WO2022097625A1 - Composition de résine de polyamide et article moulé comprenant la composition de résine de polyamide - Google Patents

Composition de résine de polyamide et article moulé comprenant la composition de résine de polyamide Download PDF

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WO2022097625A1
WO2022097625A1 PCT/JP2021/040348 JP2021040348W WO2022097625A1 WO 2022097625 A1 WO2022097625 A1 WO 2022097625A1 JP 2021040348 W JP2021040348 W JP 2021040348W WO 2022097625 A1 WO2022097625 A1 WO 2022097625A1
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polyamide resin
resin composition
mass
functional group
polyamide
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PCT/JP2021/040348
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English (en)
Japanese (ja)
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貞義 須原
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宇部興産株式会社
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Publication of WO2022097625A1 publication Critical patent/WO2022097625A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polyamide resin composition and a molded product containing the polyamide resin composition.
  • Polyamide resin is widely used as an engineering plastic in automobiles, electrical and electronic equipment, etc. because it has excellent physical and chemical properties such as mechanical properties, electrical properties, and oil resistance. In particular, in automobile applications, polyamide resins having excellent oil resistance are often used.
  • polyamide resin is a resin with excellent slidability, it has higher slidability and more accurate dimensional stability when used as a component material for hydraulic equipment such as pistons, cylinders, and drive shaft washers. And mechanical properties such as stronger rigidity are required.
  • a method of adding a fibrous reinforcing material such as a fluororesin and a carbon fiber to a polyamide resin is known.
  • a polyamide resin composition containing a polyamide resin, a fluororesin, carbon fibers and fibrous zonotrite in a predetermined ratio has been proposed, and the composition has the original oil resistance and heat resistance of a polyamide resin. It has been shown to have high slidability and dimensional stability as well as stability, mechanical properties and moldability (see, for example, Patent Document 1).
  • a polyamide resin composed of a terephthalic acid unit and an aliphatic diamine unit having 6 to 18 carbon atoms, a fluororesin having predetermined physical properties, and a fibrous filler and / or a needle-like filler are melt-kneaded at a predetermined ratio.
  • the polyamide resin composition thus obtained has been proposed, and has been shown to be excellent in productivity, slidability, mechanical properties, etc. at the time of pellet preparation (see, for example, Patent Document 2).
  • a cage for rolling bearings containing a polyamide resin containing terephthalic acid and 1,10-decanediamine as a main component, glass fiber or carbon fiber, and a fluororesin in a predetermined ratio has been proposed. It has been shown that it has high rigidity and can prevent seizure and breakage during high-speed rotation (see, for example, Patent Document 3).
  • An object of the present invention is to provide a polyamide resin composition having high fluidity and excellent mechanical properties and slidability when formed into a molded product.
  • a polyamide resin composition containing a fluororesin and carbon fibers As a result of diligent studies on a polyamide resin composition containing a fluororesin and carbon fibers, the present inventors have found that a polyamide resin composition containing a specific fluororesin in a specific ratio has high fluidity and is a molded product. It was found that the resin is excellent in mechanical properties and slidability.
  • the present invention relates to the following [1] to [12].
  • [1] 60 to 85% by mass of the aliphatic polyamide resin (A) and 0.5 to 9% by mass of the copolymerized fluororesin (B) which may have a functional group with respect to 100% by mass of the polyamide resin composition. , 5 to 20% by mass of carbon fiber (C), and 34.5% by mass or less of other component (D), a polyamide resin composition.
  • the polyamide resin composition according to [1], wherein the mass ratio of the copolymerized fluororesin (B) which may have a carbon fiber (C) / functional group is more than 1.0 and less than 20.
  • the mass ratio of the copolymerized fluororesin (B) / aliphatic polyamide resin (A) which may have a functional group is more than 0.005 and less than 0.12.
  • the copolymerized fluororesin (B) which may have a functional group The copolymerized fluororesin is an ⁇ -olefin / tetrafluoroethylene copolymer, any one of [1] to [3].
  • the content of each component in the composition is the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. means.
  • the polyamide resin composition of the present invention has 60 to 85% by mass of the aliphatic polyamide resin (A) and may have a functional group with respect to 100% by mass of the polyamide resin composition.
