chain alkyl group may be linear or branched.
  • Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group and the like.
  • Examples of the branched alkyl group include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 2-methylbutyl group and 3-methylbutyl group.
  • aryl group examples include a phenyl group and a naphthyl group.
  • Alkyl groups and aryl groups may have substituents.
  • substituents in the alkyl group include an aryl group having 6 or more and 10 or less carbon atoms.
  • substituent in the aryl group include an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms.
  • alkyl group having a substituent examples include a benzyl group and the like.
  • aryl group having a substituent examples include a tolyl group and a xylyl group.
  • R11, R12 , R21 and R22 an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
  • Y 21 is an alkylene group having 1 or more and 10 or less carbon atoms or an arylene group having 6 or more and 10 or less carbon atoms.
  • n21 is 2 or 3
  • the plurality of Y 21s existing may be the same or different, but they are preferably the same because they are easy to manufacture.
  • the alkylene group may be chain-like or cyclic, but is preferably chain-like.
  • the chain alkylene group may be linear or branched.
  • Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group and the like.
  • Examples of the branched chain alkylene group include a 1-methylethylene group and a 1-methylpropylene group.
  • Examples of the arylene group include a phenylene group and a naphthylene group.
  • the alkylene group and the arylene group may have a substituent.
  • substituent in the alkylene group include an aryl group having 6 or more and 10 or less carbon atoms.
  • substituent in the arylene group include an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms.
  • alkylene group having a substituent examples include a phenylmethylene group, a phenylethylene group, a phenyltrimethylene group, a phenyltetramethylene group and the like.
  • arylene group having a substituent examples include a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group, a tert-butylnaphthylene group and the like.
  • Y21 an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms is preferable, and a methylene group or an ethylene group is more preferable.
  • M and M' M n11 + is an n11-valent metal (M) ion
  • M'm21 + is an m21-valent metal (M') ion.
  • M and M' are independently elements belonging to Group 2 or Group 15 of the Periodic Table of the Elements, transition elements, zinc or aluminum. Examples of the element belonging to the second group of the Periodic Table of the Elements include calcium and magnesium. Examples of the element belonging to Group 15 of the Periodic Table of the Elements include bismuth and the like. Further, when x is 2, a plurality of M's existing may be the same or different, but they are preferably the same because they are easy to manufacture. Among them, as M and M', calcium, zinc or aluminum is preferable, and calcium or aluminum is more preferable.
  • (X) x represents the number of M'and is 1 or 2. x can be appropriately selected depending on the type of M'and the number of diphosphinic acids.
  • n11 represents the number of phosphinic acids and the valence of M, and is 2 or 3. n11 can be appropriately selected depending on the type and valence of M. n21 represents the number of diphosphinic acids and is an integer of 1 or more and 3 or less. n21 can be appropriately selected depending on the type and number of M'.
  • (M21) m21 represents the valence of M'and is 2 or 3.
  • the preferred phosphinate (1) for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, ethylmethylphosphine.
  • Zinc Ethylmethylphosphinate Calcium diethylphosphinate, Magnesium diethylphosphinate, Aluminum diethylphosphinate, Zinc diethylphosphinate, Calcium methyl-n-propylphosphinate, Magnesium methyl-n-propylphosphinate, Methyl-n -Aluminum propylphosphinate, zinc methyl-n-propylphosphinate, calcium methanedi (methylphosphinic acid), magnesium methanedi (methylphosphinic acid), aluminum methanedi (methylphosphinic acid), zinc methanedi (methylphosphinic acid), benzene-1 , 4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphin
  • the preferred diphosphinate (2) include methanedi (methylphosphinic acid) calcium, methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, and benzene-1.
  • 4-di (methylphosphinic acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, benzene-1,4-di (methylphosphinic acid) ) Zinc and the like can be mentioned.
  • the method for producing phosphinates is not particularly limited, and examples thereof include a method for producing phosphinic acid in an aqueous solution using phosphinic acid and a metal carbonate, a metal hydroxide, or a metal oxide. These are essentially monomeric compounds, but depending on the reaction conditions, polymer phosphinates, which are condensates having a degree of condensation of 1 or more and 3 or less depending on the environment, are also included.
  • the content of the phosphorus-based flame retardant is preferably 0.1% by mass or more and 30% by mass or less, and 5% by mass or more and 30% by mass, based on the total mass of (A) crystalline polyamide and (B) amorphous polyamide.
  • the following is more preferable, 10% by mass or more and 29% by mass or less is further preferable, and 15% by mass or more and 29% by mass or less is particularly preferable.
  • the nucleating agent means a substance that can obtain at least one of the following effects (1) to (3) by addition.
  • (1) The effect of raising the crystallization peak temperature of the polyamide composition.
  • (2) The effect of reducing the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak.
  • (3) The effect of making the spherulites of the obtained molded product finer or uniform in size.
  • nucleating agent examples include, but are not limited to, talc, boron nitride, mica, kaolin, silicon nitride, potassium titanate, molybdenum disulfide and the like.
  • the nucleating agent only one type may be used alone, or two or more types may be used in combination.
  • talc or boron nitride is preferable as the nucleating agent from the viewpoint of the effect of the nucleating agent.
  • the number average particle size of the nucleating agent is preferably 0.01 ⁇ m or more and 10 ⁇ m or less.
  • the number average particle size of the nucleating agent can be measured by the following method. First, the molded product is dissolved in a solvent in which polyamide such as formic acid is soluble. Then, for example, 100 or more nucleating agents are arbitrarily selected from the obtained insoluble components. Then, it can be obtained by observing with an optical microscope, a scanning electron microscope, or the like and measuring the particle size.
