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WO2016067962A1 - Composition de resine polyamide pour materiau d'amortissement - Google Patents

Composition de resine polyamide pour materiau d'amortissement Download PDF

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Publication number
WO2016067962A1
WO2016067962A1 PCT/JP2015/079493 JP2015079493W WO2016067962A1 WO 2016067962 A1 WO2016067962 A1 WO 2016067962A1 JP 2015079493 W JP2015079493 W JP 2015079493W WO 2016067962 A1 WO2016067962 A1 WO 2016067962A1
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Prior art keywords
polyamide resin
mass
resin composition
parts
plasticizer
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PCT/JP2015/079493
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English (en)
Japanese (ja)
Inventor
義朗 小田
智也 坪井
嘉則 長谷川
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Kao Corp
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Kao Corp
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Priority claimed from JP2015116064A external-priority patent/JP6841588B2/ja
Application filed by Kao Corp filed Critical Kao Corp
Priority to US15/521,031 priority Critical patent/US10465063B2/en
Priority to EP15854259.7A priority patent/EP3214146A4/fr
Priority to CN201580058587.4A priority patent/CN107148460B/zh
Publication of WO2016067962A1 publication Critical patent/WO2016067962A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a polyamide resin composition for a vibration damping material. More specifically, the present invention relates to a vibration damping material obtained by molding the polyamide resin composition, and use of the material for acoustic equipment, electrical products, vehicles, buildings, and industrial equipment.
  • a material having high vibration damping properties a metal plate and a vibration-absorbing material such as rubber or asphalt bonded together, or a composite material such as a vibration-damping steel plate with a vibration-absorbing material sandwiched between metal plates Is mentioned.
  • These damping materials retain their shape with a highly rigid metal plate and absorb vibration with a vibration absorbing material.
  • An alloy type material that absorbs vibration by converting kinetic energy into thermal energy by using twins or ferromagnetism even with metal alone.
  • the composite material has a problem in that the product itself becomes heavy because the processability is limited because different materials are bonded together and a metal steel plate is used. Further, the alloy type material is heavy because it uses only metal, and the vibration damping performance is insufficient.
  • a functional resin composition having a vibration suppressing function for example, in Patent Document 1, 5 to 40 parts by weight of a plasticizer and 10 to 70 reinforcing fibers are used with respect to 100 parts by weight of a polyamide resin.
  • a sound insulating resin composition composed of parts by weight is disclosed.
  • reinforcing material reinforcing fibers such as glass fiber, aramid fiber, carbon fiber and whisker are used, but it is described that fillers such as iron oxide, alumina and zinc oxide can be used in combination.
  • Patent Document 2 discloses that damping properties and fluidity are greatly improved by blending a specific amount of polyamide monomer and / or a 9-mer or less polyamide oligomer with a polyamide resin. .
  • the composition can be blended with a plasticizer or an inorganic filler. In the examples, 45 parts by weight of glass fiber is blended with 100 parts by weight of the resin.
  • the present invention relates to the following [1] to [5].
  • [1] In the polyamide resin 15 to 1 or 2 types selected from the group consisting of 7 to 35 parts by mass of a plasticizer and plate-like fillers and needle-like fillers with respect to 100 parts by mass of the polyamide resin.
  • a polyamide resin composition for vibration damping materials comprising ⁇ 80 parts by mass.
  • [2] A vibration damping material comprising the polyamide resin composition according to [1].
  • [3] Use of the polyamide resin composition according to [1] as a vibration damping material.
  • Step (1) 7 to 35 parts by mass of a plasticizer and 15 to 80 of one or more selected from plate-like fillers and needle-like fillers with respect to 100 parts by mass of the polyamide resin.
  • FIG. 1 is a diagram showing a jig used for measuring the loss factor.
  • the conventional polyamide resin composition needs further improvement. That is, it is desired to develop a polyamide resin composition capable of not only improving vibration damping by increasing vibration attenuation but also reducing the initial amplitude of vibration.
  • the present invention provides a polyamide resin composition for a vibration damping material having excellent vibration damping characteristics and excellent impact resistance despite a high flexural modulus, and a damping material containing the polyamide resin composition. Related to vibration material.
  • the polyamide resin composition of the present invention has a high flexural modulus, the vibration time is short, so in a product device, apparatus, or structure that generates vibration or sound, a casing around the generation source of vibration or sound.
  • the generated vibration is suppressed.
  • extra vibration related to product / equipment performance, or unpleasant vibration, noise and noise are suppressed. It has an excellent effect of reducing.
  • the polyamide resin composition for a vibration damping material of the present invention is a group comprising 7 to 35 parts by mass of a plasticizer, a plate-like filler and a needle-like filler with respect to 100 parts by mass of the polyamide resin. It is characterized by containing 15 to 80 parts by mass of one or more selected from the above. In this specification, such a polyamide resin composition may be referred to as a polyamide resin composition of the present invention.
  • the elastic modulus of the entire resin composition is improved while the loss factor is lowered.
  • This decrease in the loss factor is due to a decrease in the amount of energy loss in the resin portion because the proportion of the resin in the resin composition is reduced by the addition of the filler.
  • these fillers are oriented in the flow direction, and there are many interfaces that affect the friction generated when the molded body vibrates. It is estimated that the presence of friction occurs at the interface as compared with other shapes of fillers, energy loss occurs more, and the loss factor is reduced.
  • polyamide resin composition [Polyamide resin]
  • the polyamide resin in the present invention is not particularly limited as long as it is a known polyamide resin, but those described in the following (1) to (3) are preferable.
  • (1) Copolymer formed by polycondensation of diamine and dicarboxylic acid (2) Polymer formed by polycondensation of lactam or aminocarboxylic acid (3) Two types selected from the group consisting of (1) and (2) Polymer containing
  • diamine aliphatic diamine, aromatic diamine, and diamine having a cyclic structure
  • diamine aliphatic diamine, aromatic diamine, and diamine having a cyclic structure
  • Specific examples include tetramethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethyle diamine, undecamethylene diamine, dodecamethylene diamine, and metaxylylene diamine. These can be used alone or in combination of two or more. Among these, hexamethylenediamine is preferable from the viewpoint of improving vibration damping properties.
  • dicarboxylic acid aliphatic dicarboxylic acid, aromatic dicarboxylic acid, or dicarboxylic acid having a cyclic structure
  • dicarboxylic acid aliphatic dicarboxylic acid, aromatic dicarboxylic acid, or dicarboxylic acid having a cyclic structure
  • Specific examples include adipic acid, heptanedicarboxylic acid, octanedicarboxylic acid, nonanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid. These can be used alone or in combination of two or more. Of these, adipic acid is preferred from the viewpoint of improving vibration damping properties.
  • a lactam having 6 to 12 carbon atoms can be used.
  • Specific examples include ⁇ -caprolactam, enantolactam, undecane lactam, dodecane lactam, ⁇ -pyrrolidone, and ⁇ -piperidone. These can be used alone or in combination of two or more. Of these, ⁇ -caprolactam, undecane lactam, and dodecane lactam are preferable from the viewpoint of improving vibration damping properties.
  • an aminocarboxylic acid having 6 to 12 carbon atoms can be used.
  • Specific examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
  • 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid are preferable from the viewpoint of improving vibration damping properties. These can be used alone or in combination of two or more.