  • Copolymerized fluororesin (B) 0 It contains 5 to 9% by mass of carbon fiber (C), 5 to 20% by mass of carbon fiber (C), and 34.5% by mass or less of other component (D). By setting the ratio of each component in the above range, it is possible to provide a polyamide resin composition having high fluidity and excellent mechanical properties and slidability in the case of a molded product.
  • the polyamide resin composition has good toughness, heat resistance, oil resistance, solvent resistance, chemical resistance, abrasion resistance and molding processability.
  • the aliphatic polyamide resin (A) can be selected from the aliphatic homopolyamide resin (A-1) and the aliphatic copolymerized polyamide resin (A-2), and may be one kind or a combination of two or more kinds. can.
  • the aliphatic homopolyamide resin (A-1) means a polyamide resin in which one kind of monomer component constituting the aliphatic polyamide resin is alone.
  • the aliphatic homopolyamide resin (A-1) may consist of at least one of one type of lactam and an aminocarboxylic acid which is a hydrolyzate of the lactam, and one type of aliphatic diamine and one type. It may consist of a combination with an aliphatic dicarboxylic acid.
  • the monomer component constituting the aliphatic polyamide resin is a combination of an aliphatic diamine and an aliphatic dicarboxylic acid
  • one kind of monomer is a combination of one kind of aliphatic diamine and one kind of aliphatic dicarboxylic acid. It shall be regarded as an ingredient.
  • Examples of the aliphatic homopolyamide resin (A-1) include an aliphatic homopolyamide resin composed of an aliphatic diamine and an aliphatic dicarboxylic acid, an aliphatic homopolyamide resin composed of lactam or an aminocarboxylic acid, and the like.
  • the monomer component constituting the aliphatic homopolyamide resin (A-1) includes an aliphatic diamine having 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and 2 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Examples of the combination of the aliphatic dicarboxylic acid of the above, lactam or aminocarboxylic acid having 6 to 12 carbon atoms and the like can be mentioned.
  • Examples of the aliphatic diamines include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecanediamine.
  • Tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecandiamine, eikosandiamine, 2-methyl-1,8-octanediamine, 2,2,4 / 2,4,4-trimethylhexamethylene Examples include diamine.
  • the aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandionic acid, dodecandionic acid, tridecandionic acid and tetradecandione.
  • Examples thereof include acid, pentadecandionic acid, hexadecandionic acid, octadecandionic acid, eikosandionic acid and the like.
  • Examples of the combination of the aliphatic diamine and the aliphatic dicarboxylic acid include a combination of hexamethylenediamine and adipic acid, a combination of hexamethylenediamine and sebacic acid, a combination of hexamethylenediamine and dodecandionic acid, and the like. Salt is preferably used.
  • lactam examples include ⁇ -caprolactam, enantractum, undecane lactam, dodecane lactam, ⁇ -pyrrolidone, ⁇ -piperidone and the like.
  • the lactam is preferably ⁇ -caprolactam, undecane lactam or dodecane lactam from the viewpoint of productivity.
  • the aminocarboxylic acid examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
  • polyamide 6 polycaprolactam
  • polyenantractum polyamide 7
  • polyundecanelactam polyamide 11
  • polylauryllactam polyamide 12
  • Adipamide (polyamide 66), polytetramethylene dodecamide (polyamide 412), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), poly Hexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99).
  • Polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene azelamide (polyamide 109), polydecamethylene decamide (polyamide 109). 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebacamide (polyamide 1210), polydodecamethylene dodecamide. (Polyamide 1212), polyamide 122 and the like.
  • the aliphatic homopolyamide resin (A-1) is selected from the group consisting of polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11 and polyamide 12 from the viewpoint of toughness, heat resistance, oil resistance and abrasion resistance. It is preferable that the amount is one or more, and the polyamide 6 and / or the polyamide 66 is particularly preferable.
  • the aliphatic homopolyamide resin (A-1) may be used alone or in combination of two or more.
  • the aliphatic copolymerized polyamide resin (A-2) means a polyamide resin in which two or more kinds of monomer components constituting the aliphatic polyamide resin are combined.
  • the aliphatic copolymerized polyamide resin (A-2) is two or more copolymers selected from the group consisting of a combination of an aliphatic diamine and an aliphatic dicarboxylic acid, lactam and an aminocarboxylic acid.