  • the content of the nucleating agent in the polyamide composition of the present embodiment is preferably 0.001% by mass or more and 1% by mass or less, and 0.001% by mass or more and 0.5% by mass, based on the total mass of the polyamide composition. % Or less is more preferable, and 0.001% by mass or more and 0.09% by mass or less is further preferable.
  • the heat stabilizer is not limited to the following, but is not limited to, for example, a phenol-based heat stabilizer, a phosphorus-based heat stabilizer, an amine-based heat stabilizer, and Group 3, Group 4, and Group 11 to 11 of the Periodic Table of the Elements. Examples thereof include metal salts of Group 14 elements, alkali metals and halides of alkaline earth metals.
  • phenolic heat stabilizer examples include, but are not limited to, hindered phenol compounds.
  • the hindered phenol compound has a property of imparting excellent heat resistance and light resistance to resins and fibers such as polyamide.
  • the hindered phenol compound is not limited to the following, and is, for example, N, N'-hexane-1,6-diylbis [3- (3,5-di-tertbutyl-4-hydroxyphenylpropion). Amid), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4) -Hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis ⁇ 2- [3- (3- (3- (3-) tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro [5,5] undecane,
  • the hindered phenol compound includes N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide). )] Is preferable.
  • the content of the phenol-based heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less, preferably 0.1% by mass, based on the total mass of the polyamide composition. More preferably, it is by mass% or more and 1% by mass or less.
  • the content of the phenolic heat stabilizer is within the above range, the heat-resistant aging property of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.
  • the phosphorus-based heat stabilizer is not limited to, but is not limited to, for example, pentaerythritol type phosphite compound, trioctylphosphite, trilaurylphosphite, tridecylphosphite, octyldiphenylphosphite, trisisodecyl.
  • Phenyl diisodecyl phosphite Phenyl diisodecyl phosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyl (tridecyl) phosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2) , 4-Di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4'-butylidene-bis ( 3-Methyl-6-tert-butylphenyl-tetra-tridecyl) diphosphite, te
  • phosphorus-based heat stabilizers may be used alone or in combination of two or more.
  • phosphorus-based heat stabilizers pentaerythritol-type phosphite compounds and tris (2,4-di-tert-butylphenyl) are used from the viewpoint of further improving the heat-resistant aging property of the polyamide composition and reducing the amount of gas generated.
  • One or more selected from the group consisting of phosphite is preferable.
  • the pentaerythritol-type phosphite compound is not limited to the following, and is, for example, 2,6-di-tert-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di-.
  • pentaerythritol-type phosphite compounds may be used alone or in combination of two or more.
  • pentaerythritol-type phosphite compound bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2) are used from the viewpoint of reducing the amount of gas generated in the polyamide composition.
  • 6-Di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite bis (2,6-di-tert-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6) -Di-tert-octyl-4-methylphenyl) pentaerythritol diphosphite is preferably one or more selected from the group consisting of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos. Fight is more preferred.
  • the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less, preferably 0.1% by mass, based on the total mass of the polyamide composition. More preferably, it is by mass% or more and 1% by mass or less.
  • the content of the phosphorus-based heat stabilizer is within the above range, the heat-resistant aging property of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.
  • the amine-based heat stabilizer is not limited to the following, and is, for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra.
  • Methylpiperidine 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-Tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-Tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2 , 6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis
  • the content of the amine-based heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less, preferably 0.1% by mass, based on the total mass of the polyamide composition. More preferably, it is by mass% or more and 1% by mass or less.
  • the content of the amine-based heat stabilizer is within the above range, the heat-resistant aging property of the obtained molded product can be further improved, and the amount of gas generated can be further reduced.
  • the metal salts of the elements of Group 3, Group 4 and Groups 11 to 14 of the Periodic Table of the Elements are not limited as long as they are salts of metals belonging to these groups.
  • a copper salt is preferable from the viewpoint of further improving the heat-resistant aging property of the obtained molded product.
  • the copper salt is not limited to the following, and is, for example, copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, stearic acid.
  • Examples of copper and a copper complex salt in which copper is coordinated with a chelating agent can be mentioned.
  • Examples of the copper halide include copper iodide, cuprous bromide, cupric bromide, and cuprous chloride.
  • Examples of the chelating agent include ethylenediamine and ethylenediaminetetraacetic acid. These copper salts may be used alone or in combination of two or more. Among them, the copper salt is preferably at least one selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, and is composed of copper iodide and copper acetate. One or more selected from the group is more preferable.
  • the content of the copper salt in the polyamide composition is 0.01 mass by mass with respect to the total mass of the polyamide ((A) crystalline polyamide and (B) amorphous polyamide). % Or more and 0.60% by mass or less are preferable, and 0.02% by mass or more and 0.40% by mass or less are more preferable.
  • the content of the copper salt is within the above range, the heat-resistant aging property of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be more effectively suppressed.
  • the content concentration of the copper element derived from the above copper salt is 106 parts by mass of the polyamide ((A) crystalline polyamide and (B) amorphous polyamide) from the viewpoint of improving the heat aging property of the polyamide composition.
