WO2013165007A1 - Etui pour appareils électroniques - Google Patents

Etui pour appareils électroniques Download PDF

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Publication number
WO2013165007A1
WO2013165007A1 PCT/JP2013/062673 JP2013062673W WO2013165007A1 WO 2013165007 A1 WO2013165007 A1 WO 2013165007A1 JP 2013062673 W JP2013062673 W JP 2013062673W WO 2013165007 A1 WO2013165007 A1 WO 2013165007A1
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Prior art keywords
terephthalate resin
polybutylene terephthalate
acid
mass
electronic device
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PCT/JP2013/062673
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English (en)
Japanese (ja)
Inventor
陽一 平川
一也 五島
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ウィンテックポリマー株式会社
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Application filed by ウィンテックポリマー株式会社 filed Critical ウィンテックポリマー株式会社
Priority to JP2014513404A priority Critical patent/JP6117190B2/ja
Priority to CN201380022684.9A priority patent/CN104272885B/zh
Publication of WO2013165007A1 publication Critical patent/WO2013165007A1/fr

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    • 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
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences

Definitions

  • the present invention relates to an electronic device casing.
  • Polybutylene terephthalate resin is excellent in mechanical properties, electrical properties, chemical properties, and other properties, and because it has good processability, it is used as an engineering plastic for a wide range of applications such as electronic equipment parts and automotive parts. Has been.
  • a housing that is easy to touch is required to have both impact resistance and flame retardancy, and to have excellent appearance.
  • Patent Document 1 a composition in which a modified polyester, a phosphinate, and the like are blended with a polybutylene terephthalate resin is disclosed.
  • Patent Document 1 a composition in which a modified polyester, a phosphinate, and the like are blended with a polybutylene terephthalate resin.
  • An object of the present invention is to provide a casing for electronic equipment that has both impact resistance and flame retardancy, and further has excellent appearance.
  • the present inventors blend the polybutylene terephthalate resin (A) with the modified polyethylene terephthalate resin (B), the flame retardant containing no halogen atom (C), and the thermoplastic polyester elastomer (D). As a result, the present invention has been completed. More specifically, the present invention provides the following.
  • Polybutylene terephthalate resin (A), Modified polyethylene terephthalate resin (B), A flame retardant containing no halogen atom (C), and a thermoplastic polyester elastomer (D), Comprising a polybutylene terephthalate resin composition containing In the polybutylene terephthalate resin composition, the Charpy impact value measured according to ISO-179 is 7 kJ / m 2 or more,
  • the polybutylene terephthalate resin composition is a casing for electronic equipment that conforms to the 5VA standard by a test method according to the UL94 standard.
  • the polybutylene terephthalate resin (A) and the modified polyethylene terephthalate resin (B) are 100% by mass, the polybutylene terephthalate resin (A) is more than 50% by mass and 70% by mass or less.
  • fills 30 mass% or more and less than 50 mass%.
  • the mass ratio ((C) / (D)) of the flame retardant containing no halogen atom (C) and the thermoplastic polyester elastomer (D) is 4/6 or more and 6/4 or less.
  • thermoplastic polyester elastomer (D) is a polyether-polyester type elastomer or a polyester-polyester type elastomer.
  • the electronic device component is a power supply device component.
  • an electronic device casing that is provided with both impact resistance and flame retardancy and further has an excellent appearance.
  • test piece which consists of the polybutylene terephthalate resin composition of this invention used in order to measure flatness.
  • the housing for electronic equipment includes a polybutylene terephthalate resin containing a polybutylene terephthalate resin (A), a modified polyethylene terephthalate resin (B), a flame retardant containing no halogen atom (C), and a thermoplastic polyester elastomer (D). It consists of a resin composition and has predetermined properties. Hereinafter, each component etc. are demonstrated.
  • the polybutylene terephthalate resin (A) used in the present invention comprises a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.), and an alkylene having at least 4 carbon atoms.
