WO2016067961A1 - Composition de résine de polyester pour amortisseurs - Google Patents

Composition de résine de polyester pour amortisseurs Download PDF

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Publication number
WO2016067961A1
WO2016067961A1 PCT/JP2015/079492 JP2015079492W WO2016067961A1 WO 2016067961 A1 WO2016067961 A1 WO 2016067961A1 JP 2015079492 W JP2015079492 W JP 2015079492W WO 2016067961 A1 WO2016067961 A1 WO 2016067961A1
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polyester resin
resin composition
group
mass
acid
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PCT/JP2015/079492
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English (en)
Japanese (ja)
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義朗 小田
智也 坪井
嘉則 長谷川
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花王株式会社
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Priority claimed from JP2015116063A external-priority patent/JP6677456B2/ja
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to US15/519,892 priority Critical patent/US20170247527A1/en
Priority to CN201580057060.XA priority patent/CN107075342B/zh
Priority to EP15854438.7A priority patent/EP3214147B1/fr
Publication of WO2016067961A1 publication Critical patent/WO2016067961A1/fr

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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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 polyester resin composition for a vibration damping material. More specifically, the present invention relates to a vibration damping material obtained by molding the polyester 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.
  • Patent Document 1 mainly includes a crystalline thermoplastic polyester resin. It is disclosed that a material excellent in vibration damping and toughness can be obtained by blending a specific polymer selected from polyester elastomer and thermoplastic polyurethane with glass fiber having a specific shape. Yes.
  • Patent Document 2 discloses that a specific amount of a styrene / isoprene block copolymer is contained in a polylactic acid resin having a specific melt flow rate as a vibration damping material using a low environmental load polylactic acid resin. Thus, it is disclosed that the obtained molded body has excellent vibration damping properties.
  • the present invention relates to the following [1] to [5].
  • a thermoplastic polyester resin (A) composed of a dicarboxylic acid component and a diol component, one or more selected from the group consisting of a plasticizer and a styrene / isoprene block copolymer (B), and inorganic
  • a polyester resin composition for a vibration damping material comprising a filler (C).
  • a vibration damping material comprising the polyester resin composition according to [1].
  • [3] Use of the polyester resin composition according to [1] as a vibration damping material.
  • Step (1) Polyester containing a thermoplastic polyester resin (A), one or more selected from the group consisting of a plasticizer and a styrene / isoprene block copolymer (B), and an inorganic filler (C) Step of melt-kneading the resin composition to prepare a melt-kneaded product of the polyester resin composition
  • Step (2) Injection-molding the melt-kneaded product of the polyester resin composition obtained in Step (1) into a mold Process
  • FIG. 1 is a diagram showing a jig used for measuring the loss factor.
  • the conventional polyester resin composition needs further improvement. That is, there is a demand for the development of a polyester resin composition that not only improves vibration damping by increasing vibration damping but also reduces the initial amplitude of vibration.
  • the present invention relates to a polyester resin composition for a vibration damping material having excellent vibration damping characteristics despite its high flexural modulus, and a vibration damping material containing the polyester resin composition.
  • the polyester resin composition of the present invention has a high flexural modulus, so in a product device, apparatus, or structure that generates vibration or sound, a casing around the vibration or sound generation source.
  • 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 polyester resin composition for damping material of the present invention is selected from the group consisting of a thermoplastic polyester resin (A) composed of a dicarboxylic acid component and a diol component, a plasticizer and a styrene / isoprene block copolymer. Contains seeds or two or more (B), as well as inorganic filler (C). In this specification, this polyester resin composition may be described as the polyester 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. Therefore, in the present invention, by adding a plasticizer and / or a styrene / isoprene block copolymer to such a system, the loss factor is improved by adding flexibility and facilitating energy loss. It has been found that the loss factor can be suppressed while increasing the elastic modulus of the object.
  • polyester resin composition of the present invention friction occurs at the interface between the resin or plasticizer and / or styrene / isoprene block copolymer and the inorganic filler, resulting in energy loss, and a further loss factor. It is presumed that the decrease of the is suppressed.
  • thermoplastic polyester resin (A) comprises a dicarboxylic acid component and a diol component, and can be obtained by a combination of polycondensation of the dicarboxylic acid component and the diol component.
  • the dicarboxylic acid component includes dicarboxylic acid and lower ester derivatives thereof, and these are collectively referred to as a dicarboxylic acid component.
  • the dicarboxylic acid component constituting the thermoplastic polyester resin (A) aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, and dicarboxylic acid having a furan ring can be used.
  • the aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 26 carbon atoms.
  • the alicyclic dicarboxylic acid is preferably an alicyclic dicarboxylic acid having a total carbon number of 5 to 26, and examples thereof include adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid, and decalin dicarboxylic acid.
  • the aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having a total carbon number of 8 to 26.
  • terephthalic acid isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2 , 6-Naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylendanedicarboxylic acid, anthracene dicarboxylic acid, phenanthrene
  • the dicarboxylic acid having a furan ring is preferably a dicarboxylic acid having a furan ring having a total carbon number of 6 to 26, and examples thereof include 2,5-furandicarboxylic acid. These can be used alone or in combination of two or more.
  • succinic acid glutaric acid, adipic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid,
  • One or two selected from the group consisting of 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,5-furandicarboxylic acid More preferably, one or more selected from the group consisting of succinic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 2,5-furandicarboxylic acid are more preferable, One or two selected from the group consisting of terephthalic acid and 2,5-furandicarboxylic acid are more preferable, One or two selected from the group consisting of terephthalic acid and 2,
  • an aliphatic diol As the diol component constituting the thermoplastic polyester resin (A), an aliphatic diol, an alicyclic diol, an aromatic diol, or a diol having a furan ring can be used.
  • the aliphatic diol is preferably an aliphatic diol having 2 to 26 carbon atoms and a polyalkylene glycol, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, Examples include 4-butanediol, 1,2-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.
  • the alicyclic diol is preferably an alicyclic diol having 3 to 26 carbon atoms, and examples thereof include cyclohexanedimethanol, hydrogenated bisphenol A, spiroglycol, and isosorbide.
  • aromatic diol aromatic diols having 6 to 26 carbon atoms are preferable.
  • bisphenol A bisphenol A alkylene oxide adduct, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9, Examples include 9′-bis (4-hydroxyphenyl) fluorene and 2,2′bis (4′- ⁇ -hydroxyethoxyphenyl) propane.