  • (1 million parts by mass) 10 parts by mass or more and 2000 parts by mass or less are preferable, 30 parts by mass or more and 1500 parts by mass or less are more preferable, and 50 parts by mass or more and 500 parts by mass or less are further preferable.
  • halides of the alkali metal and the alkaline earth metal include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride and the like.
  • the halides of these alkali metals and alkaline earth metals one type may be used alone, or two or more types may be used in combination.
  • the halide of the alkali metal and the alkaline earth metal one or more selected from the group consisting of potassium iodide and potassium bromide is preferable from the viewpoint of improving heat aging property and suppressing metal corrosion, and iodide. Potassium is more preferred.
  • the content of the alkali metal and alkaline earth metal halides in the polyamide composition is determined by the polyamide ((A) crystalline polyamide and (B) amorphous polyamide). ) With respect to 100 parts by mass, 0.05 parts by mass or more and 20 parts by mass or less are preferable, and 0.2 parts by mass or more and 10 parts by mass or less are more preferable.
  • the content of the halide of the alkali metal and the alkaline earth metal is within the above range, the heat-resistant aging property of the obtained molded body is further improved, and the precipitation of copper and the metal corrosion are suppressed more effectively. be able to.
  • the component of the heat stabilizer described above only one kind may be used alone, or two or more kinds may be used in combination.
  • a mixture of a copper salt and a halide of an alkali metal and an alkaline earth metal is preferable from the viewpoint of further improving the heat aging property of the obtained molded product.
  • the content ratio of the copper salt to the halides of the alkali metal and the alkaline earth metal is preferably 2/1 or more and 40/1 or less as the molar ratio of halogen to copper (halogen / copper), 5/1 or more and 30 /. 1 or less is more preferable.
  • the molar ratio of halogen to copper (halogen / copper) is within the above range, the heat-resistant aging property of the obtained molded product can be further improved. Further, when the molar ratio of halogen to copper (halogen / copper) is at least the above lower limit value, precipitation of copper and metal corrosion can be suppressed more effectively.
  • the other polymer is not particularly limited as long as it is other than polyamide, and examples thereof include polyester, liquid crystal polyester, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyarylate, phenol resin, and epoxy resin. ..
  • polyester include, but are not limited to, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate and the like.
  • the content of the other polymer is preferably 1% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 20% by mass or less, and 5% by mass or more and 15% by mass or less with respect to the total amount of polyamide in the polyamide composition. Is even more preferable.
  • the content of the other polymer is within the above range, a polyamide composition having excellent heat resistance and releasability can be obtained.
  • the polyamide composition of the present embodiment may contain other additives commonly used in the polyamide composition as long as the effects of the polyamide composition of the present embodiment are not impaired.
  • Other additives include, for example, colorants such as pigments and dyes (including colored master batches), flame retardants, fibrillation agents, fluorescent bleaching agents, plasticizing agents, antioxidants, ultraviolet absorbers, antistatic agents, etc. Examples include a fluidity improving agent and a spreading agent.
  • the content of the other additives varies depending on the type, use of the polyamide composition, etc., and therefore the polyamide obtained by the production method of the present embodiment. There is no particular limitation as long as the effect of the composition is not impaired.
  • the method for producing the polyamide composition of the present embodiment is particularly limited as long as it is a production method including a step of melt-kneading the raw material components including (A) crystalline polyamide and (B) amorphous polyamide. is not.
  • a step of melt-kneading the raw material components including (A) crystalline polyamide and (B) amorphous polyamide with an extruder is included, and the set temperature of the extruder is set to the melting peak temperature Tm2 + 30 ° C. of the above-mentioned polyamide composition.
  • the following method is preferable.
  • the raw material component containing polyamide for example, the above-mentioned (A) crystalline polyamide, the above-mentioned (B) amorphous polyamide and other raw materials are mixed by using a tumbler, a Henschel mixer or the like, and melt-kneaded.
  • a method of supplying to a machine and kneading, a method of blending other raw materials from a side feeder into the above (A) crystalline polyamide and the above (B) amorphous polyamide melted by a single-screw or twin-screw extruder, etc. Can be mentioned.
  • all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports.
  • the melt-kneading temperature is preferably about 250 ° C. or higher and 350 ° C. or lower in terms of resin temperature.
  • the melt-kneading time is preferably about 0.25 minutes or more and 5 minutes or less.
  • the apparatus for performing melt kneading is not particularly limited, and for example, a known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, or a mixing roll can be used.
  • the melt kneader it is preferable to use a twin-screw extruder having a screw diameter (D) of 30 mm or more in the same direction. Further, in the twin-screw extruder, the ratio (L / D) of the extruder length (L) to the screw diameter (D) is preferably 35 or more, and more preferably 50 or more.
  • the screw rotation speed (N) is required for efficient kneading so as to have the number average particle size of the domains of (A) amorphous polyamide dispersed in (A) crystalline polyamide. Is preferably 300 rpm or more, and the ratio Q / N of the screw rotation speed (N) and the discharge amount (Q) is preferably 0.5 or more.
  • the inorganic filler is added, in order for the inorganic filler to improve the kneading efficiency, (A) crystalline polyamide and (B) amorphous polyamide are dry-blended and then the upstream side of the twin-screw extruder. It is preferable to supply the material from the supply port and supply the inorganic filler from the first supply port on the downstream side of the twin-screw extruder.
  • the molecular weight, molecular weight distribution, melting point Tm2, terminal amount sealed with a sealant, amino terminal amount and carboxy terminal amount, and bending elastic modulus of the polyamide composition of the present embodiment can have the following configurations, which will be described later. It can be measured by the method described in the Examples.