  • the polycondensation between the diamine and the dicarboxylic acid and the polycondensation of lactam or aminocarboxylic acid are not particularly limited and can be performed according to a known method.
  • the obtained polyamide resin gives rigidity that enables shape support when processed as an extrusion-molded body such as an injection-molded body, a film, a sheet, or a thermoformed body.
  • the glass transition temperature (Tg) is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, still more preferably 30 ° C. or higher, and still more preferably 35 ° C. or higher. Further, from the viewpoint of improving vibration damping properties, it is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower, and still more preferably 130 ° C. or lower.
  • the glass transition temperature of the resin and the elastomer can be measured according to the method described in Examples described later.
  • the polyamide resin in the present invention preferably has crystallinity.
  • the resin matrix composed of only the amorphous part or the crystal part has a uniform structure, and thus a large strain is generated with respect to vibration. Energy loss is small.
  • the resin matrix in which the crystal part and the amorphous part coexist forms a non-uniform continuous morphology having different elastic moduli, and when the vibration is applied, the resin matrix is locally localized in the amorphous part having a low elastic modulus. As a result, shear strain based on the strain is generated and energy loss is improved.
  • the polyamide resin generally has a high proportion of amorphous parts, but it is considered that the energy loss of the resin matrix can be further improved by providing crystallinity in the present invention.
  • a method for preparing a polyamide resin having crystallinity a method using a high purity of diamine, dicarboxylic acid, lactam or aminocarboxylic acid, a diamine, dicarboxylic acid, lactam or aminocarboxylic acid having a small side chain is selected, etc. The method is mentioned.
  • having crystallinity means that the resin is heated from 25 ° C. to 300 ° C.
  • a resin having a crystallization enthalpy ⁇ Hmc of preferably 5 J / g or more, more preferably 10 J / g or more, still more preferably 15 J / g or more, and even more preferably 30 J / g or more is used. Is good.
  • polyamide resin examples include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polycaproamide / polyhexamethylene adipamide copolymer (polyamide 6/66), polytetramethylene adipa Amide (polyamide 46), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecamide (polyamide 11), polydodecamide (polyamide 12), polyhexamethylene adipamide / polyhexamethylene terephthalate Amide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyhexa Tylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6
  • polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66 copolymer, polyamide 66 / 6I copolymer, polyamide 66 / 6I / 6 copolymer are preferable, and polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 6/66 are more preferable, and polyamide 6, polyamide 66, polyamide 11, and polyamide 12 are more preferable.
  • the content of the polyamide resin is preferably 30% by mass or more, more preferably 40% by mass or more in the polyamide resin composition from the viewpoint of improving the flexural modulus, suppressing the loss factor, and having impact resistance.
  • 50% by mass or more is more preferable, 55% by mass or more is more preferable, and 60% by mass or more is more preferable.
  • 90 mass% or less is preferable, 80 mass% or less is more preferable, 75 mass% or less is further more preferable, and 70 mass% or less is still more preferable.
  • the polyamide resin composition of the present invention contains a plasticizer as a vibration damping material from the viewpoint of improving the loss factor and impact resistance.
  • the plasticizer in the present invention is not particularly limited as long as it is a plasticizer applicable to a polyamide resin, but an amide plasticizer, an ester plasticizer, and an amide ester plasticizer can be used.
  • amide plasticizer examples include a carboxylic acid amide plasticizer and a sulfonamide plasticizer.
  • the carboxylic acid amide plasticizer includes at least one acid selected from the group consisting of benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid and anhydrides thereof, and an alkyl group having 2 to 8 carbon atoms.
  • examples include amides with dialkylamines.
  • Examples of the dialkylamine having 2 to 8 carbon atoms in the alkyl group include diethylamine, dipropylamine, dibutylamine, dihexylamine, di2-ethylhexylamine, dioctylamine and the like.
  • the molecular weight of the carboxylic acid amide plasticizer is preferably 250 or more and 2000 or less, more preferably 300 or more and 1500 or less, and still more preferably 350 or more and 1000 or less.
  • sulfonamide plasticizer examples include aromatic sulfonamide plasticizers. Specifically, N-butylbenzenesulfonamide, benzenesulfonamide, p-toluenesulfonamide, o, p-toluenesulfonamide, N Examples include-(2-hydroxypropyl) benzenesulfonamide, N-ethyl-o, p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, and N-methyl-p-toluenesulfonamide. N-butylbenzenesulfonamide is preferable.
  • ester plasticizers include monoester plasticizers, diester plasticizers, triester plasticizers, and polyester plasticizers.
  • monoester plasticizers examples include benzoate plasticizers and stearate plasticizers.
  • Benzoic acid ester plasticizers include benzoic acid and an aliphatic alcohol having 6 to 20 carbon atoms or an alkylene oxide adduct having 2 to 4 carbon atoms of the aliphatic alcohol (the number of added alkylene oxide is 10 mol or less).
  • the acid ester include 2-ethylhexyl p-oxybenzoate and 2-hexyldecyl p-oxybenzoate.
  • the stearic acid ester plasticizer include stearic acid and an aliphatic alcohol having 1 to 18 carbon atoms or an alkylene oxide adduct having 2 to 4 carbon atoms of the aliphatic alcohol (the number of added alkylene oxide is 10 mol or less).
  • An acid ester is mentioned, Specifically, a methyl stearate, an ethyl stearate, a butyl stearate, a hexyl stearate is mentioned.
  • diester plasticizer examples include phthalic acid, terephthalic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, and one or more acids selected from the group consisting of these anhydrides, aliphatic alcohols, Examples thereof include diester plasticizers composed of one or two or more alcohols selected from the group consisting of alicyclic alcohols and aromatic alcohols.
  • butylbenzyl phthalate dilauryl phthalate, diheptyl phthalate, Dibutyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, diethyl phthalate, diisodecyl phthalate, dioctyl phthalate, dioctyl adipate, diisodecyl adipate, di (butoxyethyl) adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl male Chromatography, dibutyl maleate, dioctyl sebacate, and dibutyl sebacate.
  • triester plasticizer examples include one or more acids selected from the group consisting of citric acid, trimellitic acid, phosphoric acid, and anhydrides thereof, aliphatic alcohols, alicyclic alcohols, and aromatics.
  • Triester plasticizers composed of one or more alcohols selected from the group consisting of group alcohols.
  • citric acid triesters such as triethyl citrate, tributyl citrate, 2-ethylhexyl citrate; trimellitic triesters such as tributyl trimellitic acid, trioctyl trimellitic acid, and trimellitic acid tris (2-ethylhexyl) Esters; tricresyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, trioctyl phosphate, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (butoxyethyl) phosphate, tris ( ⁇ -Phosphoric triesters such as -chloropropyl) phosphate, triphenyl phosphate, octyl diphenyl phosphate.
  • the polyester plasticizer is a plasticizer having four or more ester groups, and examples thereof include pyromellitic acid compounds and acetyltrialkyl citrate compounds.
  • amide ester plasticizer examples include one or more acids selected from the group consisting of phthalic acid, trimellitic acid, pyromellitic acid and anhydrides thereof, and dialkyl having an alkyl group with 2 to 8 carbon atoms.
  • acids selected from the group consisting of phthalic acid, trimellitic acid, pyromellitic acid and anhydrides thereof, and dialkyl having an alkyl group with 2 to 8 carbon atoms.