  • the polybutylene terephthalate resin is not limited to a homopolybutylene terephthalate resin, but may be a copolymer containing 90 mol% or more of butylene terephthalate units.
  • examples of dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives include, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4 C 8-14 aromatic dicarboxylic acids such as 4,4'-dicarboxydiphenyl ether; C 4-16 alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C 5-10 such as cyclohexanedicarboxylic acid And cycloalkane dicarboxylic acids of the above; ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components can be used alone or in combination of two or more.
  • C 8-12 aromatic dicarboxylic acids such as isophthalic acid
  • C 6-12 alkanedicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.
  • glycol components (comonomer components) other than 1,4-butanediol for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, C 2-10 alkylene glycol such as neopentyl glycol and 1,3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol and dipropylene glycol; alicyclic diol such as cyclohexanedimethanol and hydrogenated bisphenol A Aromatic diols such as bisphenol A and 4,4′-dihydroxybiphenyl; ethylene oxide 2-mol adduct of bisphenol A, propylene of bisphenol A Kisaido such as a three molar adduct, alkylene oxide adducts of C 2-4 of bisphenol A; or ester-forming derivatives of these glycols
  • C 2-6 alkylene glycol such as ethylene glycol and trimethylene glycol
  • polyoxyalkylene glycol such as diethylene glycol
  • alicyclic diol such as cyclohexanedimethanol
  • Examples of the comonomer component that can be used in addition to the dicarboxylic acid component and the glycol component include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4′-hydroxybiphenyl, and the like.
  • any of the polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as the polybutylene terephthalate resin (A). Further, as the polybutylene terephthalate resin (A), a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer are combined so that the butylene terephthalate unit in the obtained polybutylene terephthalate resin (A) is 90 mol% or more. May be used.
  • the amount of terminal carboxyl groups of the polybutylene terephthalate resin (A) used in the present invention is not particularly limited as long as the object of the present invention is not impaired.
  • the amount of terminal carboxyl groups of the polybutylene terephthalate resin used in the present invention is preferably 30 meq / kg or less, more preferably 25 meq / kg or less.
  • the resulting polybutylene terephthalate resin composition is less susceptible to strength reduction due to hydrolysis in a moist heat environment.
  • the lower limit value of the terminal carboxyl group amount of the polybutylene terephthalate resin (A) is not particularly limited, but is preferably 10 meq / kg or more, more preferably 5 meq / kg or more. In general, it is difficult to produce a polybutylene terephthalate resin having a terminal carboxyl group of less than 5 meq / kg.
  • the intrinsic viscosity of the polybutylene terephthalate resin (A) used in the present invention is not particularly limited as long as the object of the present invention is not impaired.
  • the intrinsic viscosity (IV) of the polybutylene terephthalate resin (A) is 0.60 dL / g or more and 1.2 dL / g or less because the resulting polybutylene terephthalate resin composition has particularly excellent moldability. Is preferred. More preferably, it is 0.65 dL / g or more and 0.9 dL / g or less.
  • the intrinsic viscosity can also be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities.
  • a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g is prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL / g. Can do.
  • the intrinsic viscosity (IV) of the polybutylene terephthalate resin (A) can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.
  • Modified polyethylene terephthalate resin (B) Conventionally, polyethylene terephthalate resin not containing a modified component, modified polybutylene terephthalate resin containing 10 mol% or more of a modified component, etc. are used as an alloying partner material having excellent compatibility with the polybutylene terephthalate resin (A). I came. However, in the present invention, by using the polybutylene terephthalate resin composition containing the modified polyethylene terephthalate resin (B) containing a predetermined modifying component, an electronic device housing having particularly excellent fluidity, warpage, and flame retardancy. You can get a body.
  • the modified polyethylene terephthalate resin (B) used in the present invention is 1) terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.) 2) ethylene glycol or an ester-forming derivative thereof (acetylated product, etc.), and 3) Dicarboxylic acids other than terephthalic acid, ester-forming derivatives thereof (C 1-6 alkyl esters, acid halides, etc.), glycols other than ethylene glycol, or ester-forming derivatives thereof (acetylated products, etc.) It is a polyester resin obtained by polycondensation of a modifying component according to a known method.