  • a weight average molecular weight (Mw) can be used as an index of the molecular weight of the polyamide composition.
  • the weight average molecular weight (Mw) of the polyamide composition is preferably 15,000 or more and 50,000 or less, more preferably 15,000 or more and 45,000 or less, further preferably 15,000 or more and 39000 or less, further preferably 15,000 or more and 35,000 or less, and particularly preferably 15,000 or more and 34,000 or less. , 25,000 or more and 32,000 or less are most preferable.
  • the weight average molecular weight (Mw) When the weight average molecular weight (Mw) is in the above range, a polyamide composition excellent in mechanical properties when formed into a molded body, particularly water absorption rigidity, thermal rigidity, fluidity, corrosion resistance and the like can be obtained. Further, the polyamide composition containing a component typified by an inorganic filler has a better surface appearance.
  • Examples of the method for controlling the Mw of the polyamide composition within the above range include the use of (A) crystalline polyamide and (B) amorphous polyamide having a weight average molecular weight in the above range.
  • the measurement of Mw can be measured by using gel permeation chromatography (GPC) as described in the following examples.
  • the molecular weight distribution of the polyamide composition of the present embodiment uses the weight average molecular weight (Mw) / number average molecular weight (Mn) as an index. Measurements of Mw and Mn can be made using gel permeation chromatography (GPC), as described in the Examples below.
  • the lower limit of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the polyamide composition of the present embodiment is preferably 1.0, more preferably 1.2, still more preferably 1.5, and 1.8. Even more preferable, 1.9 is particularly preferable, and 2.0 is most preferable.
  • the upper limit of Mw / Mn of the polyamide composition of the present embodiment is preferably 3.5, more preferably 3.0, still more preferably 2.6, still more preferably 2.4, and 2.2. Particularly preferred, 2.1 is most preferred.
  • the Mw / Mn of the polyamide composition of the present embodiment is preferably 1.0 or more and 3.5 or less, more preferably 1.2 or more and 3.0 or less, still more preferably 1.5 or more and 2.6 or less, and 1.8. More preferably 2.4 or more, more preferably 1.9 or more and 2.2 or less, and most preferably 2.0 or more and 2.1 or less.
  • the proportion of polyamide molecules having a three-dimensional structure of the molecule can be further lowered, and the three-dimensional structure of the molecule can be more preferably prevented during high-temperature processing, and the fluidity can be improved. Can be kept better. This tends to improve the surface appearance of the molded product obtained from the polyamide composition containing a component typified by an inorganic filler.
  • the melting point Tm2 of the polyamide composition is preferably 200 ° C. or higher, more preferably 220 ° C. or higher and 270 ° C. or lower, further preferably 230 ° C. or higher and 265 ° C. or lower, particularly preferably 240 ° C. or higher and 260 ° C. or lower, and 250 ° C. or higher and 260 ° C. or lower. Is the most preferable.
  • the melting point Tm2 of the polyamide composition is at least the above lower limit value, it tends to be possible to obtain a polyamide composition having superior thermal rigidity and the like.
  • the melting point Tm2 of the polyamide composition is not more than the above upper limit value, there is a tendency that thermal decomposition of the polyamide composition in melt processing such as extrusion and molding can be further suppressed.
  • the terminal amount sealed with the encapsulant in the polyamide composition is 0 ⁇ mol equivalent per 1 g of at least one selected from the group consisting of the (A) crystalline polyamide and the (B) amorphous polyamide. It can be g or more and 200 ⁇ mol equivalent / g or less, preferably 5 ⁇ mol equivalent / g or more and 180 ⁇ mol equivalent / g or less, 10 ⁇ mol equivalent / g or more and 170 ⁇ mol equivalent / g or less, and 15 ⁇ mol equivalent / g or more and 160 ⁇ mol equivalent / g or less.
  • the amount of the terminal sealed with the sealant is within the above range, the generation of mold deposit (MD) during molding is suppressed, and the surface appearance, thermal rigidity, vibration damping and noise suppression of the molded product are suppressed. A composition having an excellent effect can be obtained.
  • the total amount of amino-terminal amounts and carboxy-terminal amounts in the polyamide composition is 70 ⁇ mol equivalent / g per 1 g of at least one selected from the group consisting of the (A) crystalline polyamide and the (B) amorphous polyamide. G or more and 145 ⁇ mol equivalent / g or less are preferable, 80 ⁇ mol equivalent / g or more and 140 ⁇ mol equivalent / g or less are more preferable, 90 ⁇ mol equivalent / g or more and 130 ⁇ mol equivalent / g or less are further preferable, and 100 ⁇ mol equivalent / g or more and 120 ⁇ mol equivalent / g or less are particularly preferable. preferable.
  • the total amount of the amino terminal amount and the carboxy terminal amount in the polyamide composition is in the above range, a polyamide composition having better fluidity and the like can be obtained.
  • the surface appearance of the molded product obtained from the polyamide composition containing a component typified by an inorganic filler becomes more excellent.
  • the ratio of the molar equivalent of the amino terminal to the total molar equivalent of the amino terminal amount and the carboxy terminal amount in the polyamide composition ⁇ amino terminal amount / (amino terminal amount + carboxy terminal amount) ⁇ is 0.25 or more and less than 0.4. It is preferable that it is 0.35 or more and less than 0.4, and more preferably 0.25 or more and less than 0.35.
  • the ratio of the molar equivalent of the amino terminal to the total molar equivalent of the amino-terminal amount and the carboxy-terminal amount is at least the above lower limit value, corrosion of the extruder or the molding machine at the time of molding can be suppressed more effectively.
  • the polyamide composition is excellent in discoloration to heat and light when formed into a molded product. Can be done.
  • the flexural modulus of a dumbbell having a thickness of 4 mm conforming to ISO178, which is formed by molding a polyamide composition, measured according to ISO178 at 23 ° C. is preferably 10 GPa or more, and more preferably 11 GPa or more. , 12 GPa or more is more preferable.