  • the diol having a furan ring is preferably a diol having a furan ring having a total carbon number of 4 to 26, and examples thereof include 2,5-dihydroxyfuran. These can be used alone or in combination of two or more. Among these, from the viewpoint of improving vibration damping properties, ethylene glycol, 1,3-propanediol, 1,4-butanediol, cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenol A, bisphenol A alkylene oxide adduct, 1 , 3-benzenedimethanol, 1,4-benzenedimethanol, and 2,5-dihydroxyfuran are preferably selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4 -One or more selected from the group consisting of butanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and 2,5-dihydroxyfuran is more preferable.
  • either the aromatic ring, the alicyclic ring, or the furan ring is either dicarboxylic acid or diol. It is preferable to include in one or both.
  • the dicarboxylic acid component is one or more selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and dicarboxylic acids having a furan ring, preferably an aliphatic diol
  • the dicarboxylic acid component is an aliphatic dicarboxylic acid
  • it is preferably a combination with one or more selected from the group consisting of aromatic diols, alicyclic diols, and diols having a furan ring, and more
  • it is a combination with one or more aromatic diols.
  • the polycondensation of the dicarboxylic acid component and the diol component is not particularly limited and can be performed according to a known method.
  • the resulting thermoplastic polyester resin (A) gives the rigidity that enables shape support when processed as an extruded or thermoformed body such as an injection-molded body, film or sheet, and improves molding processability.
  • 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 from the viewpoint of improving heat resistance. 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 In order for the glass transition temperature to be the above temperature, it is effective to control the skeleton structure of the polyester resin. For example, it is possible to increase the glass transition temperature by preparing a thermoplastic polyester resin using a rigid component such as an aromatic dicarboxylic acid component or an alicyclic diol component as a raw material.
  • the glass transition temperature of the resin and the elastomer can be measured according to the method described in Examples described later.
  • the thermoplastic polyester resin (A) 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 thermoplastic polyester 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.
  • the plasticizer and / or the styrene / isoprene block copolymer (B) are dispersed, the amorphous part is softened or softened by the component (B), and more elastic modulus is obtained. Since the above-mentioned effect increases and the loss increases, it is presumed that the loss factor is further increased, and a polyester resin composition having more excellent vibration damping properties can be obtained.
  • Examples of a method for preparing a thermoplastic polyester resin having crystallinity include a method using a dicarboxylic acid component and a diol component having high purity, and a method using a dicarboxylic acid component having a small side chain and a diol component.
  • having crystallinity means that the resin is heated from 25 ° C. to 300 ° C. at a rate of temperature increase of 20 ° C./min according to JIS K7122 (1999), and kept in that state for 5 minutes. Next, it is a resin in which an exothermic peak accompanying crystallization is observed when cooled at ⁇ 20 ° C./min so as to be 25 ° C. or lower.
  • thermoplastic polyester resin (A) constituting the present invention has 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 further preferably 30 J / g or more. It is preferable to use a resin.
  • thermoplastic polyester resin (A) examples include polyethylene terephthalate composed of terephthalic acid and ethylene glycol (PET resin, Tg: 70 ° C.), terephthalic acid and 1 from the viewpoint of rigidity, heat resistance, and vibration damping properties.
  • the content of the thermoplastic polyester resin (A) is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, in the polyester resin composition. More preferably, it is more than 60% by mass and more preferably 60% by mass. Moreover, from a viewpoint of improving an elasticity modulus, 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.
  • a plasticizer and a styrene / isoprene block copolymer As the component (B) in the present invention, one or more selected from the group consisting of a plasticizer and a styrene / isoprene block copolymer are used. In the present specification, one or more selected from the group consisting of a plasticizer and a styrene / isoprene block copolymer may be collectively referred to as a component (B).
  • the plasticizer in the present invention includes one or more selected from the group consisting of a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer. Is preferred.
  • polyester plasticizer are preferably dicarboxylic acids having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and preferably dialcohols having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms.
  • polyester by the (poly) oxyalkylene adduct can be mentioned.
  • dicarboxylic acid include succinic acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, and isophthalic acid.
  • dialcohol examples include propylene glycol, 1,3-butanediol, 1,4-butanediol, , 6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol and the like.
  • the hydroxyl group and carboxy group of the polyester terminal may be esterified with monocarboxylic acid or monoalcohol and blocked.
  • polyhydric alcohol ester plasticizer examples include a polyhydric alcohol or an (poly) oxyalkylene adduct thereof, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 carbon atom. And mono-, di- or triesters with 1 to 4 monocarboxylic acids.
  • polyhydric alcohol examples include polyethylene glycol, polypropylene glycol, glycerin and the above dialcohol.
  • monocarboxylic acid examples include acetic acid and propionic acid.
  • polyvalent carboxylic acid ester plasticizer examples include polyvalent carboxylic acids, monoalcohols having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms, or their (poly).
  • the mono-, di-, or triester with an oxyalkylene adduct can be mentioned.
  • polyvalent carboxylic acid examples include trimellitic acid and the above dicarboxylic acid.
  • monoalcohol include methanol, ethanol, 1-propanol, 1-butanol, and 2-ethylhexanol.
  • a bisphenol plasticizer a bisphenol and a monoalkyl halide having 1 to 18 carbon atoms, more preferably 2 to 14 carbon atoms, still more preferably 4 to 10 carbon atoms, or a (poly) oxyalkylene adduct thereof.
  • examples thereof include mono- or diether.
  • bisphenol include bisphenol A and bisphenol S.
  • the monoalkyl halide include 1-octyl bromide, 1-dodecyl bromide, and 2-ethylhexyl bromide.
  • the plasticizer preferably has a (poly) oxyalkylene group or an alkylene group having 2 to 10 carbon atoms, a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid.
  • the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
  • the oxyalkylene group preferably has an alkylene group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • An oxyethylene group, an oxypropylene group, or an oxybutylene group is further included.
  • An oxyethylene group or an oxypropylene group is more preferable.
  • the plasticizer preferably contains one or more selected from the group consisting of the following compound groups (A) to (C) from the viewpoint of improving the loss factor, and includes the following compound group (A): And more preferably one or more selected from the group consisting of (B).
  • Compound group (A) An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound is an average of 2 to 3 alkylene oxides per hydroxyl group.
  • Ester compound group (B) which is an alcohol added with 5 to 5 moles Formula (I): R 1 O—CO—R 2 —CO — [(OR 3 ) m O—CO—R 2 —CO—] n OR 1 (I) (Wherein R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is an alkylene group having 2 to 4 carbon atoms, R 3 is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6) And n represents a number from 1 to 12, provided that all R 2 may be the same or different, and all R 3 may be the same or different. (C) An ester compound having two or more ester groups in the molecule, wherein the alcohol component constituting the ester compound is a monoalcohol
  • the ester compound contained in the compound group (A) is a polyhydric alcohol ester or polyhydric carboxylic acid ether ester having two or more ester groups in the molecule, and at least one of the alcohol components constituting the ester compound. Preference is given to ester compounds in which the seed is an alcohol obtained by adding an average of 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms per hydroxyl group.