  • dicarboxylic acids other than terephthalic acid and ester-forming derivatives thereof include those similar to those exemplified for the component (A).
  • isophthalic acid it is preferable to use isophthalic acid as a modifying component.
  • glycols other than ethylene glycol or ester-forming derivatives thereof propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, C 2-10 alkylene glycol such as 1,3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol and dipropylene glycol; alicyclic diol such as cyclohexanedimethanol and hydrogenated bisphenol A; bisphenol A, Bisphenols such as aromatic diols such as 4,4′-dihydroxybiphenyl; bisphenol A ethylene oxide 2-mole adducts, bisphenol A propylene oxide 3-mole adducts, etc. Alkylene oxide adducts of C 2-4 of A; or ester-forming derivatives of these glycols (acetylated, etc.).
  • the modified component used in the production of the modified polyethylene terephthalate resin (B) used in the present invention may contain a hydroxycarboxylic acid component, a lactone component, etc. as long as the object of the present invention is not impaired.
  • the amount of the repeating unit derived from these components is preferably 5 mol% or more and 30 mol% or less, more preferably 7 mol% or more and 20 mol% or less, and more preferably 10 mol in all repeating units in the (B) polyethylene terephthalate resin. % To 15 mol% is particularly preferable.
  • hydroxycarboxylic acid component contained in the modified component examples include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4′-hydroxybiphenyl; Aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; or ester-forming derivatives of these hydroxycarboxylic acids (C 1-6 alkyl ester derivatives, acid halides, acetylates, etc.). These hydroxycarboxylic acid components can be used alone or in combination of two or more.
  • lactone component contained in the modifying component examples include C 3-12 lactones such as propiolactone, butyrolactone, valerolactone, and caprolactone (eg, ⁇ -caprolactone). These lactone components can be used alone or in combination of two or more.
  • the melting point of the modified polyethylene terephthalate resin (B) is preferably 245 ° C. or less, particularly preferably 240 ° C. or less.
  • the melting point of the modified polyethylene terephthalate resin (B) can be measured using a differential scanning calorimeter (DSC) according to JIS K7121.
  • the modified polyethylene terephthalate resin (B) is, when the total of the polybutylene terephthalate resin (A) and the modified polyethylene terephthalate resin (B) is 100% by mass, It is preferable that the polybutylene terephthalate resin (A) is more than 50% by mass and 70% by mass or less, and the modified polyethylene terephthalate resin (B) is preferably 30% by mass or more and less than 50% by mass, and the polybutylene terephthalate resin (A) is 55% by mass. % To 65% by mass and the modified polyethylene terephthalate resin (B) is more preferably 35% by mass to 45% by mass.
  • the polybutylene terephthalate resin composition When the total of the polybutylene terephthalate resin (A) and the modified polyethylene terephthalate resin (B) is 100% by mass, and the polybutylene terephthalate resin (A) is 50% by mass or less, the polybutylene terephthalate resin composition There is a possibility that the moldability of the product is lowered. Molding obtained when the total of the polybutylene terephthalate resin (A) and the modified polyethylene terephthalate resin (B) is 100% by mass, and the polybutylene terephthalate resin (A) is more than 70% by mass. The appearance, warpage and flame retardancy of the product may be undesirable.
  • the amount of the modified polyethylene terephthalate resin (B) used in the polybutylene terephthalate resin composition used in the present invention is preferably 30 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). More preferably, it is 40 parts by mass or more and less than 100 parts by mass.
  • the amount of the modified polyethylene terephthalate resin (B) used is less than 30 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A), the appearance, warpage, and flame retardancy of the resulting electronic device casing are preferable. There is no possibility.