  • the upper limit of the flexural modulus is not particularly limited, but may be, for example, 50 GPa. When the flexural modulus is within the above numerical range, the mechanical properties of the obtained molded product can be improved.
  • the polyamide composition of the present embodiment is suitably used for a molded body for suppressing vibration or sound propagation of an apparatus that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower.
  • the molded product of the present embodiment is used to suppress vibration or sound propagation of a device that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower.
  • the molded product of the present embodiment is formed by molding the above-mentioned polyamide composition.
  • the method for producing the molded product is not particularly limited, and a known molding method can be used.
  • Known molding methods are not limited to the following, but are not limited to, for example, press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multi-layer molding, and melt spinning. Etc., generally known plastic molding methods can be mentioned.
  • the frequency range of vibration or sound generated by the device is not particularly limited, but is preferably 10 Hz or more and 10000 Hz or less, more preferably 10 Hz or more and 6000 Hz or less, and more preferably 50 Hz or more and 6000 Hz or less. More preferred.
  • the molded product of the present embodiment can particularly effectively suppress vibration or sound in the frequency range within the above range.
  • the molded body of the present embodiment is excellent in the effect of suppressing vibration or sound propagation with respect to a molded body made of a metal such as aluminum or a conventional resin composition, particularly even in a frequency region of 1500 Hz or higher.
  • the vibration suppressing effect exerted by the molded body of the present embodiment is a vibration damping effect. That is, the molded product of the present embodiment can be said to be a vibration damping molded product of an apparatus that generates vibration in a high temperature environment of 80 ° C. or higher and 140 ° C. or lower.
  • vibration suppression here means a method of converting vibration energy into heat energy and attenuating the vibration, and by converting the vibration energy into heat energy in the same frequency region as the vibration source, the resonance point. It is a method of reducing the acceleration in the vibration to attenuate the vibration.
  • the acceleration (m / s 2 ) at the resonance point when the molded body of the present embodiment is used is relative to the acceleration (m / s 2 ) at the resonance point when the molded body of the present embodiment is not used. It is usually reduced to a value of 60% or less, preferably 50% or less, more preferably 30% or less, still more preferably 20% or less, and particularly preferably 15% or less.
  • the sound pressure level (dB) in the frequency range of 1500 Hz or more and 6000 Hz or less when the molded body of the present embodiment is used and the frequency range of 1500 Hz or more and 6000 Hz or less when the molded body of the present embodiment is not used. It can be reduced to a value of usually 60% or less, preferably 50% or less, more preferably 30% or less, still more preferably 20% or less, and particularly preferably 15% or less with respect to the sound pressure level (dB). ..
  • the thickness of the molded product of the present embodiment can be appropriately designed according to the type of the device to be covered, but can be, for example, 1 mm or more and 5 mm or less.
  • the molded body of the present embodiment has good flexural modulus and tensile strength in a high temperature environment of about 80 ° C. or higher and 140 ° C. or lower, and is excellent in vibration damping effect of a device that generates vibration in a high temperature environment.
  • automobile parts include intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, electrical components, and the like.
  • the automobile intake system component is not particularly limited, and examples thereof include an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body.
  • the automobile cooling system component is not particularly limited, and examples thereof include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an alternator, and a delivery pipe.
  • the automobile fuel system parts are not particularly limited, and examples thereof include fuel delivery pipes and gasoline tank cases.
  • the automobile interior parts are not particularly limited, and examples thereof include instrumental panels, console boxes, glove boxes, steering wheels, trims, and the like.
  • the automobile exterior parts are not particularly limited, and examples thereof include moldings, lamp housings, front grilles, mudguards, side bumpers, door mirror stays, roof rails, and the like.
  • the automobile electrical components are not particularly limited, and examples thereof include connectors, wire harness connectors, motor components, lamp sockets, sensor in-vehicle switches, combination switches, and the like.
  • the molded body of the present embodiment has good bending elasticity and tensile strength in a high temperature environment of about 80 ° C. or higher and 140 ° C. or lower, and is excellent in the vibration damping effect of a device that generates vibration in a high temperature environment.
  • Electric vehicle field that is, hybrid vehicle (HV), plug-in hybrid vehicle (PHV), electric vehicle (EV), fuel cell vehicle (FCV), etc. equipped with a lithium ion secondary battery and powered by an electric motor.
  • HV hybrid vehicle
  • PGV plug-in hybrid vehicle
  • EV electric vehicle
  • FCV fuel cell vehicle
  • a case for accommodating a motor mount, a power module, a converter, a capacitor, an insulator, a motor terminal block, a battery, an electric compressor, a battery current sensor, a junction block, etc., and particularly a case for an ignition coil of a DLI system can be mentioned.
  • the molded product of the present embodiment has a high surface gloss value.
  • the surface gloss value of the molded product of the present embodiment is preferably 45% or more, more preferably 50% or more, further preferably 65% or more, still more preferably 70% or more.
  • the surface gloss value is a value obtained by measuring a 60-degree gloss according to JIS-K7150 using a gloss meter.
  • the obtained molded body can be used for electric and electronic parts, home appliance parts, OA (Office Automation) equipment parts, portable equipment parts, industrial equipment parts, etc. It can be suitably used as various parts for daily necessities and household goods, and for extrusion applications.
  • the molded body of the present embodiment having an excellent surface appearance is suitably used as an automobile part, an electric and electronic part, a home electric appliance part, an OA equipment part, or a portable equipment part.