  • Specific compounds include esters of acetic acid and glycerin with an average of 3 to 6 moles of ethylene oxide adduct (addition of 1 to 2 moles of ethylene oxide per hydroxyl group), and the average number of moles of acetic acid and ethylene oxide added is 4 to 4 6 Esters with polyethylene glycol, Esters with polyethylene glycol monomethyl ether having an average addition mole number of succinic acid and ethylene oxide of 2 to 3 (addition of 2 to 3 mol of ethylene oxide per hydroxyl group), Adipic acid and diethylene glycol monomethyl Esters with ether, esters with terephthalic acid and ethylene oxide with an average addition mole number of polyethylene glycol monomethyl ether of 2 to 3 (addition of 2 to 3 moles of ethylene oxide per hydroxyl group), 1,3,6-hexanetricarboxylic acid Acid and di Esters of Chi glycol monomethyl ether.
  • R 1 in formula (I) represents an alkyl group having 1 to 4 carbon atoms, and two of them exist in one molecule and exist at both ends of the molecule.
  • R 1 may be linear or branched as long as it has 1 to 4 carbon atoms.
  • the number of carbon atoms of the alkyl group is preferably 1 to 4 and more preferably 1 to 2 from the viewpoint of developing coloring resistance and a plasticizing effect.
  • Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and an iso-butyl group.
  • methyl Group and ethyl group are preferable, and methyl group is more preferable.
  • R 2 in the formula (I) represents an alkylene group having 2 to 4 carbon atoms, and a linear alkylene group is a preferred example.
  • Specific examples include ethylene group, 1,3-propylene group, and 1,4-butylene group. From the viewpoint of improving the loss factor, ethylene group, 1,3-propylene group, and 1,4-butylene group are preferred.
  • an ethylene group is more preferable.
  • all R 2 may be the same or different.
  • R 3 in formula (I) represents an alkylene group having 2 to 6 carbon atoms, and OR 3 is present in the repeating unit as an oxyalkylene group.
  • R 3 may be linear or branched as long as it has 2 to 6 carbon atoms.
  • the number of carbon atoms of the alkylene group is preferably 2 to 6 and more preferably 2 to 3 from the viewpoint of improving the loss factor.
  • all R 3 may be the same or different.
  • M represents the average number of repeating oxyalkylene groups, and from the viewpoint of heat resistance, the number is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.
  • N represents the average number of repeating units (average degree of polymerization) and is a number from 1 to 12.
  • the damping material is preferably a number of 1 to 12, more preferably a number of 1 to 6, and even more preferably a number of 1 to 5.
  • the average degree of polymerization may be determined by analysis such as NMR, but can be calculated according to the method described in Examples below.
  • R 1 is all methyl group
  • R 2 is ethylene group or 1,4-butylene group
  • R 3 is ethylene group or 1,3-propylene group
  • M is a number from 1 to 4
  • n is a number from 1 to 6
  • R 1 is all methyl group
  • R 2 is ethylene group or 1,4-butylene group
  • R 3 is ethylene group or 1
  • More preferred is a compound which is a 3-propylene group, wherein m is a number of 1 to 3, and n is a number of 1 to 5.
  • the compound represented by the formula (I) is not particularly limited as long as it has the above structure, but is preferably obtained by reacting the following raw materials (1) to (3).
  • (1) and (2) or (2) and (3) may form an ester compound.
  • (2) may be an acid anhydride or an acid halide.
  • the monohydric alcohol having an alkyl group having 1 to 4 carbon atoms is an alcohol containing R 1 , specifically, methanol,
  • Examples include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and tert-butanol.
  • methanol, ethanol, 1-propanol and 1-butanol are preferable, methanol and ethanol are more preferable, and methanol is further preferable.
  • Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms is a dicarboxylic acid containing R 2 , specifically, succinic acid, Examples include glutaric acid, adipic acid, and derivatives thereof such as succinic anhydride, glutaric anhydride, dimethyl succinate, dibutyl succinate, dimethyl glutarate, dimethyl adipate, and the like.
  • succinic acid, adipic acid and derivatives thereof for example, succinic anhydride, dimethyl succinate, dibutyl succinate, and dimethyl adipate are preferable, and succinic acid and derivatives thereof, for example, More preferred are succinic anhydride, dimethyl succinate, and dibutyl succinate.
  • Dihydric alcohol having an alkylene group having 2 to 6 carbon atoms is a dihydric alcohol containing R 3 , specifically, Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,5-hexanediol, Examples include 1,6-hexanediol and 3-methyl-1,5-pentanediol.
  • diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and 1,4-butanediol are preferable, and diethylene glycol, triethylene glycol, 1,2-propanediol and 1,3-propanediol are more preferable, and diethylene glycol, triethylene glycol and 1,3-propanediol are more preferable.
  • the monohydric alcohol is one or more selected from the group consisting of methanol, ethanol, 1-propanol, and 1-butanol; (2) the dicarboxylic acid is succinic acid, adipic acid, glutaric acid, and One or more selected from the group consisting of these derivatives, (3) dihydric alcohol is diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and It is preferably one or more selected from the group consisting of 1,4-butanediol, (1) The monohydric alcohol is one or more selected from the group consisting of methanol and ethanol, and (2) the dicarboxylic acid is selected from the group consisting of succinic acid, adipic acid, and derivatives thereof, or And (3) the dihydric alcohol is one or more selected from the group consisting of diethylene glycol, triethylene glycol, 1,2-propanediol, and 1,
  • the monohydric alcohol is methanol
  • the dicarboxylic acid is one or more selected from the group consisting of succinic acid and derivatives thereof
  • the dihydric alcohol is diethylene glycol, triethylene glycol, And one or more selected from the group consisting of 1,3-propanediol.
  • the method for obtaining the ester compound represented by the formula (I) by reacting the above (1) to (3) is not particularly limited, and examples thereof include the following methods 1 and 2.
  • Aspect 1 (2) Step of synthesizing dicarboxylic acid ester by performing esterification reaction of (2) dicarboxylic acid with (1) monohydric alcohol, and (3) Step of esterifying reaction of obtained dicarboxylic acid ester with dihydric alcohol
  • a method comprising the steps of: (1) monohydric alcohol, (2) dicarboxylic acid, and (3) dihydric alcohol reacting together
  • the method of aspect 1 is preferable from the viewpoint of adjusting the average degree of polymerization.
  • reaction of each above-mentioned process can be performed in accordance with a well-known method.
  • the compound represented by the formula (I) preferably has an acid value of 1.50 mgKOH / g or less, more preferably 1.00 mgKOH / g or less, from the viewpoint of improving the loss factor, and the hydroxyl value has a loss factor. From the viewpoint of improving the viscosity, it is preferably 10.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or less, still more preferably 3.0 mgKOH / g or less.