  • the amount of the modified polyethylene terephthalate resin (B) used is 100 parts by mass or more with respect to 100 parts by mass of the polybutylene terephthalate resin (A), the moldability of the polybutylene terephthalate resin composition may be lowered.
  • Flame retardant containing no halogen atom (C) Although it does not specifically limit as a flame retardant (C) which does not contain the halogen atom used in this invention, A phosphorus flame retardant, an antimony flame retardant, a nitrogen flame retardant, etc. are mentioned.
  • the phosphorus flame retardant is not particularly limited as long as it is a compound having a phosphorus atom, and examples thereof include an organic phosphorus flame retardant and an inorganic phosphorus flame retardant.
  • Organic phosphorus flame retardants include phosphoric acid esters (aromatic phosphoric acid esters such as triphenyl phosphate), phosphoric acid ester amides, phosphonitrile compounds (such as (poly) phenoxyphosphazene), and organic phosphonic acid compounds (methanephosphone).
  • Phosphonic acid esters such as diphenyl acid and diethyl phenylphosphonate
  • organic phosphinic acid compounds such as methyl phosphinate
  • phosphine oxides such as triphenylphosphine oxide and tricresylphosphine oxide
  • Inorganic phosphorus flame retardants include red phosphorus, orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid (metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, etc.), polyphosphorous acid (metaphosphorous acid)
  • Non-condensed or condensed (phosphite) phosphates metal salts such as calcium
  • antimony flame retardant examples include antimony trioxide, antimony pentoxide, and sodium antimonate.
  • nitrogen-based flame retardant include a salt of a triazine compound and cyanuric acid or isocyanuric acid, a double salt of an amino group-containing nitrogen compound and polyphosphoric acid, and the like.
  • an organophosphorus flame retardant in that no toxic gas is generated and a high flame retardant effect can be obtained.
  • said flame retardant can be used individually or in combination of 2 or more types.
  • the flame retardant (C) containing no halogen atom is a mass ratio of the flame retardant (C) containing no halogen atom and the thermoplastic polyester elastomer (D) described later ( (C) / (D)) is preferably used in a range of 4/6 or more and 6/4 or less.
  • the mass ratio of the flame retardant containing no halogen atom (C) and the thermoplastic polyester elastomer (D) within the above range, it is preferable to achieve both flame retardancy and impact resistance of the resulting housing for electronic devices. it can.
  • the mass ratio of the flame retardant containing no halogen atom (C) and the thermoplastic polyester elastomer (D) is less than 4/6, sufficient flame retardancy may not be imparted to the resulting electronic device casing. There is sex. If the mass ratio of the flame retardant containing no halogen atom (C) and the thermoplastic polyester elastomer (D) is more than 6/4, the resulting electronic device casing may have insufficient impact resistance. .
  • the usage-amount of the flame retardant (C) which does not contain a halogen atom in the polybutylene terephthalate resin composition used in this invention is 40 mass parts or more and 100 masses with respect to 100 mass parts of polybutylene terephthalate resin (A). Is preferably 40 parts by mass or more and 65 parts by mass or less.
  • the flame retardant (C) containing no halogen atom is contained in the above-mentioned blending amount in the electronic device casing of the present invention, the electronic device casing can be preferably made flame-retardant.
  • the casing for electronic equipment of the present invention is environmentally preferable because it is made flame-retardant by a flame retardant containing no halogen atom, and therefore there is little risk of generating harmful substances.
  • the thermoplastic polyester elastomer (D) used in the present invention is generally a block copolymer having a structure in which a hard block (a hard segment made of an aromatic polyester or the like) and a soft block (a soft segment) are bonded.
  • the thermoplastic polyester elastomer (D) is classified into a polyester-polyester type elastomer and a polyether-polyester type elastomer depending on the type of the soft block, both of which can be suitably used in the present invention, and two or more types should be used in appropriate combination. Can do.
  • Polyether in terms of low hydrolyzability, not sacrificing the flame retardancy exhibited by the flame retardant (C) that does not contain halogen atoms even when the amount of elastomer is increased, and suitable for outdoor use -Polyester type elastomers are more preferred.