  • examples thereof include amide esters of an amine and an aliphatic alcohol having 6 to 20 carbon atoms or an alkylene oxide adduct having 2 to 4 carbon atoms of the aliphatic alcohol (the number of added alkylene oxide is 10 mol or less).
  • dialkylamine having 2 to 8 carbon atoms in the alkyl group examples include diethylamine, dipropylamine, dibutylamine, dihexylamine, di2-ethylhexylamine, dioctylamine and the like.
  • aliphatic alcohol having 6 to 20 carbon atoms examples include n-hexanol, 2-ethylhexanol, n-octanol, i-nonyl alcohol, decanol, lauryl alcohol, cetyl alcohol, i-tridecanol, hexyl decanol, oleyl alcohol, octyldodeca Nord etc. are mentioned.
  • the alkylene oxide adduct having 2 to 4 carbon atoms of the aliphatic alcohol having 6 to 20 carbon atoms may be one or more of ethylene oxide, propylene oxide, butylene oxide of the aliphatic alcohol having 6 to 20 carbon atoms. Of adducts.
  • the number of moles of alkylene oxide added is preferably 10 moles or less, more preferably 5 moles or less, per mole of alcohol.
  • the molecular weight of the amide ester plasticizer is preferably 250 or more and 2000 or less, more preferably 300 or more and 1500 or less, and still more preferably 350 or more and 1000 or less.
  • epoxy plasticizers plasticizers for rubber, chlorinated paraffin, polyhydric alcohols and derivatives thereof, alcohols, caprolactams, oligoamides, metal halides, and the like can be used.
  • the content of one or more selected from the group consisting of an amide plasticizer, an ester plasticizer, and an amide ester plasticizer is a damping material, from the viewpoint of improving the loss factor, Preferably it is 50 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.
  • “substantially 100% by mass” refers to a case in which a trace amount of impurities is inevitably included.
  • the content of the plasticizer means the total content when a plurality of compounds are contained.
  • the content of the plasticizer may be 7 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the polyamide resin, but preferably 10 parts by mass or more from the viewpoint of improving impact resistance and loss factor. Preferably, it is 15 parts by mass or more, and from the viewpoint of improving the flexural modulus, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 18 parts by mass or less. .
  • the content of the plasticizer is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 9% by mass or more, from the viewpoint of improving impact resistance and loss factor. More preferably, it is 10% by mass or more, and from the viewpoint of improving the flexural modulus, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
  • the polyamide resin composition of the present invention contains a filler from the viewpoint of improving the flexural modulus.
  • a filler in this invention the 1 type (s) or 2 or more types chosen from the group which consists of the plate-shaped filler and needle-shaped filler normally used for reinforcement
  • the plate-like filler has an aspect ratio (the length of the longest side of the maximum surface of the plate-like body / the thickness of the surface) of 2 or more and 150 or less, and extends in the longitudinal direction determined by the following formula.
  • the ratio of the major axis to the minor axis (cross section length / short ratio) in a cross section substantially perpendicular to the axis is 2 or more and less than 150.
  • Cross section length / short ratio longest diameter of the cross section substantially perpendicular to the axis extending in the longitudinal direction / the length of the shortest diameter plate-like filler of the same cross section (the length of the longest side in the maximum surface) is the polyamide resin composition
  • it is preferably 1.0 ⁇ m or more, more preferably 2 ⁇ m or more, further preferably 3 ⁇ m or more, preferably 150 ⁇ m or less, more preferably 100 ⁇ m.
  • it is more preferably 50 ⁇ m or less, further preferably 30 ⁇ m or less, and further preferably 15 ⁇ m or less.
  • the thickness is not particularly limited, from the same viewpoint, it is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, still more preferably Is 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • the aspect ratio of the plate-like filler is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and preferably 120 or less, more preferably 90 or less, from the same viewpoint. Preferably it is 70 or less, More preferably, it is 50 or less.
  • the cross-sectional length ratio of the plate-like filler is preferably 3 or more, more preferably 5 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 10 or less. More preferably, it is 8 or less.
  • Specific examples of the plate filler include, for example, glass flakes, non-swellable mica, swellable mica, graphite, metal foil, talc, clay, mica, sericite, zeolite, bentonite, organically modified bentonite, montmorillonite, and organically modified.
  • Examples include montmorillonite, dolomite, smectite, hydrotalcite, plate-like iron oxide, plate-like calcium carbonate, plate-like magnesium hydroxide, and plate-like barium sulfate.
  • talc, mica, and plate-like barium sulfate are preferable, talc and mica are more preferable, and talc is more preferable from the viewpoint of improving the flexural modulus and suppressing the decrease in loss factor.
  • the side length and thickness of the plate-like filler can be obtained by observing 100 randomly selected fillers with an optical microscope and calculating the number average thereof.
  • the needle-shaped filler has an aspect ratio (particle length / particle diameter) in the range of 2 to 150, and the ratio of the major axis to the minor axis in the cross section obtained by the above formula (cross section length / short ratio). Is 1 or more and less than 2.
  • the length of the acicular filler (particle length) is preferably 1.0 ⁇ m or more, more preferably from the viewpoint of obtaining good dispersibility in the polyamide resin composition, improving flexural elasticity, and suppressing loss factor reduction.
  • the particle size is not particularly limited, but from the same viewpoint, it is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.5 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and further Preferably it is 10 micrometers or less.
  • the aspect ratio of the needle-like filler is preferably 3 or more, more preferably 5 or more, and preferably 120 or less, more preferably 90 or less, still more preferably 70 or less, from the same viewpoint. Preferably it is 50 or less, More preferably, it is 30 or less, More preferably, it is 20 or less, More preferably, it is 10 or less. Further, the cross-sectional length ratio of the acicular filler is preferably 1.2 or more, more preferably 1.5 or more, and preferably 1.8 or less.
  • the acicular filler include, for example, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, asbestos, zonolite, phosphate fiber, elastadite, slag fiber, gypsum fiber, Examples thereof include silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber. Of these, potassium titanate whiskers and wollastonite are preferable.
  • the particle length and particle diameter of the acicular filler can be determined by observing 100 randomly selected fillers with an optical microscope and calculating the number average. When the particle diameter has a minor axis and a major axis, the major axis is used for calculation.
  • plate-like fillers and needle-like fillers can be used alone or in combination of two or more, and the shape when combined is not particularly limited.
  • the content of one or more selected from the group consisting of a plate-like filler and an acicular filler may be 15 to 80 parts by mass with respect to 100 parts by mass of the polyamide resin. From the viewpoint of improving the elastic modulus, it is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass or more, and from the viewpoint of suppressing the loss factor, preferably 60 parts by mass or less, More preferably, it is 50 parts by mass or less.
  • the content of one or more selected from the group consisting of a plate-like filler and an acicular filler is preferably 50 from the viewpoint of suppressing a loss factor loss.
  • % By mass more preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably substantially 100% by mass, and even more preferably 100%.
  • % By mass “substantially 100 mass%” refers to the case where impurities are inevitably included.
  • content of a filler means a total content, when a several compound contains.
  • a filler other than the plate-like filler and the needle-like filler can be used as long as the effects of the present invention are not impaired.
  • Specific examples include fibrous fillers and granular fillers that are usually used for reinforcing thermoplastic resins. Among these, fibrous fillers are preferred.
  • the fibrous filler has an aspect ratio (average fiber length / average fiber diameter) exceeding 150.