  • the combination of the aliphatic diamine and the aliphatic dicarboxylic acid is regarded as one kind of monomer component by the combination of one kind of aliphatic diamine and one kind of aliphatic dicarboxylic acid.
  • Examples of the aliphatic diamine include the same as those exemplified as the raw material of the aliphatic homopolyamide resin (A-1).
  • Examples of the aliphatic dicarboxylic acid include the same as those exemplified as the raw material of the aliphatic homopolyamide resin (A-1).
  • lactam examples include those similar to those exemplified as the raw material of the aliphatic homopolyamide resin (A-1).
  • aminocarboxylic acid examples include the same as those exemplified as the raw material of the aliphatic homopolyamide resin (A-1).
  • aliphatic diamines aliphatic dicarboxylic acids, lactams and aminocarboxylic acids may be used alone or in combination of two or more.
  • aliphatic copolymerized polyamide resin (A-2) examples include a caprolactam / hexamethylene diaminoadipic acid copolymer (polyamide 6/66) and a caprolactam / hexamethylene diaminoazeline acid copolymer (polyamide 6/69).
  • a caprolactam / hexamethylene diaminosevacinic acid copolymer polyamide 6/610
  • caprolactam / hexamethylene diaminoundecanedicanoic acid copolymer polyamide 6/611
  • caprolactam / hexamethylene diaminododecanedicarboxylic acid copolymer polyamide 6
  • the aliphatic copolymerized polyamide resin (A-2) may be used alone or in combination of two or more.
  • the aliphatic polyamide resin (A) 1 g of the aliphatic polyamide resin (A) is dissolved in 100 ml of 96% sulfuric acid according to JIS K 6920, and the relative viscosity measured at 25 ° C. is 2.61 to 2.85. It is preferable to have.
  • the relative viscosity of the aliphatic polyamide resin (A) is preferably 2.63 to 2.83, more preferably 2.65 to 2.81.
  • the relative viscosity of the aliphatic polyamide resin (A) is preferably measured as described above, but each polyamide resin.
  • the average value calculated by multiplying the respective relative viscosities by the mixing ratio may be used as the relative viscosity of the aliphatic polyamide resin (A). ..
  • the terminal amino group concentration of the aliphatic polyamide resin (A) is preferably 15 ⁇ mol / g or more, preferably 20 ⁇ mol / g or more and 110 ⁇ mol, as the terminal amino group concentration obtained by dissolving in a mixed solvent of phenol and methanol and performing neutralization titration.
  • the range of / g or less is more preferable, and the range of 30 ⁇ mol / g or more and 70 ⁇ mol / g or less is particularly preferable. Within the above range, the molding processability of the molded product using the polyamide resin composition is good.
  • the terminal amino group concentration in the aliphatic polyamide resin (A) is measured by the above neutralization pruning.
  • the average value calculated by multiplying each terminal amino group concentration by the mixing ratio is used as the aliphatic. It may be the terminal amino group concentration of the polyamide resin (A).
  • Examples of the equipment for producing the aliphatic polyamide resin (A) include a batch type reaction kettle, a single-tank or multi-tank continuous reaction device, a tubular continuous reaction device, a uniaxial kneading extruder, a twin-screw kneading extruder, and the like.
  • Known polyamide production equipment such as a reaction extruder can be mentioned.
  • As a polymerization method known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be carried out by repeating operations such as normal pressure, reduced pressure, and pressurization. These polymerization methods can be used alone or in combination as appropriate.
  • the polyamide resin composition is more fluid than the case where a homopolymer of a fluorine-containing monomer such as tetrafluoroethylene is blended by blending the copolymerized fluororesin (B) which may have a functional group.
  • the properties and the mechanical properties and slidability of the molded product are improved.
  • the copolymerized fluororesin (B) which may have a functional group may be one kind or a combination of two or more kinds.
  • the copolymerized fluororesin of the copolymerized fluororesin (B) which may have a functional group has at least a repeating unit derived from a fluorine-containing monomer and a repeating unit derived from a non-fluorine-containing monomer. It is a copolymer having one kind.
  • the functional group means a group that reacts with the terminal amino group of the aliphatic polyamide resin (A), and specifically, a carboxyl group, an acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal salt, and a carboxylic acid imide. Examples include a group, a carboxylic acid amide group, an epoxy group and the like.