  • thermoplastic polyester elastomer (D) will be described in the order of hard segment, soft segment, and polyester elastomer.
  • the hard segment is made of hard polyester such as aromatic polyester.
  • the hard polyester can be obtained by polycondensation of dicarboxylic acid and diol, polycondensation of oxycarboxylic acid, or the like.
  • the hard polyester is preferably an aromatic polyester obtained by polycondensation of a monomer containing at least one aromatic monomer.
  • aromatic monomers used for the production of aromatic polyesters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl ether; hydroquinone , Aromatic diols such as resorcin, 4,4′-dihydroxybiphenyl, bisphenol A; 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4′-hydroxybiphenyl, etc.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl ether
  • hydroquinone Aromatic diols such as resorcin, 4,4′-dihydroxybiphenyl, bisphenol A; 4-hydroxybenzoic acid, 3-hydroxybenz
  • These aromatic monomers can be used in appropriate combination of two or more.
  • the aromatic polyester may be one obtained by copolymerizing other comonomer components of the above aromatic monomers.
  • comonomer components include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1,3-octanediol, and other alkylene glycols; diethylene glycol, triethylene glycol, Polyoxyalkylene glycols such as dipropylene glycol; Cycloaliphatic diols such as cyclohexanedimethanol and hydrogenated bisphenol A; Alkane dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, and sebacic acid; Cycloalkane dicarboxylic acids such as cyclohexanedicarboxylic acid Acids; Aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C 1-6 alkyl esters, acid
  • the aromatic polyester constituting the hard segment is not particularly limited as long as it is obtained using an aromatic monomer.
  • Suitable aromatic polyester constituting the hard segment is, for example, all obtained by polycondensation of one or more monomers selected from the group consisting of aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids.
  • Aromatic polyester aromatic polyester obtained by polycondensation of aromatic dicarboxylic acid and non-aromatic diol (aliphatic diol, alicyclic diol, etc.); non-aromatic dicarboxylic acid (alkane dicarboxylic acid, cycloalkane dicarboxylic acid) Etc.) and an aromatic diol, and an aromatic polyester obtained by copolymerizing an aromatic hydroxycarboxylic acid and an aliphatic hydroxycarboxylic acid.
  • the aromatic polyester constituting the hard segment may be a crystalline aromatic polyester or a liquid crystal polyester, and a crystalline aromatic polyester is preferably used.
  • Suitable crystalline aromatic polyesters constituting the hard segment include, for example, C 2-4 alkylene arylates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate; 1 mol% or more based on the total amount of monomers Examples thereof include a modified C 2-4 alkylene arylate modified with a comonomer component of 30 mol% or less (more preferably 3 mol% or more and 25 mol% or less, particularly preferably 5 mol% or more and 20 mol% or less).
  • thermoplastic polyester elastomer (D) is a polyester elastomer having a polybutylene terephthalate segment as a hard segment because the resulting polybutylene terephthalate resin composition is easy to mold and the resulting molded article has high mechanical properties. Is preferably used.
  • the polyester-polyester type elastomer is composed of the above-mentioned hard segment and a soft segment made of soft polyester.
  • the soft polyester constituting the soft segment can be obtained by polycondensation of dicarboxylic acid and diol, polycondensation of hydroxycarboxylic acid or lactone, and the like.
  • the soft polyester is a polyester having a softer structure than the hard polyester constituting the hard segment, and is usually obtained by polycondensing a monomer containing at least one aliphatic monomer component.
  • Examples of the aliphatic monomer component used as the monomer for the soft polyester include alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, and 1,3-octanediol.
  • alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, and 1,3-octanediol.
  • Polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol; alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid, and sebacic acid; fats such as glycolic acid and hydroxycaproic acid Hydroxycarboxylic acids; lactones such as propiolactone, butyrolactone, valerolactone, caprolactone ( ⁇ -caprolactone, etc.); these aliphatic monomer components C 1-6 alkyl esters, acid halides, esters forming derivatives such as acetylated. These aliphatic monomer components can be used in an appropriate combination of two or more. These aliphatic monomer components can be used in combination with non-aromatic monomers such as alicyclic diols and cycloalkanedicarboxylic acids as necessary.
  • alkanedicarboxylic acids such as succinic acid, adip
  • the soft polyester constituting the soft segment of the polyester-polyester type elastomer is preferably an aliphatic polyester obtained from an alkanedicarboxylic acid and an aliphatic diol, or a polylactone obtained by ring-opening polymerization of a lactone.
  • thermoplastic polyester elastomer (D) the polyether-polyester type elastomer is composed of the above-described hard segment and a soft segment having a polyether unit.
  • Polyether units contained in the soft segment of the polyether-polyester elastomer include aliphatic polyethers containing polyoxy C 2-6 alkylene glycol units such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol. And a polyester unit having an aliphatic polyether unit containing a polyoxy C 2-6 alkylene glycol unit.
  • aliphatic polyether unit a unit derived from polyoxy C 2-4 alkylene glycol such as polyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol is preferable.
  • polyester unit having an aliphatic polyether unit a polyester unit obtained from polyoxyalkylene glycol and a non-aromatic dicarboxylic acid such as alkanedicarboxylic acid or cycloalkanedicarboxylic acid or an ester-forming derivative of nonaromatic dicarboxylic acid Is preferred.
  • a non-aromatic dicarboxylic acid such as alkanedicarboxylic acid or cycloalkanedicarboxylic acid or an ester-forming derivative of nonaromatic dicarboxylic acid
  • thermoplastic polyester elastomer (D) used in the present invention can be prepared by copolymerizing the above-mentioned component that gives a hard segment and the component that gives a soft segment according to a known method.
  • polyester-polyester type elastomers used in the present invention include polybutylene terephthalate resins, aromatic crystalline polyesters such as copolymers of polybutylene terephthalate resins and copolymer components (ethylene glycol, isophthalic acid, etc.), Or, a block copolymer composed of a hard segment made of a liquid crystal polyester and a soft segment made of an aliphatic polyester obtained by copolymerization of C 2-6 alkylene glycol and C 6-12 alkanedicarboxylic acid. .
  • suitable polyether-polyester type elastomers used in the present invention include polybutylene terephthalate resins and aromatic crystalline polyesters such as copolymers of polybutylene terephthalate resins and copolymerization components (ethylene glycol, isophthalic acid, etc.). Or a block copolymer composed of a hard segment made of liquid crystal polyester and a soft segment made of polyester obtained by polycondensation of polyoxy C 2-4 alkylene glycol such as polyoxytetramethylene glycol and dicarboxylic acid. It is done.
  • the mass ratio of the hard segment to the soft segment is preferably 10/90 or more and 90/10 or less, and more preferably 20/80 or more and 80/20 or less as the mass ratio of the soft segment / hard segment. More preferably, 30/70 or more and 70/30 or less is particularly preferable, and 40/60 or more and 60/40 or less is most preferable.
  • the content of the thermoplastic polyester elastomer (D) in the polybutylene terephthalate resin composition used in the present invention can satisfactorily improve the impact resistance of the resulting molded article, and a molded article having excellent mechanical properties can be obtained. Therefore, it is preferably 30 parts by mass or more and 120 parts by mass or less, and more preferably 40 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin (A).
  • thermoplastic polyester elastomer (D) used in the present invention preferably has a hardness specified by durometer hardness (D scale) in JIS K7215 of 20 or more and 80 or less.
  • D scale durometer hardness
  • Durometer hardness can be adjusted by the copolymerization ratio of soft segment / hard segment. Specifically, the hardness can be lowered by increasing the copolymerization ratio of the soft segment contained in the component (D). On the other hand, the hardness can be increased by increasing the copolymerization ratio of the hard segment contained in the component (D).