  • the length of the fibrous filler (average fiber length) is preferably 0.15 mm or more, more preferably 0.2 mm or more, and still more preferably 0.5 mm, from the viewpoint of improving the flexural modulus and suppressing the decrease in loss factor. More preferably, it is 1 mm or more, preferably 30 mm or less, more preferably 10 mm or less, and still more preferably 5 mm or less.
  • the average fiber diameter is not particularly limited, but from the same viewpoint, it is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, More preferably, it is 20 ⁇ m or less.
  • the aspect ratio is preferably 160 or more, more preferably 180 or more, further preferably 200 or more, and preferably 10,000 or less, more preferably 5000 or less, still more preferably 1000 or less, from the same viewpoint. More preferably, it is 800 or less, More preferably, it is 500 or less, More preferably, it is 300 or less.
  • the fibrous filler examples include glass fiber, carbon fiber, graphite fiber, metal fiber, and cellulose fiber. Among these, from the same viewpoint, carbon fiber and glass fiber are preferable, and glass fiber is more preferable.
  • the fiber length and fiber diameter of the fibrous filler can be determined by observing 100 randomly selected fillers with an optical microscope and calculating the number average thereof. If the fiber diameter has a minor axis and a major axis, the major axis is used for calculation.
  • the fibrous filler is cut by the shearing force in the kneading part and averaged.
  • the average fiber length of the fibrous filler in the resin is preferably 100 to 800 ⁇ m, more preferably 200 to 700 ⁇ m, and still more preferably 300 to 600 ⁇ m from the same viewpoint.
  • the fibrous fillers can be used alone or in combination of two or more.
  • the content of the fibrous filler is preferably 1 part by mass with respect to 100 parts by mass of the polyamide resin from the viewpoint of improving the flexural modulus of the resin composition and suppressing a decrease in loss factor and a decrease in impact resistance. As mentioned above, More preferably, it is 3 mass parts or more, Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less, More preferably, it is 7 mass parts or less. Further, in the filler used in the present invention, the content of the fibrous filler is preferably 3% by mass or more from the viewpoint of suppressing the decrease in loss factor and the impact resistance with the improvement in flexural modulus. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.
  • the mass ratio [(plate shape + needle shape) / fibrous shape] of one type or two or more types of fillers selected from the group consisting of a plate-like filler and a needle-like filler and a fibrous filler is: 70/30 to 95/5 is preferable, 80/20 to 90/10 is more preferable, and 85/15 to 90/10 is more preferable from the viewpoint of improving the flexural modulus and suppressing the loss factor and the impact resistance. Further preferred.
  • the granular filler includes not only a spherical shape but also an elliptical cross section or a substantially oval shape to some extent, and the aspect ratio (longest diameter of granular material / shortest diameter of granular material) is A value of 1 or more and less than 2 is preferred.
  • the average particle diameter of the granular filler is preferably 1.0 ⁇ m or more, more preferably 5 ⁇ m or more, from the viewpoint of obtaining good dispersibility in the polyamide resin composition, improving the flexural modulus, and suppressing the decrease in loss factor.
  • kaolin finely divided silicic acid, feldspar powder, granular calcium carbonate, granular magnesium hydroxide, granular barium sulfate, aluminum hydroxide, magnesium carbonate, calcium oxide, aluminum oxide, magnesium oxide, titanium oxide, aluminum silicate, Examples include various balloons, various beads, silicon oxide, gypsum, novacurite, dosonite, and clay.
  • the diameter of a granular filler can be calculated
  • the granular fillers can be used alone or in combination of two or more.
  • the content of the particulate filler is preferably 3 parts by mass or more with respect to 100 parts by mass of the polyamide resin, from the viewpoint of suppressing the decrease in loss coefficient and the decrease in impact resistance as well as improving the flexural modulus of the resin composition. More preferably, it is 4 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 6 parts by mass or less. is there.
  • the plate-like, granular, or acicular filler is coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.
  • a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.
  • a coupling agent such as aminosilane or epoxysilane.
  • the filler in the present invention may be one containing at least one selected from the group consisting of plate-like fillers and needle-like fillers. Among them, the bending elastic modulus is improved, and the loss factor. 1 type or 2 or more types selected from the group consisting of plate-like fillers and needle-like fillers, and 1 or 2 types selected from the group consisting of granular fillers and fibrous fillers It is preferable to use the above together, and it is more preferable to use one or more selected from the group consisting of plate-like fillers and needle-like fillers and one or more of fibrous fillers in combination. . Specifically, mica and / or talc and glass fiber are preferably used, and talc and glass fiber are more preferably used.
  • 15 to 80 parts by mass of one or more selected from the group consisting of plate-like fillers and needle-like fillers may be used.
  • the total content of the fillers used may be polyamide resin 100 From the viewpoint of improving the flexural modulus relative to parts by mass, it is preferably at least 20 parts by mass, more preferably at least 25 parts by mass, even more preferably at least 30 parts by mass, and even more preferably at least 35 parts by mass, and the loss factor. From the viewpoint of suppressing the decrease in the amount, it is preferably 55 parts by mass or less, more preferably 50 parts by mass or less.
  • the total content of the fillers used in the polyamide resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20 from the viewpoint of improving impact resistance and flexural modulus. From the viewpoint of suppressing loss factor loss, it is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and further preferably 30% by mass or less.
  • the mass ratio of one or two or more fillers selected from the group consisting of plasticizers, plate-like fillers and needle-like fillers Is preferably from 0.15 to 0.8, more preferably from 0.25 to 0.6, and still more preferably from 0.3 to 0.4, from the viewpoint of improving the flexural modulus and suppressing the loss factor. preferable.
  • the polyamide resin composition of the present invention can contain an organic crystal nucleating agent from the viewpoint of improving the crystallization speed of the polyamide resin, improving the crystallinity of the polyamide resin, and improving the flexural modulus.
  • organic crystal nucleating agent known organic crystal nucleating agents can be used, such as organic carboxylic acid metal salts, organic sulfonates, carboxylic acid amides, phosphorus compound metal salts, rosin metal salts, and alkoxy metal salts. Etc. can be used.
  • organic carboxylic acid metal salts include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate.
  • Examples of the organic sulfonate include sodium p-toluenesulfonate and sodium sulfoisophthalate.
  • Examples of the carboxylic acid amide include stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, and trimesic acid tris (t-butylamide).
  • Examples of the phosphorus compound metal salt include sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate.
  • metal salts of rosins include sodium dehydroabietic acid and sodium dihydroabietic acid.
  • Examples of the alkoxy metal salt include 2,2-methylbis (4,6-di-t-butylphenyl) sodium.
  • Other organic crystal nucleating agents include benzylidene sorbitol and its derivatives.
  • the content of the organic crystal nucleating agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts from the viewpoint of improving impact resistance, flexural modulus, and loss factor with respect to 100 parts by mass of the polyamide resin. From the viewpoint of improving impact resistance, flexural modulus, and loss factor, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 0.5 parts by mass or more. Is 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.
  • the content of the organic crystal nucleating agent means the total content of all the organic crystal nucleating agents contained in the polyamide resin composition.
  • the polyamide resin composition of the present invention can contain a styrene / isoprene block copolymer as a component other than the above as long as the effects of the present invention are not impaired.