  • the copolymerized fluororesin having no functional group means a copolymer having no functional group that reacts with the terminal amino group of the aliphatic polyamide resin (A).
  • a copolymerized fluororesin having a functional group introduces a functional group by copolymerizing a monomer having a functional group or reacting the copolymer having no functional group with a compound having a functional group. Means the copolymer.
  • fluorine-containing monomer examples include tetrafluoroethylene (TFE), trifluoroethylene, vinylidene fluoride (VDF), vinyl fluoride (VF), chlorotrifluoroethylene (CTFE), trichlorofluoroethylene, and hexafluoropropylene (HFP).
  • TFE tetrafluoroethylene
  • VDF vinylidene fluoride
  • VF vinyl fluoride
  • CFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • n an integer of 2 or more and 10 or less.
  • the n in the compound represented by ()) has an effect of modifying the copolymerized fluororesin (B) which may have a functional group (for example, during molding of the copolymer and suppression of crack generation in the molded product). It is an integer of 2 or more and 10 or less from the viewpoint of ensuring sufficient polymerization reactivity and obtaining sufficient polymerization reactivity.
  • the compound represented by CF (CF 2 ) n H is preferable, and n in the formula is more preferably 2 or more and 4 or less.
  • Non-fluorine-containing monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1 -Tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl -1-Pentene, 4-Methyl-1-Pentene, 4-Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 ⁇ -olefins such as -ethyl-1-hexen
  • n-butyl, methyl crotonate examples thereof include vinyl ethers such as methyl vinyl ether (MVE), ethyl vinyl ether (EVE), butyl vinyl ether (BVE), isobutyl vinyl ether (IBVE), cyclohexyl vinyl ether (CHVE), and glycidyl vinyl ether.
  • MVE methyl vinyl ether
  • EVE ethyl vinyl ether
  • BVE butyl vinyl ether
  • IBVE isobutyl vinyl ether
  • CHVE cyclohexyl vinyl ether
  • glycidyl vinyl ether examples thereof include vinyl ethers such as methyl vinyl ether (MVE), ethyl vinyl ether (EVE), butyl vinyl ether (BVE), isobutyl vinyl ether (IBVE), cyclohexyl vinyl ether (CHVE), and glycidyl vinyl ether.
  • ⁇ -olefins such as ethylene and
  • the copolymerized fluororesin of the copolymerized fluororesin (B) which may have a functional group is an ⁇ -olefin / tetrafluoroethylene copolymer.
  • an ⁇ -olefin / tetrafluoroethylene copolymer having 2 to 4 carbon atoms is more preferable, and an ethylene / tetrafluoroethylene copolymer is particularly preferable.
  • a copolymerized fluororesin having a functional group introduces a functional group by copolymerizing a monomer having a functional group or reacting the copolymer having no functional group with a compound having a functional group. It is a copolymer.
  • the functional group is preferably a carboxyl group, a carboxylic acid ester group and / or an acid anhydride group from the viewpoint of reactivity with the terminal amino group of the aliphatic polyamide resin (A).
  • the copolymerized fluororesin having a functional group may have a plurality of types of functional groups. Further, the functional group may be located at the end of the copolymerized fluororesin or in the chain.
  • Examples of the monomer and / or compound having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, and cis-4-cyclohexene-1,2. -Dicarboxylic acid, endobicyclo- [2.2.1] -5-hepten-2,3-dicarboxylic acid and the like can be mentioned.
  • Examples of the monomer and / or compound having a carboxylic acid ester group include alkyl esters, hydroxyalkyl esters and aminoalkyl esters of the monomer and / or compound having a carboxyl group.
  • Examples of the monomer and / or compound having an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, and endobicyclo- [2.2.1] -5-hepten-2,3-dicarboxylic acid anhydride.
  • Examples thereof include dicarboxylic acid anhydrides having ⁇ , ⁇ -unsaturated bonds such as substances. These can be used alone or in combination of two or more. Among these, dicarboxylic acid anhydride having an ⁇ , ⁇ -unsaturated bond is preferable, maleic anhydride and itaconic anhydride are more preferable, and maleic anhydride is particularly preferable.