  • the acid value and hydroxyl value of a plasticizer can be measured according to the method as described in the below-mentioned Example.
  • the number average molecular weight of the compound represented by the formula (I) is preferably 300 to 1500, more preferably 300 to 1000 from the viewpoint of coloring resistance from the viewpoint of improving the loss factor.
  • the number average molecular weight of the plasticizer can be calculated according to the method described in Examples described later.
  • the saponification value of the compound represented by the formula (I) is preferably 500 to 800 mgKOH / g, more preferably 550 to 750 mgKOH / g, from the viewpoint of improving the loss factor.
  • the saponification value of a plasticizer can be measured according to the method as described in the below-mentioned Example.
  • the compound represented by the formula (I) preferably has an alkyl esterification rate (terminal alkyl esterification rate) with respect to two molecular ends of 95% or more, more preferably 98% or more. It is.
  • the terminal alkyl esterification rate of the plasticizer can be calculated according to the method described in Examples described later.
  • the ether group value of the compound represented by the formula (I) is preferably 0 to 8 mmol / g, more preferably 0 to 6 mmol / g from the viewpoint of shortening the vibration time.
  • the ether group value of the plasticizer can be calculated according to the method described in Examples described later.
  • ester compound included in the compound group (C) include an ester of adipic acid and 2-ethylhexanol (Example: DOA), and an ester of phthalic acid and 2-ethylhexanol (Example: DOP). ) Is preferred.
  • plasticizers one or more contents selected from the group consisting of polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers, and bisphenol plasticizers, preferably ( Selected from the group consisting of a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer having a poly) oxyalkylene group or an alkylene group having 2 to 10 carbon atoms.
  • the content of one or more selected compounds is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and further preferably 95%, from the viewpoint of improving the loss factor. It is 100 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.
  • “substantially 100% by mass” means a state that inevitably contains a trace amount of impurities.
  • the content of the plasticizer means the total content when a plurality of compounds are contained.
  • the content of the plasticizer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A) from the viewpoint of improving the loss factor. More preferably, it is 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 18 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass from the viewpoint of suppressing a decrease in flexural modulus. It is not more than part by mass, more preferably not more than 30 parts by mass, still more preferably not more than 25 parts by mass.
  • the content of the plasticizer is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and further preferably 8%, from the viewpoint of improving the loss factor. From the viewpoint of suppressing a decrease in flexural modulus, 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 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 10 parts by mass or more, more preferably 15 parts by mass or more from the viewpoint of improving the loss factor in the low temperature range with respect to 100 parts by mass of the thermoplastic polyester resin (A). More preferably, 18 parts by mass or more is further preferable, 20 parts by mass or more is further preferable, and 25 parts by mass or more is further preferable. Moreover, from a viewpoint of suppressing the fall of a bending elastic modulus, 50 mass parts or less are preferable, 40 mass parts or less are more preferable, and 35 mass parts or less are still more preferable.
  • the content of the styrene / isoprene block copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, from the viewpoint of improving the loss factor. From the viewpoint of suppressing a decrease in flexural modulus, it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.
  • a plasticizer and a styrene / isoprene block copolymer may be used in combination.
  • the plasticizer may be used alone or two or more and the styrene / isoprene block copolymer may be used alone or in combination. It can be used in combination with more than one species.
  • the total content of the plasticizer and the styrene / isoprene block copolymer when used in combination is preferably 15 parts by mass or more and 20 parts by mass from the viewpoint of improving the loss factor with respect to 100 parts by mass of the thermoplastic polyester resin (A). Part or more is more preferable, and 25 parts by mass or more is still more preferable. Moreover, from a viewpoint which suppresses a elasticity modulus fall, 60 mass parts or less are preferable, 50 mass parts or less are more preferable, and 40 mass parts or less are still more preferable.
  • the mass ratio of the plasticizer and the styrene / isoprene block copolymer (plasticizer / styrene / isoprene block copolymer) used in combination is preferably 30/70 to 70/30 from the viewpoint of suppressing a decrease in elastic modulus. 40/60 to 60/40 is more preferable.
  • the polyester resin composition of the present invention contains an inorganic filler (C) from the viewpoint of improving the flexural modulus.
  • the inorganic filler (C) in the present invention is not particularly limited as long as it is a known inorganic filler, and is usually an inorganic filler used for reinforcing a thermoplastic resin, specifically, a plate-like filler, 1 type (s) or 2 or more types chosen from the group which consists of a granular filler, an acicular filler, and a fibrous filler can be used.
  • the plate-like filler is one having an aspect ratio (the length of the longest side of the maximum surface of the plate-like body / the thickness of the surface) of 20 or more and 150 or less.
  • the length of the plate-like filler (the length of the longest side in the maximum surface)
  • it is 1.0 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, still more preferably 40 ⁇ m or less, More preferably, it is 30 ⁇ m or less.
  • the thickness is not particularly limited, but 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, still more preferably 0.2 ⁇ m or more, preferably 5 ⁇ m or less, More preferably, it is 3 micrometers or less, More preferably, it is 2 micrometers or less, More preferably, it is 1 micrometers or less, More preferably, it is 0.5 micrometers or less.
  • the aspect ratio of the plate-like filler is preferably 30 or more, more preferably 40 or more, still more preferably 50 or more, and preferably 120 or less, more preferably 100 or less, from the same viewpoint. Preferably it is 90 or less, More preferably, it is 80 or less.
  • 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, and talc and mica are more preferable from the viewpoint of improving the flexural modulus and suppressing the 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 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 particulate filler is preferably 1.0 ⁇ m or more, more preferably from the viewpoint of obtaining good dispersibility in the polyester resin composition, improving the flexural modulus, and / or improving the loss factor.
  • the diameter of a granular filler can be calculated
  • Needle-shaped fillers are those having an aspect ratio (particle length / particle diameter) in the range of 2 or more and less than 20.
  • the length of the acicular filler (particle length) is preferably 1.0 ⁇ m from the viewpoint of obtaining good dispersibility in the polyester resin composition, improving the flexural modulus, and / or improving the loss factor. Or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, further preferably 20 ⁇ m or more, further preferably 30 ⁇ m or more, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 80 ⁇ m or less, still more preferably 60 ⁇ m or less. It is.
  • 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. Further, the aspect ratio of the acicular filler is preferably 5 or more and preferably 10 or less from the same viewpoint.
  • 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.