  • the styrene / isoprene block copolymer in the present invention is a block copolymer having polystyrene blocks at both ends and having at least one of a polyisoprene block or a vinyl-polyisoprene block therebetween. Further, an isoprene block or a butadiene block may be copolymerized or a hydrogenated structure may be used.
  • styrene / isoprene block copolymer examples include polystyrene-isoprene block copolymer (SIS), polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS), polystyrene-vinyl-polyisoprene.
  • SIS polystyrene-isoprene block copolymer
  • SEPS polystyrene-hydrogenated polyisoprene-polystyrene block copolymer
  • polystyrene-vinyl-polyisoprene examples include polystyrene-vinyl-polyisoprene.
  • SHIVS Polystyrene block copolymer
  • polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene-polystyrene block copolymer polystyrene-hydrogenated polybutadiene-polyisoprene-polystyrene block copolymer, and the like. These may be used alone or in combination of two or more. In the present invention, it is preferable to use a polystyrene-vinyl-polyisoprene-polystyrene block copolymer, and a commercially available product of such a block copolymer includes “Hibler” series manufactured by Kuraray Plastics. .
  • the styrene content in the styrene / isoprene block copolymer is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 30% by mass from the viewpoint of improving vibration damping properties in a high temperature region and a low temperature region. % Or less, more preferably 25% by mass or less.
  • the high temperature region means 35 to 80 ° C.
  • the low temperature region means ⁇ 20 to 10 ° C.
  • the styrene content in the copolymer is described in Examples described later. It can be measured according to the method.
  • the styrene / isoprene block copolymer has a glass transition temperature Tg of preferably ⁇ 40 ° C. or higher, and preferably 20 ° C. or lower, from the viewpoint of improving vibration damping properties in a high temperature region and a low temperature region.
  • the content of the styrene / isoprene block copolymer is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the polyamide resin, from the viewpoint of improving the loss factor in the low temperature range. Part or more is more preferable, and 13 parts by mass or more is more preferable. Moreover, from a viewpoint of suppressing the fall of a bending elastic modulus, 40 mass parts or less are preferable, 30 mass parts or less are more preferable, and 20 mass parts or less are still more preferable.
  • the content of the styrene / isoprene block copolymer is preferably 3% by mass or more, more preferably 5% by mass or more from the viewpoint of improving the loss factor, and the bending elastic modulus is decreased. From a viewpoint of suppressing, it is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
  • the polyamide resin composition of the present invention comprises one or more selected from the group consisting of 7 to 35 parts by weight of a plasticizer, a plate-like filler and a needle-like filler with respect to 100 parts by weight of the polyamide resin. If it contains 15 to 80 parts by mass of filler, it can be prepared without any particular limitation.
  • a known kneader such as a closed kneader, a single or twin screw extruder, an open roll type kneader is used for a raw material containing a polyamide resin, a plasticizer, and the above-described filler and, if necessary, various additives. And can be prepared by melt kneading.
  • the melt-kneaded product may be dried or cooled according to a known method.
  • the raw materials can be melt-kneaded after being uniformly mixed in advance using a Henschel mixer, a super mixer or the like, and the remaining raw materials are added after pre-impregnating a plasticizer with a polyamide resin. You may melt-knead.
  • a supercritical gas may be present and melt mixed.
  • the melt kneading temperature is not generally set depending on the type of polyamide resin to be used, but from the viewpoint of improving the moldability and prevention of deterioration of the polyamide resin composition, it is preferably 220 ° C. or higher, more preferably 225 ° C. or higher. 230 ° C. or higher, and preferably 300 ° C. or lower, more preferably 290 ° C. or lower, further preferably 280 ° C. or lower, more preferably 260 ° C. or lower, still more preferably 250 ° C. or lower, and further preferably 240 ° C. or lower.
  • the melt-kneading time cannot be generally determined depending on the melt-kneading temperature and the type of the kneader, but is preferably 15 to 900 seconds.
  • the melt-kneaded material thus obtained has excellent vibration damping characteristics and excellent impact resistance despite its high flexural modulus, and therefore has various properties such as injection molding, extrusion molding, and thermoforming.
  • the molding method it can be suitably used as a product such as an acoustic device, an electric product, a building, or an industrial device, or a component or casing thereof.
  • the polyamide resin composition of the present invention has a high flexural modulus even with a single material, it has excellent vibration damping performance that can sufficiently hold the shape with a single material without using a highly rigid material such as a metal steel plate.
  • it can also be preferably used for products such as automobiles, railways, aircrafts, etc.
  • the present invention also provides a polyamide resin containing one or more kinds selected from 7 to 35 parts by mass of a plasticizer, a plate-like filler and a needle-like filler with respect to 100 parts by mass of the polyamide resin.
  • a polyamide resin composition containing 15 to 80 parts by mass of the agent can be used as a vibration damping material.
  • polyamide resin composition of the present invention to products such as acoustic equipment, electrical products, vehicles, buildings, industrial equipment, or parts or casings thereof, is a method for manufacturing the parts, casing, apparatus, and equipment, It can set suitably according to an application location and the desired objective, and can be used according to the conventional method of the said technical field. That is, by molding the polyamide resin composition of the present invention according to a known method, a product such as an acoustic device, an electric product, a vehicle, a building, an industrial device, or a part or casing thereof can be obtained.
  • the polyamide resin composition pellets are filled into an injection molding machine and injected into a mold. And obtained by molding.
  • a known injection molding machine can be used.
  • those having a cylinder and a screw inserted into the cylinder as main components [J75E-D, J110AD-180H (manufactured by Nippon Steel Works), etc.] can be mentioned.
  • the raw material of the said polyamide resin composition may be supplied to a cylinder and melt-kneaded as it is, it is preferable to fill the injection-molding machine with what was previously melt-kneaded.
  • the set temperature of the cylinder is preferably 220 ° C. or higher, and more preferably 235 ° C. or higher. Moreover, 290 degrees C or less is preferable, 280 degrees C or less is more preferable, 260 degrees C or less is further more preferable, and 255 degrees C or less is still more preferable.
  • a melt kneader means the set temperature of the cylinder of the kneader when melt kneading.
  • the cylinder is equipped with a heater, and the temperature is adjusted accordingly. Although the number of heaters varies depending on the model and is not determined unconditionally, the heater adjusted to the set temperature is preferably at least on the melt-kneaded product discharge port side (nozzle tip side).
  • the mold temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower, from the viewpoint of improving the crystallization speed and workability of the polyamide resin composition. Moreover, 20 degreeC or more is preferable, 30 degreeC or more is more preferable, and 40 degreeC or more is still more preferable.
  • the holding time in the mold cannot be generally determined depending on the temperature of the mold, but is preferably 5 to 100 seconds from the viewpoint of improving the productivity of the molded body.
  • the polyamide resin composition of the present invention is used for speakers, televisions, radio cassettes, headphones, audio components, microphones, and the like as acoustic device casing materials;
  • Electric tools such as electric drivers, computers, projectors, servers, electrical products with cooling fans such as POS systems, washing machines, clothes dryers, air conditioner indoor units, sewing machines, dishwashers, fan heaters, multifunction machines, printers, scanners , For hard disk drives, video cameras, etc .; for electric toothbrushes, electric shavers, massage machines, etc., as parts and components for electrical products with vibration sources;
  • generators, etc . refrigerated as materials for casings and parts of electrical products with compressors , Vending machines, air conditioner outdoor units, dehumidifiers, home generators; automotive parts materials such as dashboards, instrument panels, floors, doors, roofs, interior materials, oil pans, front covers, rocker covers For materials around engines such as: For materials for railway parts, interior materials such as floors, walls, side panels, ceilings, doors, chairs,
  • the present invention also provides a method for producing a part or casing containing the polyamide resin composition of the present invention.