  • the electric and electronic components are not particularly limited, and examples thereof include connectors, reflectors for light emitting devices, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, motor end caps, and the like.
  • Reflectors for light emitting devices include optical semiconductors such as laser diodes (LDs) in addition to light emitting diodes (LEDs), fott diodes, charge-coupled devices (CCDs), complementary metal oxide semiconductors (CMOS), and other semiconductor packages. Can be widely used in.
  • LDs laser diodes
  • LEDs light emitting diodes
  • CCDs charge-coupled devices
  • CMOS complementary metal oxide semiconductors
  • the portable device component is not particularly limited, and examples thereof include a housing and a structure of a mobile phone, a smartphone, a personal computer, a portable game device, a digital camera, and the like.
  • the industrial equipment parts are not particularly limited, and examples thereof include gears, cams, insulating blocks, valves, power tool parts, agricultural machinery parts, engine covers, and the like.
  • the daily necessities and household items are not particularly limited, and examples thereof include buttons, food containers, office furniture, and the like.
  • the extrusion application is not particularly limited, but is used for, for example, a film, a sheet, a filament, a tube, a rod, a hollow molded body, or the like.
  • the molded product of the present embodiment since the molded product of the present embodiment has an excellent surface appearance, it is also preferably used as a molded product having a coating film formed on the surface of the molded product.
  • the method for forming the coating film is not particularly limited as long as it is a known method, and for example, coating such as a spray method or an electrostatic coating method can be used.
  • the paint used for painting is not particularly limited as long as it is known, and melamine crosslinked type polyester polyol resin paint, acrylic urethane paint and the like can be used.
  • the molded body of the present embodiment is excellent in mechanical strength, toughness, heat resistance, and vibration fatigue resistance, and is therefore suitable as a component material for automobiles, and further is excellent in slidability. , Especially suitable as a component material for gears and bearings. Further, since it is excellent in mechanical strength, toughness, and heat resistance, it is suitable as a component material for electricity and electronics.
  • the method of the present embodiment is a method of suppressing the propagation of vibration or sound of the device, which comprises using the above-mentioned molded product for a device that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower. Is.
  • the molded body by using the molded body, it is possible to effectively suppress the vibration or sound propagation of the device that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower.
  • the molded body those exemplified in the above ⁇ molded body> can be used.
  • the acceleration at the resonance point (m / s 2 ) when the molded body is used is the acceleration (m / s 2 ) at the resonance point when the molded body is not used. ), It can be reduced to a value of usually 60% or less, preferably 50% or less, more preferably 30% or less, still more preferably 20% or less, and particularly preferably 15% or less.
  • the sound pressure level (dB) in the range of the frequency of 1500 Hz or more and 6000 Hz or less when the molded body is used is set to the frequency of 1500 Hz or more and 6000 Hz or less when the molded body is not used.
  • the sound pressure level (dB) in the range of it is usually reduced to a value of 60% or less, preferably 50% or less, more preferably 30% or less, still more preferably 20% or less, and particularly preferably 15% or less. be able to.
  • B-3 Polyamide 6IT-40 (manufactured by Rankses, M
  • C-1 Hydrogenated styrene-based thermoplastic elastomer (modified SEBS) (Asahi Kasei Corporation, Tough Tech (registered trademark) MP10)
  • D-1 Glass fiber (GF) (manufactured by Nippon Electric Glass, trade name "ECS03T275H", number average fiber diameter (average particle size): 10 ⁇ m (round shape), cut length: 3 mm)
  • the average fiber diameter of the glass fiber was measured as follows. First, the polyamide composition was placed in an electric furnace to incinerate the organic substances contained in the polyamide composition. From the residue after the treatment, 100 or more glass fibers arbitrarily selected were observed with a scanning electron microscope (SEM), and the fiber diameters of these glass fibers were measured to determine the number average fiber diameter. ..
  • SEM scanning electron microscope
  • E-1 Carbon black with an average primary particle size of 18 nm
  • F-1 Calcium montanate (manufactured by Clariant, trade name “Licomont CaV102")
  • F-2 Sodium montanate (manufactured by Clariant, trade name "Licomont NaV101”)
  • A-1) Adipic acid (ADA) (manufactured by Wako Pure Chemical Industries, Ltd.)
  • A-2) Isophthalic acid (IPA) manufactured by Wako Pure Chemical Industries, Ltd.
  • the internal temperature was raised to 220 ° C.
  • the autoclave was boosted to 1.8 MPa.
  • the reaction was carried out for 1 hour as it was until the internal temperature reached 245 ° C., while the water vapor was gradually removed and the pressure was maintained at 1.8 MPa.
  • the pressure was reduced over 1 hour.
  • the inside of the autoclave was maintained in a vacuum device under a reduced pressure of 650 torr for 10 minutes.
  • the final internal temperature of the polymerization was 265 ° C. After that, it is pressurized with nitrogen to form a strand from the lower spun (nozzle), water-cooled, cut, discharged in pellet form, dried at 100 ° C.
  • the internal temperature was raised to 220 ° C.
  • the autoclave was boosted to 1.8 MPa.
  • the reaction was carried out for 1 hour as it was until the internal temperature reached 245 ° C., while the water vapor was gradually removed and the pressure was maintained at 1.8 MPa.
  • the pressure was reduced over 30 minutes.
  • the inside of the autoclave was maintained in a vacuum device under a reduced pressure of 650 torr for 10 minutes.
  • the final internal temperature of the polymerization was 265 ° C. After that, it is pressurized with nitrogen to form a strand from the lower spun (nozzle), water-cooled, cut, discharged in pellet form, dried at 100 ° C.
  • the temperature from the upstream supply port to the die is set to the melting point Tm2 + 20 ° C. of each (A) crystalline polyamide manufactured in the above production example, the screw rotation speed is set to 300 rpm, and the discharge rate is set to 400 kg / h. did.