  • 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, still more preferably 0.5 mm or more, from the viewpoint of improving the flexural modulus and loss factor. More preferably, it is 1 mm or more, Preferably it is 30 mm or less, More preferably, it is 10 mm or less, More preferably, it is 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, preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less. Further, from the same viewpoint, the aspect ratio is preferably 200 or more, more preferably 250 or more, further preferably 500 or more, preferably 10,000 or less, more preferably 5000 or less, still more preferably 1000 or less, More preferably, it is 800 or less.
  • Specific examples of the fibrous filler 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 viewpoint of the flexural modulus.
  • the granular, plate-like or needle-like filler may be coated or focused with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin. It may be treated with a coupling agent such as silane.
  • a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin. It may be treated with a coupling agent such as silane.
  • fillers can be used alone or in combination of two or more, and fillers having different shapes may be combined.
  • preferably one or more selected from the group consisting of plate-like fillers, needle-like fillers, and fibrous fillers More preferably, they are 1 type (s) or 2 or more types chosen from the group which consists of a plate-shaped filler and an acicular filler, More preferably, they are 1 type or 2 or more types of a plate-shaped filler.
  • mica, talc, and glass fiber are preferably used, more preferably mica and talc, and still more preferably mica.
  • the content of the plate-like filler in the inorganic filler is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, from the viewpoint of suppressing loss factor loss.
  • the content of the inorganic filler (C) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, from the viewpoint of improving the flexural modulus with respect to 100 parts by mass of the thermoplastic polyester resin (A). More preferably, it is more preferably 30 parts by mass or more, and still more preferably 35 parts by mass or more. Further, from the viewpoint of suppressing the loss factor, 80 parts by mass or less is preferable, 70 parts by mass or less is more preferable, 60 parts by mass or less is further preferable, 50 parts by mass or less is further preferable, and 45 parts by mass or less is still more preferable. .
  • content of an inorganic filler is a total mass of the inorganic filler used, and when a several compound is contained, it means the total content.
  • the content of the inorganic filler is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably, from the viewpoint of improving the flexural modulus. Is 20% by mass or more, more preferably 23% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less, from the viewpoint of suppressing the loss factor. .
  • the mass ratio of the component (B) and the inorganic filler (C) is 10/90 to 60 / from the viewpoint of improving the elastic modulus and improving the loss factor.
  • 40 is preferable, 25/75 to 50/50 is more preferable, and 40/60 to 45/55 is still more preferable.
  • the polyester resin composition of the present invention can contain an organic crystal nucleating agent from the viewpoint of improving the crystallization speed of the polyester resin, improving the crystallinity of the polyester 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, alkoxy metal salts,
  • organic nitrogen-containing compounds 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.
  • alkoxy metal salt examples include 2,2-methylbis (4,6-di-t-butylphenyl) sodium.
  • organic nitrogen-containing compound examples include Adeka Stub NA-05 (trade name) manufactured by Adeka Corporation.
  • Other organic crystal nucleating agents include benzylidene sorbitol and its derivatives.
  • the content of the organic crystal nucleating agent (D) is preferably 0.01 parts by mass or more, more preferably from the viewpoint of improving the flexural modulus and loss factor with respect to 100 parts by mass of the thermoplastic polyester resin (A). Is 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and from the viewpoint of improving the flexural modulus and loss factor, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. Is 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 1 part 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 polyester resin composition.
  • the polyester resin composition of the present invention includes an inorganic crystal nucleating agent, a hydrolysis inhibitor, a flame retardant, an antioxidant, a hydrocarbon wax, a lubricant that is an anionic surfactant, ultraviolet rays, as components other than those described above.
  • An absorber, an antistatic agent, an antifogging agent, a light stabilizer, a pigment, an antifungal agent, an antibacterial agent, a foaming agent, and the like can be contained as long as the effects of the present invention are not impaired.
  • other polymer materials and other resin compositions can be contained within a range that does not impair the effects of the present invention.
  • the polyester resin composition of the present invention comprises a thermoplastic polyester resin (A), a plasticizer and one or more selected from the group consisting of a styrene / isoprene block copolymer (B) and an inorganic filler (C). If it contains, it can prepare without limitation.
  • a raw material containing one or more selected from the group consisting of a thermoplastic polyester resin, a plasticizer and a styrene / isoprene block copolymer, an inorganic filler, and various additives as required It can be prepared by melt-kneading using a known kneader such as a monoaxial or biaxial extruder or an open roll type kneader.
  • the melt-kneaded product may be dried or cooled according to a known method.
  • the raw materials can be subjected to melt kneading after being uniformly mixed in advance using a Henschel mixer, a super mixer, or the like.
  • it may be melt-mixed in the presence of a supercritical gas.
  • the melt kneading temperature is not generally set depending on the type of the thermoplastic polyester resin to be used, but is preferably 220 ° C. or higher, more preferably 225 ° C. or higher, from the viewpoint of improving the moldability and deterioration prevention of the polyester resin composition.
  • it is 230 degreeC or more, and preferably 300 degreeC or less, More preferably, it is 290 degreeC or less, More preferably, it is 280 degreeC or less, More preferably, it is 260 degreeC or less, More preferably, it is 250 degreeC or less, More preferably, it is 240 degreeC or less .
  • 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 despite its high flexural modulus, and therefore, by using various molding methods such as injection molding, extrusion molding, thermoforming, etc. It can be suitably used as a product such as a device, an electric product, a building, or an industrial device, or a component or casing thereof. Further, since the polyester 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. However, it can also be preferably used for products such as automobiles, railways, aircrafts, etc. that require weight reduction of vehicles, or parts or casings thereof.
  • the present invention also contains one or more selected from the group consisting of a thermoplastic polyester resin (A), a plasticizer and a styrene / isoprene block copolymer (B), and an inorganic filler (C).
  • a polyester resin composition can be used as a vibration damping material.
  • polyester resin composition of the present invention to products such as audio equipment, electrical products, vehicles, buildings, industrial equipment, or parts or casings thereof is a method of 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 polyester resin composition of the present invention according to a known method, it is possible to obtain products such as acoustic equipment, electrical products, vehicles, buildings, industrial equipment, or parts or casings thereof.
  • the polyester 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 polyester 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 230 ° C or higher. Moreover, 290 degrees C or less is preferable, 280 degrees C or less is more preferable, 270 degrees C or less is still more preferable, 260 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 still more preferably 130 ° C. or lower, from the viewpoint of improving the crystallization speed and workability of the polyester 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 polyester resin composition of the present invention is used for speakers, televisions, radio cassettes, headphones, audio components, microphones and the like as acoustic device housing 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 . cool as parts and housing materials for electrical products with compressors Storage room, vending machine, air conditioner outdoor unit, dehumidifier, household generator; automotive parts materials such as dashboards, instrument panels, floors, doors, roofs, interior materials, oil pans, front covers, lockers For engine surrounding materials such as covers;
  • As materials for railway parts interior materials such as floors, walls, side panels, ceilings, doors, chairs, tables, casings and parts around motor
  • the present invention also provides a method for producing a part or casing containing the polyester resin composition of the present invention.