  • the copolymerized fluororesin (B), which may have a functional group, is anhydrous from the viewpoint of enhancing the reactivity of the aliphatic polyamide resin (A) with the terminal amino group and improving the fluidity of the resin composition. It is preferable that the ⁇ -olefin / tetrafluoroethylene copolymer having maleic acid introduced therein, that is, the ⁇ -olefin / tetrafluoroethylene copolymer having a group derived from maleic anhydride bonded therein, and the group derived from maleic anhydride is preferable. Particularly preferred is a bonded ethylene / tetrafluoroethylene copolymer.
  • Examples of the apparatus for producing the copolymerized fluororesin (B) which may have a functional group include a one-tank or multi-tank type stirring type polymerization device, a tube type polymerization device and the like, and may be a batch type or a continuous type. As an operation, the copolymerized fluororesin (B) can be produced.
  • the polymerization method is not particularly limited, and for example, a polymerization method using a generally used radical polymerization initiator is used.
  • polymerization method bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, alcohols and hydrocarbons, aqueous media and, if necessary, suitable organic solvents are used.
  • organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, alcohols and hydrocarbons
  • aqueous media and, if necessary, suitable organic solvents are used.
  • Known methods such as suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifier, etc. can be adopted.
  • Carbon fiber (C) By containing the carbon fiber (C) in the polyamide resin composition, it is possible to improve the mechanical properties and slidability of a molded product.
  • the carbon fiber (C) may be one kind or a combination of two or more kinds.
  • Examples of the carbon fiber (C) include PAN-based carbon fiber obtained by carbonizing polyacrylonitrile fiber, pitch-based carbon fiber obtained by carbonizing pitch fiber obtained by carbonizing coal tar or heavy petroleum content, and the like. ..
  • the fiber length of the carbon fiber may be a short fiber or a long fiber of up to 1,000 mm depending on the application, but from the viewpoint of productivity, the fiber length before kneading is preferably 0.1 to 20 mm. It is more preferably 0.0 to 15 mm.
  • the fiber diameter of the carbon fiber is not particularly limited, but is preferably 5 to 15 ⁇ m, more preferably 6 to 9 ⁇ m from the viewpoint of mechanical properties and productivity. It is preferable to use fine carbon fibers in a master batch in which the resin contains a high amount of carbon fibers in advance, or in which carbon fibers are granulated, because the carbon fibers are less likely to be defibrated during the production of the polyamide resin composition.
  • the carbon fiber may be surface-treated. That is, the carbon fiber may be a surface-treated carbon fiber.
  • Specific examples of the surface treatment agent include a silane coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent, and the like. Only one of the above surface treatment agents may be used, or a plurality of types of surface treatment agents may be mixed and used.
  • the polyamide resin composition may contain other components (D) as long as the object of the present invention is not impaired.
  • Other components (D) include polyamide resins other than the aliphatic polyamide resin (A), for example, polyamide resins having an alicyclic or aromatic group in the main chain or side chain; thermoplastics other than the component (B).
  • the polyamide resin composition is substantially free of fibrous zonotrite.
  • “Substantially free” means that it is intentionally not included unless, for example, it is unavoidably mixed with an industrial raw material. Specifically, it means that the content of fibrous zonotrite in 100% by mass of the polyamide resin composition is less than 0.1% by mass, preferably less than 0.05% by mass, and more preferably 0.03% by mass. Less than%.
  • the other component (D) is not the aliphatic polyamide resin (A), the copolymerized fluororesin (B) which may have a functional group, and the carbon fiber (C).
  • the polyamide resin composition preferably contains at least one selected from the group consisting of antioxidants and heat resistant agents as the other component (D).
  • the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, and the like.
  • the antioxidant is preferably a phenol-based antioxidant or a phosphorus-based antioxidant.
  • the heat resistant agent potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide , A metal halide compound such as cupric iodide, and a triazine ring compound such as melamine can be exemplified.
  • the heat resistant agent is preferably a mixture of cuprous iodide and potassium halide, a mixture of cuprous bromide and potassium halide, melamine, or a mixture thereof, preferably cuprous iodide.
  • the heat resistant agent is preferably a mixture of cuprous iodide, potassium halide and melamine, or a mixture of cuprous bromide, potassium halide and melamine, and cuprous iodide and potassium iodide.