  • the hardness of 20 or more and less than 40 is low hardness
  • the hardness of 40 or more and less than 60 is medium hardness
  • the hardness of 60 or more and 80 or less is high hardness.
  • thermoplastic polyester elastomer (D) having medium hardness (durometer hardness (D scale); less than 40 to 60) and high hardness (durometer hardness (D scale); It is preferable in that the impact resistance and the decrease in tensile strength can be suppressed in a well-balanced manner.
  • the polybutylene terephthalate resin composition used in the present invention preferably contains an inorganic filler in addition to the essential components.
  • an inorganic filler any of a fibrous filler, a granular filler, a plate-like filler, and the like may be used, and two or more kinds may be used in combination.
  • a fibrous filler it is preferable to use. This is because by using the fibrous filler, a reinforcing effect on the molded body can be obtained, and the mechanical properties of the molded body can be improved.
  • the fibrous fillers glass fibers are particularly preferred.
  • the glass fiber any known glass fiber is preferably used, and the glass fiber diameter, the shape of a cylinder, a bowl-shaped cross section, an oval cross section, etc., or the length and glass cut when used for the production of chopped strands, rovings, etc. It does not depend on the method.
  • E glass or corrosion resistant glass containing zirconium element in the composition is preferably used in terms of quality.
  • the fiber length and fiber diameter of the glass fiber may be in the general range. For example, a fiber having a fiber length of 2.0 mm to 6.0 mm and a fiber diameter of 9.0 ⁇ m to 14.0 ⁇ m can be used.
  • the content of the fibrous filler in the polybutylene terephthalate resin composition is not particularly limited, but is preferably 100 parts by mass or more and 200 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin. Part or more and 150 parts by weight or less.
  • a fibrous filler and a plate-like filler in combination.
  • warpage can be greatly reduced while imparting impact resistance to the molded body.
  • a particularly preferred combination is glass fiber and glass flake.
  • the sum total of the usage-amount of a fibrous filler and a plate-shaped filler is 100 mass parts or more and 200 mass parts with respect to 100 mass parts of polybutylene terephthalate resin.
  • the mass part or less is preferable.
  • the ratio of the fibrous filler and the plate-like filler can be appropriately selected within a range that does not impair the purpose of the present application.
  • the polybutylene terephthalate resin composition used in the present invention preferably contains a flame retardant aid in addition to the above essential components.
  • a good flame retardant effect can be obtained by using a flame retardant and a flame retardant aid in combination.
  • the type of flame retardant aid is not limited as long as the object of the present invention is not impaired, and a suitable flame retardant aid can be selected and used according to the type of flame retardant (C) not containing a halogen atom.
  • an organic phosphorus flame retardant as the flame retardant (C) containing no halogen atom used in the present invention, it is preferable to use a nitrogen-containing flame retardant auxiliary as a flame retardant auxiliary. Among them, it is particularly preferable to use melamine cyanurate.
  • the content of the flame retardant aid in the polybutylene terephthalate resin composition is not particularly limited, but is preferably 20 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin.
  • the polybutylene terephthalate resin composition used in the present invention may further contain other components other than those described above as long as the effects of the present invention are not impaired.
  • other components include additives such as nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and dripping inhibitors, and other resins.
  • the content of other components in the polybutylene terephthalate resin composition is not particularly limited, but the content of the other components is usually 30 parts by mass or less in total with respect to 100 mass of the polybutylene terephthalate resin (A). Preferably, it is 20 parts by mass or less.
  • a resin composition can be prepared by a known equipment and method for preparing a resin composition or a molded product thereof. Specifically, necessary components can be mixed and kneaded using a single or biaxial extruder or other melt kneader to prepare a pellet for molding. A plurality of extruders or other melt kneaders may be used. Moreover, all the components may be charged simultaneously from the hopper, or some components may be charged from the side feed port.
  • the electronic device casing of the present invention is composed of the polybutylene terephthalate resin composition described above.