  • the production method is not particularly limited as long as it includes a step of molding the polyester resin composition of the present invention according to a known method, and examples thereof include a method including a step of injection molding the polyester resin composition of the present invention.
  • a process can be added as appropriate.
  • Step (1) Polyester containing a thermoplastic polyester resin (A), one or more selected from the group consisting of a plasticizer and a styrene / isoprene block copolymer (B), and an inorganic filler (C) Step of melt-kneading the resin composition to prepare a melt-kneaded product of the polyester resin composition
  • Step (2) Injection-molding the melt-kneaded product of the polyester resin composition obtained in Step (1) into a mold Process
  • Step (1) is a step of preparing a melt-kneaded product of the polyester resin composition.
  • one or more types (B) selected from the group consisting of a thermoplastic polyester resin (A), a plasticizer and a styrene / isoprene block copolymer, and an inorganic filler (C), various types as required.
  • the raw material containing the additive 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. More preferably, it can be prepared by melt-kneading at 260 ° C. or lower, more preferably 250 ° C. or lower, more preferably 240 ° C. or lower.
  • Step (2) is a step of injection molding a melt-kneaded product of the polyester resin composition.
  • the melt-kneaded product obtained in the step (1) is preferably 220 ° C. or higher, more preferably 230 ° C. or higher, preferably 290 ° C. or lower, more preferably 280 ° C. or lower, still more preferably 270.
  • 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 polyester resin composition and use thereof.
  • Thermoplastic polyester resin (A) composed of a dicarboxylic acid component and a diol component, one or more selected from the group consisting of a plasticizer and a styrene / isoprene block copolymer (B), and inorganic A polyester resin composition for a vibration damping material containing a filler (C).
  • thermoplastic polyester resin (A) consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and dicarboxylic acids having a furan ring
  • the diol component constituting the thermoplastic polyester resin (A) is one or more selected from the group consisting of an aliphatic diol, an alicyclic diol, an aromatic diol, and a diol having a furan ring.
  • the dicarboxylic acid component constituting the thermoplastic polyester resin (A) is one or more selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and dicarboxylic acids having a furan ring. In the case, preferably it is a combination of one or more selected from the group consisting of aliphatic diols, aromatic diols, alicyclic diols, and diols having a furan ring, more preferably aliphatic diols and The polyester resin composition according to any one of ⁇ 1> to ⁇ 3>, which is a combination of one or more selected from the group consisting of aromatic diols.
  • the dicarboxylic acid component constituting the thermoplastic polyester resin (A) is an aliphatic dicarboxylic acid, it is preferably selected from the group consisting of an aromatic diol, an alicyclic diol, and a diol having a furan ring.
  • the dicarboxylic acid component constituting the thermoplastic polyester resin (A) includes succinic acid, glutaric acid, adipic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1 , 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and one or more selected from the group consisting of 2,5-furandicarboxylic acid are preferred.
  • Succinic acid, cyclohexane One or more selected from the group consisting of dicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 2,5-furandicarboxylic acid are more preferable.
  • One or two selected from the group consisting of acids is more preferable, ⁇ 1> to ⁇ 5>
  • the diol component constituting the thermoplastic polyester resin (A) includes ethylene glycol, 1,3-propanediol, 1,4-butanediol, cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenol A, and bisphenol.
  • thermoplastic polyester resin (A) has a glass transition temperature (Tg) of preferably 20 ° C. or higher, more preferably 25 ° C. or higher, still more preferably 30 ° C.
  • the polyester resin composition according to any one of ⁇ 1> to ⁇ 7>, which 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 thermoplastic polyester resin (A) is heated from 25 ° C. to 300 ° C. at a rate of temperature increase of 20 ° C./min.
  • 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 even more preferably 30 J / g.
  • the thermoplastic polyester resin (A) includes polyethylene terephthalate composed of terephthalic acid and ethylene glycol, polytrimethylene terephthalate composed of terephthalic acid and 1,3-propanediol, terephthalic acid and 1,4-butane.
  • the content of the thermoplastic polyester resin (A) in the polyester resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and further 55% by mass or more.
  • 60% by mass or more 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
  • 70% by mass or less is more preferable
  • the plasticizer contains one or more selected from the group consisting of polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers, and bisphenol plasticizers.
  • the plasticizer preferably has a (poly) oxyalkylene group or an alkylene group having 2 to 10 carbon atoms, a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, And a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid having a (poly) oxyalkylene group, more preferably one or two or more selected from the group consisting of bisphenol plasticizers
  • the polyester resin composition according to any one of ⁇ 1> to ⁇ 12> comprising one or more selected from the group consisting of an ester plasticizer and a bisphenol plasticizer.
  • the plasticizer preferably includes one or more selected from the group consisting of the following compound groups (A) to (C), and includes the following compound groups (A) and (B).
  • the polyester resin composition according to any one of ⁇ 1> to ⁇ 13>, more preferably containing one or more selected from the group.
  • Compound group (A) An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound is an average of 2 to 3 alkylene oxides per hydroxyl group.
  • Ester compound group (B) which is an alcohol added with 5 to 5 moles Formula (I): R 1 O—CO—R 2 —CO — [(OR 3 ) m O—CO—R 2 —CO—] n OR 1 (I) (Wherein R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is an alkylene group having 2 to 4 carbon atoms, R 3 is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6) And n represents a number from 1 to 12, provided that all R 2 may be the same or different, and all R 3 may be the same or different.
  • a plasticizer a polyester
  • a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer having an alkylene group having 2 to 10 carbon atoms a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer having an alkylene group having 2 to 10 carbon atoms.
  • the above content more preferably a polyester plasticizer having a (poly) oxyalkylene group, a polyvalent alcohol A content of one or more selected from the group consisting of a ruester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer, and a group consisting of the compound groups (A) to (C)
  • the content of one or more selected compounds is preferably 50% 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, and still more preferably substantially.
  • the polyester resin composition according to any one of ⁇ 12> to ⁇ 14>, which is 100% by mass, more preferably 100% by mass.
  • the content of the plasticizer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, more preferably 100 parts by mass of the thermoplastic polyester resin (A). 10 parts by mass or more, more preferably 15 parts by mass or more, further preferably 18 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, and further preferably 25 parts by mass.
  • the polyester resin composition according to any one of ⁇ 1> to ⁇ 15>, wherein the polyester resin composition is not more than part by mass.
  • the content of the plasticizer is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and still more preferably 10% by mass or more.