  • a mixture of melamine, or a mixture of cuprous bromide, potassium bromide and melamine is particularly preferred.
  • the antioxidant and the heat resistant agent may be one type or a combination of two or more types, respectively.
  • the polyamide resin composition has 60 to 85% by mass of the aliphatic polyamide resin (A) and 0.5 to 0.5% of the copolymerized fluororesin (B) which may have a functional group with respect to 100% by mass of the polyamide resin composition. It contains 9% by mass, carbon fiber (C) 5 to 20% by mass, and other component (D) 34.5% by mass or less.
  • the proportion of the component (A) is less than 60% by mass, it causes deterioration of mechanical properties and fluidity, and if it exceeds 85% by mass, it causes deterioration of mechanical properties. If the proportion of the component (B) is less than 0.5% by mass, it causes deterioration of fluidity and slidability, and if it exceeds 9% by mass, it causes deterioration of mechanical properties. If the proportion of the component (C) is less than 5% by mass, the requirements for mechanical properties and slidability are not satisfied, and if it exceeds 20% by mass, molding may become difficult. If the proportion of the component (D) exceeds 34.5% by mass, the fluidity and the mechanical properties and slidability of the molded product cannot be ensured.
  • the component (A) is 70 to 85% by mass
  • the component (B) is 0.8 to 5.0% by mass
  • the component (C) is 10 to 10 to 100% by mass with respect to 100% by mass of the polyamide resin composition. It is preferable to contain 20% by mass and 5.0% by mass or less of the component (D), 80 to 85% by mass of the component (A), 1.0 to 3.0% by mass of the component (B), and (C). It is more preferable to contain 12.5 to 17.5% by mass of the component and 1.5% by mass or less of the component (D), 80 to 85% by mass of the component (A), and 1.1 to mass% of the component (B).
  • the component (B) is contained in an amount of 1.5 to 3.0% by mass
  • the component (C) is contained in an amount of 12.5 to 17.5% by mass
  • the component (D) is contained in an amount of 1.0% by mass or less.
  • the polyamide resin composition can be a composition containing only the aliphatic polyamide resin (A), the copolymerized fluororesin (B) which may have a functional group, and the carbon fiber (C).
  • the polyamide resin composition contains 71 to 85% by mass of the component (A), 0.5 to 9% by mass of the component (B), and the component (C) with respect to 100% by mass of the polyamide resin composition. It is preferable to contain 6 to 20% by mass, the component (A) is 79.5 to 85% by mass, the component (B) is 1.0 to 3.0% by mass, and the component (C) is 12.5 to 17. It is more preferable to contain 5% by mass, the component (A) is 79.5 to 85% by mass, the component (B) is 1.1 to 3.0% by mass, and the component (C) is 12.5-17.5. It is particularly preferable to contain% by mass.
  • the mass ratio of the copolymerized fluororesin (B) which may have a carbon fiber (C) / functional group is more than 1.0 and less than 20, the carbon fibers are uniformly dispersed in the polyamide resin composition. Easy and preferable.
  • the mass ratio of the copolymerized fluororesin (B), which may have a carbon fiber (C) / functional group is more preferably 3.0 to 18, and even more preferably 4.0 to 16. It is particularly preferably 4.0 to 14.
  • the mass ratio of the copolymerized fluororesin (B) / aliphatic polyamide resin (A) which may have a functional group is more than 0.005 and less than 0.12, the functional group is contained in the polyamide resin composition. It is preferable that the copolymerized fluororesin (B) which may be possessed is easily uniformly dispersed.
  • the mass ratio of the copolymerized fluororesin (B) / aliphatic polyamide resin (A), which may have a functional group is more preferably 0.008 to 0.060, more preferably 0.010 to 0.040. Is more preferable, and 0.013 to 0.040 is particularly preferable.
  • the polyamide resin composition used was a mold having a width of 15 mm, a length of 360 mm, and a thickness of 1 mm, and the pressure was 100 MPa, the cylinder temperature was 285 ° C, the mold temperature was 80 ° C, and the injection speed was 38 mm / sec. It is preferable that the injection flow length of the molded product obtained by injection molding under the conditions of an injection time of 4 seconds and a cooling time of 15 seconds is 150 mm or more because it is easy to fill the mold.