  • the production method is not particularly limited as long as it includes a step of molding the polyamide resin composition of the present invention according to a known method, and examples thereof include a method including a step of injection molding the polyamide resin composition of the present invention.
  • a process can be added as appropriate.
  • Step (1) 7 to 35 parts by mass of a plasticizer and 15 to 80 of one or more selected from plate-like fillers and needle-like fillers with respect to 100 parts by mass of the polyamide resin.
  • Step (1) is a step of preparing a melt kneaded product of the polyamide resin composition.
  • the polyamide resin is used in an amount of 7 to 35 parts by weight of a plasticizer, 15 or 80 kinds of one or more selected from plate-like fillers and needle-like fillers with respect to 100 parts by weight of the polyamide resin.
  • the raw material containing various parts as necessary, preferably 220 ° C. or higher, more preferably 225 ° C. or higher, further preferably 230 ° C. or higher, preferably 300 ° C. or lower, more preferably 290 ° C. or lower, More preferably, it can be prepared by melt kneading at 280 ° C. or less, more preferably 260 ° C. or less, more preferably 250 ° C. or less, more preferably 240 ° C. or less.
  • Step (2) is a step of injection molding a melt-kneaded product of the polyamide resin composition.
  • the melt-kneaded product obtained in step (1) is preferably 220 ° C. or higher, more preferably 225 ° C. or higher, preferably 290 ° C. or lower, more preferably 280 ° C. or lower, and still more preferably 260.
  • the injection molded product of the present invention thus obtained can be suitably used as a part or casing containing a vibration damping material.
  • the present invention further discloses the following polyamide resin composition and use thereof.
  • polyamide resin 15 to 1 or 2 types selected from the group consisting of 7 to 35 parts by mass of a plasticizer and plate-like fillers and needle-like fillers with respect to 100 parts by mass of the polyamide resin.
  • a polyamide resin composition for vibration damping materials comprising ⁇ 80 parts by mass.
  • (1) Copolymer formed by polycondensation of diamine and dicarboxylic acid (2) Polymer formed by polycondensation of lactam or aminocarboxylic acid (3) Two types selected from the group consisting of (1) and (2) Polymer ⁇ 3> including the above
  • the diamine an aliphatic diamine, an aromatic diamine, or a diamine having a cyclic structure is preferably used.
  • Tetramethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethyle diamine, undecamethylene The polyamide resin composition according to ⁇ 2>, wherein diamine, dodecamethylenediamine, and metaxylylenediamine are more preferable, and hexamethylenediamine is more preferable.
  • the dicarboxylic acid is preferably an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a dicarboxylic acid having a cyclic structure, and adipic acid, heptanedicarboxylic acid, octanedicarboxylic acid, nonanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid,
  • ⁇ 5> As the lactam, a lactam having 6 to 12 carbon atoms is preferable, and ⁇ -caprolactam, enantolactam, undecane lactam, dodecane lactam, ⁇ -pyrrolidone, ⁇ -piperidone are more preferable, and ⁇ -caprolactam, undecane lactam, dodecane lactam. Is more preferable, The polyamide resin composition as described in said ⁇ 2>.
  • the aminocarboxylic acid is preferably an aminocarboxylic acid having 6 to 12 carbon atoms, more preferably 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, or 12-aminododecanoic acid.
  • the polyamide resin has a glass transition temperature (Tg) of preferably 20 ° C. or higher, more preferably 25 ° C. or higher, still more preferably 30 ° C.
  • the polyamide resin composition according to any one of ⁇ 1> to ⁇ 6>, which is 150 ° C. or lower, more preferably 140 ° C. or lower, and still more preferably 130 ° C. or lower.
  • the polyamide resin is heated from 25 ° C. to 300 ° C. at a temperature rising rate of 20 ° C./min, held in that state for 5 minutes, and then cooled at ⁇ 20 ° C./min so as to be 25 ° C. or lower.
  • the crystallization enthalpy ⁇ Hmc determined from the area of the exothermic peak accompanying crystallization is preferably 5 J / g or more, more preferably 10 J / g or more, still more preferably 15 J / g or more, and further preferably 30 J / g or more.
  • Polyamide resins such as polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polycaproamide / polyhexamethylene adipamide copolymer (polyamide 6/66), polytetramethylene adipa Amide (polyamide 46), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecamide (polyamide 11), polydodecamide (polyamide 12), polyhexamethylene adipamide / polyhexamethylene terephthalate Amide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyhexamethyl Renterephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T
  • the content of the polyamide resin in the polyamide resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 55% by mass or more, and 60% by mass.
  • the above is more preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, 75% by mass or less is further preferable, and 70% by mass or less is further preferable, any one of the above items ⁇ 1> to ⁇ 9> Polyamide resin composition.
  • the plasticizer is preferably one or more selected from the group consisting of an amide plasticizer, an ester plasticizer, and an amide ester plasticizer, wherein any of the above ⁇ 1> to ⁇ 10> Polyamide resin composition.
  • amide plasticizer is preferably one or more selected from the group consisting of a carboxylic acid amide plasticizer and a sulfonamide plasticizer.
  • the ester plasticizer is preferably one or more selected from the group consisting of a monoester plasticizer, a diester plasticizer, a triester plasticizer, and a polyester plasticizer, ⁇ 11 > The polyamide resin composition described.
  • Examples of the amide ester plasticizer include one or more acids selected from the group consisting of phthalic acid, trimellitic acid, pyromellitic acid and anhydrides thereof, and an alkyl group having 2 to 2 carbon atoms.
  • the content of one or more selected from the group consisting of an amide plasticizer, an ester plasticizer, and an amide ester plasticizer in the plasticizer is preferably 50% by mass or more, more preferably.
  • any of the above ⁇ 11> to ⁇ 14> which is 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, more preferably substantially 100% by mass, and still more preferably 100% by mass.
  • the polyamide resin composition as described. ⁇ 16> The content of the plasticizer is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, with respect to 100 parts by mass of the polyamide resin.
  • the content of the plasticizer is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 9% by mass or more, and further preferably 10% by mass or more.
  • the ratio of the major axis to the minor axis in the cross section substantially perpendicular to the axis extending in the longitudinal direction determined by the longest diameter of the cross section substantially perpendicular to the axis extending in the direction / the shortest diameter of the cross section (cross section length ratio) is 2 or more.
  • the needle-like filler has an aspect ratio (particle length / particle diameter) in the range of 2 to 150, and the ratio of the major axis to the minor axis in the cross section obtained by the above formula (cross section length). 1) to less than 2, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, zonolite, phosphate fiber, elastadite, slag fiber, gypsum fiber, silica fiber Silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber are preferable, and potassium titanate whisker and wollastonite are more preferable, and the polyamide resin composition according to any one of ⁇ 1> to ⁇ 18>.
  • the content of one or more selected from the group consisting of plate-like fillers and needle-like fillers is preferably 20 parts by mass or more, more preferably 25 parts by mass with respect to 100 parts by mass of the polyamide resin. Part or more, more preferably 30 parts by weight or more, preferably 60 parts by weight or less, more preferably 50 parts by weight or less, in any one of the above items ⁇ 1> to ⁇ 19>.