  • the styrene / isoprene block copolymer is a block copolymer having a polystyrene block at both ends, and having at least one of a polyisoprene block or a vinyl-polyisoprene block therebetween.
  • polyester resin composition according to any one of the above. ⁇ 19>
  • styrene / isoprene block copolymer polystyrene-isoprene block copolymer, polystyrene-hydrogenated polyisoprene-polystyrene block copolymer, polystyrene-vinyl-polyisoprene-polystyrene block copolymer, polystyrene-hydrogen.
  • the polyester resin composition according to any one of> to ⁇ 18>.
  • the styrene content in the styrene / isoprene block copolymer is preferably 10% by mass or more, more preferably 15% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less.
  • the polyester resin composition according to any one of ⁇ 1> to ⁇ 19>. ⁇ 21> The polyester resin composition according to any one of ⁇ 1> to ⁇ 20>, wherein the styrene / isoprene block copolymer has a glass transition temperature Tg of preferably ⁇ 40 ° C. or higher, preferably 20 ° C. or lower. object.
  • the content of the styrene / isoprene block copolymer is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 18 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A).
  • the polyester resin composition according to any one of the above.
  • the content of the styrene / isoprene block copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 30% by mass. % Or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, according to any one of ⁇ 1> to ⁇ 22>.
  • a plasticizer and a styrene / isoprene block copolymer may be used in combination, and the plasticizer may be used alone or in combination of two or more and the styrene / isoprene block copolymer alone or in combination of two or more.
  • the polyester resin composition according to any one of the above ⁇ 1> to ⁇ 23>. ⁇ 25> The total content of the plasticizer and the styrene / isoprene block copolymer is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, with respect to 100 parts by mass of the thermoplastic polyester resin (A).
  • the mass ratio of the plasticizer and the styrene / isoprene block copolymer is preferably 30/70 to 70/30, more preferably 40/60 to 60/40.
  • the inorganic filler (C) includes one or more selected from the group consisting of a plate-like filler, a granular filler, a needle-like filler, and a fibrous filler.
  • the plate-like filler has an aspect ratio (length of the longest side of the maximum surface of the plate-like body / thickness of the surface) of 20 or more and 150 or less, glass flakes, non-swellable mica, Swellable mica, graphite, metal foil, talc, clay, mica, sericite, zeolite, bentonite, organic modified bentonite, montmorillonite, organic modified montmorillonite, dolomite, smectite, hydrotalcite, plate-like iron oxide, plate-like calcium carbonate,
  • the plate-like magnesium hydroxide and plate-like barium sulfate are preferable, talc, mica and plate-like barium sulfate are more preferable, and talc and mica are more preferable,
  • 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,
  • the polyester resin composition as described in said ⁇ 27>.
  • the needle-shaped filler has an aspect ratio (particle length / particle diameter) in the range of 2 or more and less than 20, and includes potassium titanate whisker, aluminum borate whisker, magnesium whisker, and 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, potassium titanate whisker
  • the aspect ratio is more than 150, and glass fiber, carbon fiber, graphite fiber, metal fiber, and cellulose fiber are preferable, carbon fiber,
  • the granular, plate-like, or needle-like 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.
  • the inorganic filler (C) is preferably one or more selected from the group consisting of plate-like fillers, needle-like fillers, and fibrous fillers, more preferably plate-like fillers and
  • ⁇ 34> The polyester resin composition according to any one of ⁇ 1> to ⁇ 33>, wherein mica, talc, and glass fiber are preferably used, more preferably mica and talc, and still more preferably mica.
  • the content of the plate-like filler in the inorganic filler (C) is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more, ⁇ 27> to ⁇ 34 >
  • the content of the inorganic filler (C) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A).
  • the polyester resin composition according to any one of ⁇ 1> to ⁇ 35>, wherein the content is further preferably 45 parts by mass or less.
  • the content of the inorganic filler is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, and further preferably.
  • the mass ratio of the component (B) to the inorganic filler (C) (component (B) / inorganic filler (C)) is preferably 10/90 to 60/40, and preferably 25/75 to 50/50.
  • the content of the organic crystal nucleating agent (D) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 100 parts by mass of the thermoplastic polyester resin (A). Is 0.2 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and further preferably 1 part by mass or less.
  • ⁇ 41> Melting and kneading a raw material containing a thermoplastic polyester resin (A), a plasticizer and one or more selected from the group consisting of a styrene / isoprene block copolymer (B) and an inorganic filler (C)
  • the polyester resin composition according to any one of the above ⁇ 1> to ⁇ 40>, which is prepared as described above.
  • 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.
  • a method for manufacturing a component or a housing including the following steps.
  • Step (1) Polyester containing a thermoplastic polyester resin (A), one or more selected from the group consisting of a plasticizer and a styrene / isoprene block copolymer (B), and an inorganic filler (C) Step of melt-kneading the resin composition to prepare a melt-kneaded product of the polyester resin composition
  • Step (2) Injection-molding the melt-kneaded product of the polyester resin composition obtained in Step (1) into a mold Process
  • Saponification value Analysis is performed according to the test method of JIS K 0070, except that the temperature of the water bath is 95 ° C. and the heating time is 1 hour.
  • the molecular weight of the ester compound (B) means the number average molecular weight, and is calculated from the acid value, hydroxyl value, and saponification value according to the following formula.
  • Average molecular weight M (M 1 + M 2 ⁇ M 3 ⁇ 2) ⁇ n + M 1 ⁇ (M 3 ⁇ 17.01) ⁇ 2 + (M 3 ⁇ 17.01) ⁇ p + (M 2 ⁇ 17.01) ⁇ q + 1.
  • Terminal alkyl esterification rate The molecular terminal alkyl esterification rate (terminal alkyl esterification rate) can be calculated from the following formula. The larger the value of the molecular terminal alkyl esterification rate, the free carboxyl group or hydroxyl group There are few, and it shows that the molecular terminal is fully alkylesterified.
  • Terminal alkyl esterification rate (%) (p ⁇ 2) ⁇ 100
  • M 1 molecular weight of diester of dicarboxylic acid used as raw material and monohydric alcohol used as raw material
  • M 2 molecular weight of dihydric alcohol used as raw material
  • M 3 molecular weight of monohydric alcohol used as raw material
  • p in one molecule
  • q Number of terminal hydroxyl groups in one molecule
  • Ether group number The ether group number, which is the number of millimoles (mmol) of ether groups in 1 g of carboxylic acid ester, is calculated from the following formula.
  • m average number of repeating oxyalkylene groups
  • m-1 represents the number of ether groups in one molecule of dihydric alcohol
  • molecular weight uses the molecular weight of a number average value.