  • (A) crystalline polyamide and (B) amorphous polyamide are supplied from the upstream side supply port of the twin-screw extruder so as to have the types and ratios shown in Table 1 below.
  • Glass fiber was supplied as an inorganic filler from the first supply port on the downstream side of the twin-screw extruder, and the melt-kneaded product extruded from the die head was cooled in a strand shape and pelletized to obtain pellets of a polyamide composition.
  • the obtained pellets of the polyamide composition were dried in a nitrogen stream to reduce the water content in the polyamide composition to 500 ppm or less.
  • the temperature from the upstream supply port to the die is set to the melting point Tm2 + 20 ° C. of each (A) crystalline polyamide manufactured in the above production example, the screw rotation speed is set to 250 rpm, and the discharge rate is set to 25 kg / h. did. It was carried out in the same manner as in Example 1 except that the extruder was changed.
  • the temperature was lowered to 30 ° C. at a temperature lowering rate of 20 ° C./min.
  • the exothermic peak appearing at this time was defined as the crystallization peak
  • the crystallization peak temperature was defined as Tc
  • the crystallization peak area was defined as the crystallization enthalpy ⁇ H (J / g).
  • the temperature was raised from 30 ° C. to 280 ° C. or higher and 300 ° C. or lower depending on the melting point of the sample at a heating rate of 20 ° C./min.
  • the maximum temperature of the endothermic peak (melting peak) that appears at this time was defined as the melting point Tm2 (° C.).
  • Measurement mode Tensile waveform: Sine wave Frequency: 3.5Hz Temperature range: 0 ° C or higher and 180 ° C or lower Temperature rise step: 2 ° C / min Static load: 400g Displacement amplitude: 0.75 ⁇ m
  • the ratio (E2 / E1) of the loss elastic modulus E2 to the storage elastic modulus E1 was defined as tan ⁇ , and the highest temperature was defined as the tan ⁇ peak temperature.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • GPC manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethylmethacrylate) standard sample (converted by Polymer Laboratory)
  • the peak area of 2.47 ppm derived from the adjacent methylene hydrogen of adipic acid and the hydrogen on the adjacent benzene ring carbon of the isophthalic acid unit are derived.
  • the carboxy terminal amount was determined by calculating the integral ratio from the peak area of 8.07 ppm and the peak area of 7.85 ppm derived from hydrogen on the adjacent benzene ring carbon of the terephthalic acid unit.
  • the amount of amino terminal was determined by calculating the integral ratio from the peak area of 2.67-2.69 ppm derived from hydrogen on the adjacent methylene carbon of the hexamethylenediamine group.
  • [NH 2 ] + [COOH] was calculated from the amount of amino terminal ([NH 2 ]) measured as described above and the amount of carboxy terminal ([COOH]).
  • a rectangular cuboid molded body was manufactured as follows.
  • a rectangular cuboid molded body (width: 180 mm, depth 100 mm, height 50 mm, thickness 2 mm) was molded using an injection molding machine (PS-40E, manufactured by Nissei Resin Co., Ltd.).
  • PS-40E manufactured by Nissei Resin Co., Ltd.
  • the injection and holding pressure time was set to 20 seconds
  • the cooling time was set to 15 seconds
  • the mold temperature was set to 100 ° C
  • the cylinder temperature was set to 280 ° C.
  • the height of the resonance point acceleration peak at 23 ° C. and 100 ° C.
  • the resonance point acceleration was measured under the conditions shown below. The temperature at the time of measurement was adjusted by placing a molded body in the central portion of the temperature control cover connected to the hot air generator and blowing hot air onto the molded body. Vibration under each temperature condition where the resonance point acceleration peak height at 23 ° C is 500 m / s 2 or less and the resonance point acceleration peak height at 100 ° C is 100 m / s 2 or less. It was evaluated that the attenuation was good.
  • Vibration generator EMIC, Vibro chamber Accelerometer: EMIC, Accelerometer Temperature: From 23 ° C to 120 ° C
  • Fastening method of molded body Stepped bolt
  • Fastening torque of molded body 10 Nm (M6 standard)
  • Gasket tightening allowance 2 mm
  • Waveform Sine wave (sweep waveform from 50Hz to 1000Hz in 7 minutes)
  • Control acceleration 9.8m / s 2 (1G)
  • Vibration direction Up and down Measurement position: Central part on the temperature control cover
  • the mechanical properties such as tensile strength and flexural modulus, vibration damping effect and noise suppressing effect at 100 ° C. were good, but mold release failure occurred during molding. Further, the flexural modulus at 100 ° C. was greatly reduced, the surface appearance was poor, and the vibration damping effect at 23 ° C. was hardly observed.
  • the surface appearance, tensile strength, mechanical properties such as flexural modulus at 23 ° C, and vibration damping effect at 23 ° C were good, but the vibration damping effect at 100 ° C was almost nonexistent.
  • the noise suppression effect was poor.
  • the bending elastic modulus, the tensile strength and the appearance of the molded product are excellent, and the vibration damping of the device that generates vibration or sound in an environment of 80 ° C. or higher and 140 ° C. or lower. And it is possible to provide a polyamide composition having an excellent noise suppressing effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de polyamide utilisée dans un corps moulé pour supprimer la propagation de la vibration ou d'un son d'un dispositif qui génère une vibration ou un son dans un environnement ayant une température de 80 à 140 ºC, la composition de polyamide comprenant un polyamide cristallin (A) et un polyamide non cristallin (B). La teneur du polyamide non cristallin (B) est de 10,0 à 50,0 % en masse par rapport à la masse de tous les polyamides dans la composition de polyamide ; la température pic tanδ de la composition de polyamide est de 90 ºC ou plus ; le polyamide non cristallin (B) est dispersé dans le polyamide cristallin (A) et formant un domaine ; et la taille de particule moyenne en nombre du polyamide non cristallin (B) formant le domaine est de 10 nm à 1,0 µm, inclus.
PCT/JP2021/046776 2021-01-07 2021-12-17 Composition de polyamide, corps moulé, et procédé de suppression de la propagation d'une vibration ou d'un son de dispositif Ceased WO2022149436A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022573974A JP7524361B2 (ja) 2021-01-07 2021-12-17 ポリアミド組成物、成形体、及び装置の振動又は音の伝搬を抑制する方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021001392 2021-01-07
JP2021-001392 2021-01-07