  • the content of one or more selected from the group consisting of a plate-like filler and a needle-like filler is preferably 50% by mass or more, more preferably 70% by mass.
  • ⁇ 22> Furthermore, it is preferable to contain 1 type, or 2 or more types selected from the group consisting of a fibrous filler and a granular filler, and it is more preferable to contain 1 type or 2 or more types of fibrous fillers.
  • the fibrous filler has an aspect ratio (average fiber length / average fiber diameter) exceeding 150, and is preferably glass fiber, carbon fiber, graphite fiber, metal fiber, or cellulose fiber, and carbon fiber or glass
  • the content of the fibrous filler is preferably 1 part by mass or more, more preferably 3 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the content of the fibrous filler is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 30% by mass. % Or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less, in any one of ⁇ 22> to ⁇ 24> above.
  • the mass ratio [(plate + needle) / fibrous] of one or more fillers selected from the group consisting of a plate filler and a needle filler and a fibrous filler is 70.
  • the granular filler has an aspect ratio (longest diameter of granular material / shortest diameter of granular material) of 1 or more and less than 2, and is preferably close to 1, kaolin, finely divided silicic acid , Feldspar powder, granular calcium carbonate, granular magnesium hydroxide, granular barium sulfate, aluminum hydroxide, magnesium carbonate, calcium oxide, aluminum oxide, magnesium oxide, titanium oxide, aluminum silicate, various balloons, various beads, silicon oxide, gypsum , Novacurite, dawsonite, and clay are preferable, granular barium sulfate, aluminum hydroxide, and granular calcium carbonate are more preferable, and granular calcium carbonate and granular barium sulfate are more preferable, and
  • the content of the particulate filler is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the polyamide resin composition according to ⁇ 22> or ⁇ 27> further preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 6 parts by mass or less.
  • the plate-like, granular, or acicular filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.
  • a coupling agent such as epoxysilane.
  • One or more selected from the group consisting of plate-like fillers and needle-like fillers and one or more selected from the group consisting of granular fillers and fibrous fillers are used in combination.
  • the total content of the filler used is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and still more preferably 35 parts per 100 parts by mass of the polyamide resin.
  • the polyamide resin composition according to any one of ⁇ 1> to ⁇ 30>, wherein the polyamide resin composition is at least part by mass, preferably at most 55 parts by mass, more preferably at most 50 parts by mass.
  • the total content of the filler used in the polyamide resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 45% by mass or less.
  • the polyamide resin composition according to any one of ⁇ 1> to ⁇ 31> more preferably 40% by mass or less, further preferably 35% by mass or less, and further preferably 30% by mass or less.
  • Mass ratio of one or more fillers selected from the group consisting of plasticizers, plate-like fillers, and needle-like fillers [plasticizer / (plate-like filler + needle-like filler)] Is preferably from 0.15 to 0.8, more preferably from 0.25 to 0.6, still more preferably from 0.3 to 0.4, and the polyamide resin composition according to any one of ⁇ 1> to ⁇ 32> above .
  • the content of the organic crystal nucleating agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.5 parts by mass or more with respect to 100 parts by mass of the polyamide resin.
  • the polyamide according to ⁇ 34> preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and further preferably 3 parts by mass or less. Resin composition.
  • the content of the styrene / isoprene block copolymer is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, further preferably 100 parts by mass of the polyamide resin.
  • the polyamide resin composition according to ⁇ 36> which is 13 parts by mass or more, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.
  • ⁇ 38> 7-100 parts by mass of a plasticizer and 15-80 parts by mass of one or more selected from plate-like fillers and needle-like fillers with respect to 100 parts by mass of the polyamide resin.
  • the melt kneading temperature is preferably 220 ° C. or higher, more preferably 225 ° C. or higher, further preferably 230 ° C. or higher, preferably 300 ° C. or lower, more preferably 290 ° C. or lower, still more preferably 280 ° C. or lower.
  • ⁇ 40> Use of the polyamide resin composition according to any one of ⁇ 1> to ⁇ 39> as a vibration damping material.
  • Products such as acoustic equipment, electrical products, vehicles, buildings, industrial equipment, etc. obtained by molding the polyamide resin composition according to any one of ⁇ 1> to ⁇ 39>, or a component or housing thereof. body.
  • a method for manufacturing a component or a housing including the following steps.
  • Step (1) 7 to 35 parts by mass of a plasticizer and 15 to 80 of one or more selected from plate-like fillers and needle-like fillers with respect to 100 parts by mass of the polyamide resin.
  • Glass transition temperature of polyamide resin Using a flat plate test piece (40 mm ⁇ 5 mm ⁇ 0.4 mm) of a sample prepared in the same manner as described later, using a DMA apparatus (manufactured by SII, EXSTAR6000), with a measurement frequency of 1 Hz, a temperature increase rate of 2 ° C./min The temperature is raised from ⁇ 20 ° C. to 250 ° C., and the peak temperature of the obtained loss modulus is obtained as the glass transition point.
  • a DMA apparatus manufactured by SII, EXSTAR6000
  • Crystallization enthalpy of polyamide resin Approximately 7.5 mg of a polyamide resin sample is weighed, and the resin is heated from 25 ° C. to 300 ° C. at a heating rate of 20 ° C./min according to JIS K7122 (1999) using a DSC device (Perkin Elmer, DSC8500). Then, after maintaining for 5 minutes in this state, when cooling at ⁇ 20 ° C./min so as to be 25 ° C. or less, the crystallization enthalpy is calculated from the exothermic peak accompanying crystallization.
  • Examples 1 to 17 and Comparative Examples 1 to 14 The raw materials of the polyamide resin compositions shown in Tables 1 to 4 were melt-kneaded at 240 ° C. using a same-direction meshing twin-screw extruder (TEX-28V, manufactured by Nippon Steel Works), and the strand was cut to obtain a polyamide resin. A pellet of the composition was obtained. The obtained pellets were dehumidified and dried at 110 ° C. for 3 hours, and the water content was adjusted to 500 ppm or less.
  • TEX-28V same-direction meshing twin-screw extruder
  • the obtained pellets were injection molded using an injection molding machine (J110AD-180H manufactured by Nippon Steel Works, 6 cylinder temperature settings).
  • the cylinder temperature was set to 240 ° C. from the nozzle tip side to the 5th unit, 170 ° C. for the remaining 1 unit, and 45 ° C. under the hopper.
  • Mold temperature is set to 80 ° C., and prismatic test pieces (63 mm ⁇ 13 mm ⁇ 6.4 mm), prismatic test pieces (125 mm ⁇ 12 mm ⁇ 6 mm), and flat plate test pieces (127 mm ⁇ 12.7 mm ⁇ 1.2 mm) are molded.
  • a molded body of the polyamide resin composition was obtained.
  • Examples 18 to 19 and Comparative Examples 15 to 17 The polyamide resin composition raw materials shown in Table 5 were melt-kneaded at 280 ° C. using a twin-screw extruder with the same direction (TEX-28V, manufactured by Nippon Steel Works Co., Ltd.), strand cut, and polyamide resin composition Pellets were obtained. The obtained pellets were dehumidified and dried at 110 ° C. for 3 hours, and the water content was adjusted to 500 ppm or less.