  • Plasticizer Production Example 1 Diester of succinic acid and triethylene glycol monomethyl ether
  • a 3 L flask equipped with a stirrer, thermometer and dehydration tube was charged with 500 g of succinic anhydride, 2463 g of triethylene glycol monomethyl ether, and 9.5 g of paratoluenesulfonic acid monohydrate, and nitrogen (500 mL / min) was added to the space.
  • the reaction was carried out at 110 ° C. for 15 hours under reduced pressure (4 to 10.7 kPa) while blowing.
  • the acid value of the reaction solution was 1.6 (mgKOH / g).
  • the obtained diester had an acid value of 0.2 (mg KOH / g), a saponification value of 276 (mg KOH / g), a hydroxyl value of 1 or less (mg KOH / g), and a hue APHA200.
  • plasticizer diester of succinic acid, 1,3-propanediol and methanol, raw material (molar ratio): dimethyl succinate / 1,3-propanediol (1.5 / 1)
  • plasticizer diester of succinic acid, 1,3-propanediol and methanol, raw material (molar ratio): dimethyl succinate / 1,3-propanediol (1.5 / 1)
  • 521 g (6.84 mol) of 1,3-propanediol and 5.9 g of a methanol solution containing 28% by weight sodium methoxide as a catalyst (Sodium methoxide 0.031 mol) was added, and methanol was distilled off with stirring at normal pressure and 120 ° C. for 0.5 hour.
  • Plasticizer Production Example 3 Diester of terephthalic acid and triethylene glycol monomethyl ether
  • a four-necked flask (with a stirrer, thermometer, distillation tube, and nitrogen blowing tube) was charged with 400 g of dimethyl terephthalate, 1015 g of triethylene glycol monomethyl ether, and 0.86 g of tin (II) octylate, and nitrogen (200 mL) in the space. / Min), methanol produced by the reaction was distilled off while stirring at normal pressure and 200 ° C. for 14 hours.
  • polyester resin composition materials shown in Tables 1 to 6 were melt-kneaded at 240 ° C. using a co-directional meshing twin screw extruder (TEX-28V, manufactured by Nippon Steel Works), and the strand was cut to obtain a polyester 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 co-directional 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.
  • the mold temperature was set to 80 ° C., and prismatic test pieces (125 mm ⁇ 12 mm ⁇ 6 mm) and flat plate test pieces (127 mm ⁇ 12.7 mm ⁇ 1.2 mm) were molded to obtain a molded body of a polyester resin composition.
  • polyester resin composition shown in Table 4 or 6 is melt-kneaded at 280 ° C. using a co-directional meshing type twin screw extruder (TEX-28V, manufactured by Nippon Steel Works Co., Ltd.), strand cut, and polyester 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.
  • 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 270 ° 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 130 ° C., and prismatic test pieces (125 mm ⁇ 12 mm ⁇ 6 mm) and flat plate test pieces (127 mm ⁇ 12.7 mm ⁇ 1.2 mm) were molded to obtain a molded body of a polyester resin composition.
  • the raw materials in Tables 1 to 6 are as follows.
  • PBT Polybutylene terephthalate resin, Novaduran 5010R5 (Mitsubishi Engineering Plastics, unreinforced, glass transition temperature: 50 ° C., crystallization enthalpy ⁇ Hmc: 44 J / g)
  • PTT Polytrimethylene terephthalate resin, Sorona (registered trademark) Bright (manufactured by DuPont, unreinforced, glass transition temperature: 50 ° C., crystallization enthalpy ⁇ Hmc: 52 J / g)
  • PET Polyethylene terephthalate resin, RT-553C (Nippon Unipet, unreinforced, glass transition point: 70 ° C., crystallization enthalpy ⁇ Hmc: 42 J / g)
  • DAIFATTY-101 Mixed diester of adipic acid and diethylene glycol monomethyl ether
  • Test Example 1 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 2 [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.
  • the loss factor is preferably 0.05 or more, more preferably 0.06 or more, and it can be determined that the loss factor is high and vibration attenuation is fast. The higher the value, the higher the effect.
  • Examples 1 to 32 had higher effects in both the flexural modulus and the loss factor than Comparative Examples 1 to 10. From this, it can be seen that by adding a plasticizer and / or a styrene / isoprene block copolymer and an inorganic filler to various thermoplastic polyester resins, it becomes possible to improve rigidity and vibration damping, Application to various uses is suggested. It can also be seen that by using a plasticizer and a styrene / isoprene block copolymer in combination, the loss factor can be increased while maintaining a high flexural modulus (Examples 14 and 15). From the comparison between Examples 3 and 21 to 14, it can be seen that the use of a plate-like filler among the inorganic fillers increases both the flexural modulus and the loss coefficient, and among these, mica is preferable.
  • the polyester 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, or an industrial device, or a component 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 de polyester pour un amortisseur, la composition de résine de polyester contenant une résine de polyester thermoplastique (A) qui est composée d'un composant acide dicarboxylique et d'un composant diol, un ou plusieurs composé (B) choisis dans le groupe qui comprend un plastifiant et un copolymère séquencé de styrène et d'isoprène, et une charge inorganique (C). Cette composition de résine de polyester peut être utilisée de façon appropriée, par exemple, comme matériau pour équipement audio tel que haut-parleurs, télévisions, enregistreurs de cassette radio, écouteurs, composants audio ou microphones, ou comme amortisseur dans des produits tels que produits électriques, véhicules, bâtiments et équipement industriel ou dans les composants ou boîtiers desdits produits.
PCT/JP2015/079492 2014-10-31 2015-10-20 Composition de résine de polyester pour amortisseurs WO2016067961A1 (fr)

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US15/519,892 US20170247527A1 (en) 2014-10-31 2015-10-20 Polyester resin composition for damping material
CN201580057060.XA CN107075342B (zh) 2014-10-31 2015-10-20 减振材料用的聚酯树脂组合物
EP15854438.7A EP3214147B1 (fr) 2014-10-31 2015-10-20 Composition de résine de polyester pour amortisseurs

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JP2017197733A (ja) * 2016-04-25 2017-11-02 花王株式会社 制振材料用のポリエステル樹脂成形組成物

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JPS5141080A (ja) * 1974-10-05 1976-04-06 Yokohama Rubber Co Ltd Danpinguseifukugoban
JPH05202287A (ja) * 1991-09-30 1993-08-10 Kuraray Co Ltd 樹脂組成物
JPH10130451A (ja) * 1996-10-29 1998-05-19 Mitsubishi Chem Corp 熱可塑性エラストマー組成物及びその複合成形体
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JP2017197733A (ja) * 2016-04-25 2017-11-02 花王株式会社 制振材料用のポリエステル樹脂成形組成物
WO2017188183A1 (fr) * 2016-04-25 2017-11-02 花王株式会社 Composition de moulage de résine de polyester pour des matériaux d'amortissement
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