  • the injection flow length is an index for evaluating the fluidity of the resin composition using an injection molding machine and a mold, and is the length of the molded product when the resin is injection-filled at a constant temperature and a constant pressure. Is.
  • the injection flow length is more preferably 150 mm or more, and particularly preferably 180 mm or more.
  • the upper limit of the injection flow length is not particularly limited, but is practically 500 mm or less, preferably 300 mm or less.
  • the method for producing the polyamide resin composition is not particularly limited, and for example, the following method can be applied.
  • a uniaxial shaft is used.
  • a twin-screw extruder, a Banbury mixer, a kneader, and a commonly known melt-kneader such as a mixing roll are used.
  • a method of blending all raw materials and then melt-kneading using a twin-screw extruder a method of blending some raw materials, then melt-kneading, and then blending the remaining raw materials and melt-kneading, or a part of them. Any method may be used, such as a method of mixing the remaining raw materials using a side feeder during melt-kneading after blending the raw materials of.
  • the carbon fiber (C) may be mixed with the aliphatic polyamide resin (A) in advance and used as a masterbatch.
  • the polyamide resin composition is not particularly limited and can be used for producing a molded product using a known method. Specifically, the polyamide resin composition can be used in the production of molded products by injection molding, extrusion molding, blow molding, rotary molding and the like.
  • Molded products containing a polyamide resin composition have not only excellent properties inherent in a polyamide resin such as oil resistance, but also high slidability and mechanical properties, and oil resistance is particularly required as a sliding component.
  • sliding parts include cylinder head covers, various oil reservoirs, crankcase covers, power tool-related parts, hydraulic equipment parts, and the like.
  • hydraulic equipment parts include those used in the vehicle field, general-purpose equipment parts field, and the like. In the vehicle field, it can be used for piston-related parts of hydraulic equipment parts such as clutches, brakes, bearings and power steering. In the field of general-purpose equipment parts, it can be used as parts for vices, jacks, thrust washers, etc.
  • Preferred use is in the vehicle field as hydraulic equipment parts and in the parts field of general purpose equipment. Particularly preferred use is parts in the vehicle field.
  • a further embodiment of the present invention is a method of manufacturing a sliding component, which comprises molding a polyamide resin composition.
  • Copolymerized fluororesin (B) which may have a functional group Acid anhydride group-containing ethylene / tetrafluoroethylene copolymer (AGC Co., Ltd., Fluon (registered trademark) LM-ETFE, copolymer in which maleic anhydride is introduced into an ethylene / tetrafluoroethylene copolymer) Ethylene / tetrafluoroethylene copolymer (manufactured by AGC Inc., Fluon (registered trademark) ETFE)
  • Examples 1 to 7 and Comparative Examples 1 to 2 Using a twin-screw kneader ZSK32McPlus (manufactured by Coperion Co., Ltd., screw diameter 32 mm), among the components shown in Table 1, carbon fibers other than carbon fibers were charged from the top, and carbon fibers were charged using a side feeder.
  • the polyamide resin composition pellets of Examples 1 to 7 and Comparative Examples 1 to 2 were prepared by melt-kneading at a cylinder temperature of a twin-screw kneader at 300 ° C., a screw rotation speed of 400 rpm, and a discharge rate of 60 kg / h.
  • the unit of the composition in the table is mass%, and the entire resin composition is 100% by mass.
  • Rockwell hardness Using pellets of Examples 1 to 7 and Comparative Examples 1 and 2, a test piece was prepared according to ISO 2039-2, and Rockwell hardness (M scale) was measured. The acceptance criteria for Rockwell hardness was set to 100 or higher.
  • Charpy impact strength Using pellets of Examples 1 to 7 and Comparative Examples 1 and 2, a test piece was prepared in accordance with ISO 179 / 1eA, and the Charpy impact strength was measured. The acceptance criteria for Charpy impact strength was 4 kJ / m 2 or higher.
  • Deflection temperature under load Using pellets of Examples 1 to 7 and Comparative Examples 1 and 2, test pieces were prepared in accordance with ISO 75-2, and the deflection temperature under load (measured load 1.8 MPa) was measured. The acceptance criteria for the deflection temperature under load was set to 200 ° C or higher.