  • TEX-28V twin-screw extruder with the same direction
  • the obtained pellets were injection molded using an injection molding machine (J110AD-180H manufactured by Nippon Steel Works, 6 cylinder temperature settings).
  • the cylinder temperature was set to 275 ° C. from the nozzle tip side to the fifth unit, the remaining 1 unit to 230 ° C., and the bottom of the hopper to 45 ° C.
  • the mold temperature was set to 80 ° C., prismatic test pieces (63 mm ⁇ 13 mm ⁇ 6.4 mm), prismatic test pieces (125 mm ⁇ 12 mm ⁇ 6 mm), flat plate test pieces (127 mm ⁇ 12.7 mm ⁇ 1.2 mm) and flat plate A test piece (70 mm ⁇ 40 mm ⁇ 2 mm) was molded to obtain a molded body of a polyamide resin composition.
  • Test Example 1 [Izod impact resistance] A prismatic test piece (63 mm ⁇ 13 mm ⁇ 6.4 mm) was subjected to an impact test using a Izod impact tester (manufactured by Yasuda Seiki Seisakusyo Co., Ltd.) with a notch of 13 mm based on JIS K7110. When the Izod impact resistance is 40 J / m or more, it can be determined that the impact resistance is high, and the higher the numerical value, the higher the effect.
  • Test example 2 Bending test on a prismatic test piece (125 mm x 12 mm x 6 mm) using Tensilon (Orientec, Tensilon Universal Testing Machine RTC-1210A) based on JIS K7203 and setting the crosshead speed to 3 mm / min To obtain the flexural modulus.
  • Tensilon Orientec, Tensilon Universal Testing Machine RTC-1210A
  • JIS K7203 JIS K7203
  • Test example 3 [loss factor] A flat test piece (127 mm ⁇ 12.7 mm ⁇ 1.2 mm) is fixed to a jig shown in FIG. 1 based on JIS G0602, and from a free vibration waveform of bending vibration by a one-end fixed impact vibration method. The loss factor was determined. The maximum value Xn of the response displacement was detected with a CCD laser displacement meter (manufactured by Keyence Corporation, LK-GD5000), and time analysis was performed with an FFT analyzer (manufactured by Air Brown, Photon II). The calculation section of the response displacement was set to 3.0 mm to 0.5 mm excluding the response displacement at the time of initial impact. It can be determined that the loss coefficient is 0.06 or higher, the loss coefficient is high, and the vibration attenuation is fast, and the higher the value, the higher the effect.
  • Examples 1 to 19 were highly effective in all of impact resistance, bending elastic modulus, and loss factor compared to Comparative Examples 1 to 17.
  • the toughness is remarkably improved in addition to the rigidity and vibration damping properties when the inorganic filler is a plate-like filler. From this, it is possible to improve any of toughness, rigidity, and vibration damping properties by blending a specific amount of plasticizer, plate-like filler and / or needle-like filler with various polyamide resins. This suggests the application to various uses.
  • talc is preferable among the plate-like fillers from the viewpoint of further improving the loss factor.
  • the polyamide resin composition of the present invention is a material of an acoustic device such as a speaker, a television, a radio cassette, a headphone, an audio component or a microphone, a product such as an electric product, a vehicle, a building, an industrial device, or a part thereof, or a casing. It can be suitably used as a vibration damping material.

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

Abstract

La présente invention concerne une composition de résine polyamide pour un matériau d'amortissement, la composition de résine polyamide contenant une résine polyamide et, pour 100 parties en masse de la résine polyamide, 7 à 35 parties en masse d'un plastifiant et 15 à 80 parties en masse d'un ou plusieurs composé(s) choisi(s) dans le groupe comprenant des charges tabulaires et les charges aciculaires. Cette composition de résine polyamide est apte à être utilisée, par exemple, en tant que matériau pour équipement audio tel que des haut-parleurs, des téléviseurs, des enregistreurs de radio cassette, des écouteurs, des composants audio, ou des microphones ou en tant que matériau d'amortissement dans des produits tels que des produits électriques, des véhicules, des bâtiments, et un équipement industriel ou dans les composants ou boîtiers desdits produits.
PCT/JP2015/079493 2014-10-31 2015-10-20 Composition de resine polyamide pour materiau d'amortissement Ceased WO2016067962A1 (fr)

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US15/521,031 US10465063B2 (en) 2014-10-31 2015-10-20 Polyamide resin composition for damping material
EP15854259.7A EP3214146A4 (fr) 2014-10-31 2015-10-20 Composition de resine polyamide pour materiau d'amortissement
CN201580058587.4A CN107148460B (zh) 2014-10-31 2015-10-20 减振材料用的聚酰胺树脂组合物

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01263151A (ja) * 1988-04-15 1989-10-19 Mitsubishi Gas Chem Co Inc 自動車用ミラーステイ
JPH0489863A (ja) * 1990-08-02 1992-03-24 Bridgestone Corp 遮音性樹脂組成物
JPH09279012A (ja) * 1996-04-11 1997-10-28 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物
JP2000198974A (ja) * 1998-12-28 2000-07-18 Yokohama Rubber Co Ltd:The 制振材または防振材
JP2004149769A (ja) * 2002-10-08 2004-05-27 Mitsubishi Gas Chem Co Inc ポリアミドおよび樹脂組成物
JP2004204104A (ja) * 2002-12-26 2004-07-22 Toray Ind Inc ポリアミド樹脂組成物および成形品
JP2005187747A (ja) * 2003-12-26 2005-07-14 Mitsubishi Gas Chem Co Inc 制振材料
JP2006022238A (ja) * 2004-07-09 2006-01-26 Mitsubishi Engineering Plastics Corp 制振性ポリアミド樹脂組成物
JP2006070154A (ja) * 2004-09-02 2006-03-16 Ube Ind Ltd 制振性に優れたポリアミド樹脂組成物
JP2006117818A (ja) * 2004-10-22 2006-05-11 Toyobo Co Ltd ポリアミド樹脂組成物および複合成形体
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

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01263151A (ja) * 1988-04-15 1989-10-19 Mitsubishi Gas Chem Co Inc 自動車用ミラーステイ
JPH0489863A (ja) * 1990-08-02 1992-03-24 Bridgestone Corp 遮音性樹脂組成物
JPH09279012A (ja) * 1996-04-11 1997-10-28 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物
JP2000198974A (ja) * 1998-12-28 2000-07-18 Yokohama Rubber Co Ltd:The 制振材または防振材
JP2004149769A (ja) * 2002-10-08 2004-05-27 Mitsubishi Gas Chem Co Inc ポリアミドおよび樹脂組成物
JP2004204104A (ja) * 2002-12-26 2004-07-22 Toray Ind Inc ポリアミド樹脂組成物および成形品
JP2005187747A (ja) * 2003-12-26 2005-07-14 Mitsubishi Gas Chem Co Inc 制振材料
JP2006022238A (ja) * 2004-07-09 2006-01-26 Mitsubishi Engineering Plastics Corp 制振性ポリアミド樹脂組成物
JP2006070154A (ja) * 2004-09-02 2006-03-16 Ube Ind Ltd 制振性に優れたポリアミド樹脂組成物
JP2006117818A (ja) * 2004-10-22 2006-05-11 Toyobo Co Ltd ポリアミド樹脂組成物および複合成形体
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3214146A4 *

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