Publications (1)

Publication Number Publication Date
WO2022149436A1 true WO2022149436A1 (fr) 2022-07-14

Family

ID=82357282

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/046776 Ceased WO2022149436A1 (fr) 2021-01-07 2021-12-17 Composition de polyamide, corps moulé, et procédé de suppression de la propagation d'une vibration ou d'un son de dispositif

Country Status (2)

Country Link
JP (1) JP7524361B2 (fr)
WO (1) WO2022149436A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024167049A (ja) * 2023-05-19 2024-11-29 ユニチカ株式会社 ポリアミド樹脂組成物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03143956A (ja) * 1989-10-30 1991-06-19 Toyoda Gosei Co Ltd エンジン用制振性樹脂成形品
JP2005225988A (ja) * 2004-02-13 2005-08-25 Kishimoto Sangyo Co Ltd 制振制音樹脂組成物
JP2009544808A (ja) * 2006-07-25 2009-12-17 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリアミド類およびメルカプトベンゾイミダゾール類の振動減衰材料
JP2009544799A (ja) * 2006-07-25 2009-12-17 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 振動減衰材料、構造積層体、およびその作製方法
WO2012060392A1 (fr) * 2010-11-01 2012-05-10 東洋紡績株式会社 Composition de résine de polyamide, moulage en résine de polyamide expansée, et moulage en résine pour l'automobile
WO2018181995A1 (fr) * 2017-03-30 2018-10-04 旭化成株式会社 Composition de polyamide et article moulé
JP2018188534A (ja) * 2017-05-01 2018-11-29 旭化成株式会社 ポリアミド組成物及び成形品

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03143956A (ja) * 1989-10-30 1991-06-19 Toyoda Gosei Co Ltd エンジン用制振性樹脂成形品
JP2005225988A (ja) * 2004-02-13 2005-08-25 Kishimoto Sangyo Co Ltd 制振制音樹脂組成物
JP2009544808A (ja) * 2006-07-25 2009-12-17 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリアミド類およびメルカプトベンゾイミダゾール類の振動減衰材料
JP2009544799A (ja) * 2006-07-25 2009-12-17 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 振動減衰材料、構造積層体、およびその作製方法
WO2012060392A1 (fr) * 2010-11-01 2012-05-10 東洋紡績株式会社 Composition de résine de polyamide, moulage en résine de polyamide expansée, et moulage en résine pour l'automobile
WO2018181995A1 (fr) * 2017-03-30 2018-10-04 旭化成株式会社 Composition de polyamide et article moulé
JP2018188534A (ja) * 2017-05-01 2018-11-29 旭化成株式会社 ポリアミド組成物及び成形品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024167049A (ja) * 2023-05-19 2024-11-29 ユニチカ株式会社 ポリアミド樹脂組成物

Also Published As

Publication number Publication date
JP7524361B2 (ja) 2024-07-29
JPWO2022149436A1 (fr) 2022-07-14

Similar Documents

Publication Publication Date Title
TWI472552B (zh) 聚醯胺及聚醯胺組成物
CN110964316B (zh) 聚酰胺组合物、成型品和半芳香族聚酰胺
CN110964315B (zh) 聚酰胺组合物及其制造方法以及成型品
WO2014109300A1 (fr) Composition polyamide, et article moulé
CN103403063A (zh) 聚酰胺及聚酰胺组合物
JP2014231603A (ja) ポリアミド樹脂組成物及び成形品
JP6843698B2 (ja) ポリアミド組成物及び成形品
JP7440996B2 (ja) ポリアミド組成物及び成形品
JP2024138040A (ja) ポリアミド組成物及びその製造方法、並びに、成形品
JP7023723B2 (ja) ポリアミド組成物及び成形品
JP7524361B2 (ja) ポリアミド組成物、成形体、及び装置の振動又は音の伝搬を抑制する方法
JP7548752B2 (ja) ポリアミド組成物及びその製造方法、並びに、成形品
JP2017155150A (ja) ポリアミド組成物、ポリアミド組成物成形品およびポリアミド組成物の製造方法
JP2024010978A (ja) ポリアミド組成物、及び成形体
JP5669627B2 (ja) ポリアミド樹脂組成物及び成形品
JP2023072690A (ja) ポリアミド組成物、成形品、及び積層体
JP2023028935A (ja) ポリアミド組成物及び成形品
JP2023050575A (ja) ポリアミド組成物、成形品、及びポリアミド組成物の製造方法
WO2016031257A1 (fr) Polyamide, procédé de production de polyamide, composition de polyamide, article moulé à base d'une composition de polyamide et son procédé de production
WO2025159207A1 (fr) Composition de résine polyamide et article moulé
JP6639121B2 (ja) ポリアミド組成物、成形品、及びｌｅｄ用反射板
JP2025073909A (ja) ポリアミド組成物、成形品
WO2025089285A1 (fr) Composition de polyamide et article moulé
JP2023157584A (ja) ポリアミド組成物及び成形品
JP2022051850A (ja) ポリアミド組成物及び成形品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21917657

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022573974

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21917657

Country of ref document: EP

Kind code of ref document: A1