  • Molding Shrinkage Rate (distance between marking lines of the mold-distance between marking lines in the test piece) / distance between marking lines of the mold x 100 The acceptance criteria for the molding shrinkage in the MD and TD directions were 0.2% or less and 1.0% or less, respectively.
  • L / T flow length is 180 mm or more
  • L / T flow length is 150 mm or more and less than 180 mm
  • L / T flow length is less than 150 mm
  • test piece of 200 ⁇ 30 ⁇ t3 mm was prepared and allowed to stand for 48 hours or more under the condition of 23 ° C.
  • the test piece thus obtained is made of S45C carbon steel described in JIS standard G4051 using a Suzuki type friction and wear tester (EFM-III-EN, manufactured by Orientec Co., Ltd.) in accordance with JIS K7218.
  • Limit PV value is 6,000 kg / cm 2 ⁇ cm / sec or more
  • Limit PV value is 4,000 kg / cm 2 ⁇ cm / sec or more and less than 6,000 kg / cm 2 ⁇ cm / sec
  • Table 2 shows the evaluation results of the pellets of Examples 1 to 7 and Comparative Examples 1 and 2.
  • Examples 1, 2, 4, 6 and 7 containing 2.0% by mass or more of the copolymerized fluororesin (B) which may have a functional group with respect to 100% by mass of the polyamide resin composition.
  • the limit PV value is 6,000 kg / cm 2. cm / sec or more, and the slidability is excellent.
  • Comparative Example 1 in which polytetrafluoroethylene is used instead of the copolymerized fluororesin (B) which may have a functional group is inferior in fluidity and mechanical properties.
  • Comparative Example 2 in which the copolymerized fluororesin (B) having a functional group is used but the content thereof is outside the range of the present invention is inferior in mechanical properties and slidability.
  • the weight retention of the pellets obtained in Example 1 was evaluated as shown below. Using TGA Q5000 manufactured by TA Instruments, the pellets were rapidly heated from room temperature to 300 ° C. under air flow conditions, maintained at room temperature for 10 minutes after reaching 300 ° C., and then cooled to room temperature 23. It was allowed to stand at 50% RH for 48 hours. The weight retention rate was calculated from the weight before heating and the weight after heating. The weight retention rate of the pellets of Example 1 (residual weight after heating at 300 ° C. (holding for 10 minutes)) was as high as 99.34%.
  • the polyamide resin composition of the present invention can be used for manufacturing various molded products by injection molding, extrusion molding, blow molding, rotary molding and the like.

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Abstract

La présente invention concerne une composition de résine de polyamide qui présente une fluidité élevée et qui présente d'excellentes propriétés mécaniques et une excellente aptitude au glissement lorsqu'elle est utilisée en tant qu'article moulé.　La composition de résine de polyamide comprend de 60 à 85 % en masse d'une résine de polyamide aliphatique (A), de 0,5 à 9 % en masse d'une résine fluorée copolymère (B) qui peut avoir un groupe fonctionnel, de 5 à 20 % en masse de fibre de carbone (C), et pas plus de 34,5 % en masse d'autres composants (D), par rapport à 100 % en masse de la composition de résine de polyamide.
PCT/JP2021/040348 2020-11-04 2021-11-02 Composition de résine de polyamide et article moulé comprenant la composition de résine de polyamide WO2022097625A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0741666A (ja) * 1993-07-28 1995-02-10 Japan Synthetic Rubber Co Ltd ポリアミド樹脂組成物
JPH07286670A (ja) * 1994-02-28 1995-10-31 Ntn Corp オイルシールリング
JPH10324801A (ja) * 1996-07-19 1998-12-08 Ube Ind Ltd ポリアミド樹脂組成物
JP2020168761A (ja) * 2019-04-01 2020-10-15 旭化成株式会社 摺動部材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0741666A (ja) * 1993-07-28 1995-02-10 Japan Synthetic Rubber Co Ltd ポリアミド樹脂組成物
JPH07286670A (ja) * 1994-02-28 1995-10-31 Ntn Corp オイルシールリング
JPH10324801A (ja) * 1996-07-19 1998-12-08 Ube Ind Ltd ポリアミド樹脂組成物
JP2020168761A (ja) * 2019-04-01 2020-10-15 旭化成株式会社 摺動部材

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