  • the casing for electronic equipment of the present invention is composed of the above-mentioned polybutylene terephthalate resin composition” means that the casing for electronic equipment of the present invention is obtained by molding the resin composition. In other words, part or all of the constituent components of the casing for electronic equipment are derived from the above-mentioned polybutylene terephthalate resin composition.
  • the electronic device casing of the present invention can be manufactured by molding the polybutylene terephthalate resin composition described above using a conventional molding machine.
  • a molding machine is not particularly limited as long as it can be normally used for molding a casing for electronic equipment, and an injection molding machine, a compression molding machine, or the like can be used. It is preferable to use an injection molding machine in terms of ease of installation of metal parts in a mold, simplicity of equipment, and excellent productivity.
  • the electronic device to which the electronic device casing of the present invention is applied is not particularly limited, but any of the group consisting of OA devices, home appliances, and electric vehicles is preferable. Since the case for electronic devices of the present invention has flame retardancy and impact resistance, it can be preferably used as a case for housing components of these electronic devices.
  • the electronic device casing of the present invention has both impact resistance and flame retardancy, and also has excellent appearance, so that it is easy to touch the human eye and the outside air, and is required to have safety and good appearance. It can be preferably applied to equipment.
  • the polybutylene terephthalate resin composition used in the present invention imparts excellent impact resistance, flame retardancy, appearance and the like to molded articles. Specifically, since the polybutylene terephthalate resin composition used in the present invention has a Charpy impact value measured according to ISO-179 of 7 kJ / m 2 or more, it is composed of the polybutylene terephthalate resin composition.
  • the electronic device casing of the present invention is excellent in impact resistance.
  • the housing for electronic equipment of the present invention composed of the polybutylene terephthalate resin composition is difficult. Excellent flammability.
  • the electronic device casing of the present invention is excellent in appearance because warpage, surface roughness, and unevenness are suppressed.
  • the electronic device casing of the present invention since the electronic device casing of the present invention has a good comparative tracking index, it also has safety required for electronic devices (particularly power supply device parts).
  • Perprene S is a block copolymer having polybutylene terephthalate as a hard segment and soft polyester as a soft segment.
  • Hytrel is a block copolymer having polybutylene terephthalate as a hard segment and polyether as a soft segment, and has different hardness depending on the copolymerization ratio of the hard segment and the soft segment.
  • Paraloid EXL2314 is a copolymer of alkyl acrylate and alkyl methacrylate.
  • Paraloid EXL2602 is a copolymer of butadiene, alkyl acrylate and alkyl methacrylate.
  • N Tafmer MP0620 is a maleic anhydride modified polyolefin.
  • Hardness indicates durometer hardness (D scale) in JIS K7215.
  • Examples and Comparative Examples> The raw materials shown in Tables 1 and 2 were supplied to a twin-screw extruder (TEX-30 ⁇ manufactured by Nippon Steel Works) and melt-kneaded to produce a pellet-shaped polybutylene terephthalate resin composition.
  • the melt-kneading conditions are as follows.
  • the unit of the number showing the usage-amount of each component in Table 1 and 2 is a mass part. (Melting and kneading conditions) Cylinder temperature: 260 ° C Screw rotation speed: 170rpm Discharge rate: 20kg / hr
  • melt viscosity In accordance with ISO11443, the melt viscosity of the resin used in the test specimen for evaluation was measured.
  • test piece for evaluation (2 mm thickness) was subjected to UL94 standard vertical combustion test by Underwriters Laboratories.
  • the determination results for the UL94 V-0, V-1, and V-2 standards for each test piece are shown in “UL94” in Tables 1 and 2.
  • determination results as to whether or not the test piece conforms to 5VA among UL94 5VA and 5VB standards are shown in “5VA” in Tables 1 and 2.
  • the flatness of a flat test piece having a length of 120 mm, a width of 120 mm, and a thickness of 2 mm was measured.
  • the flatness of the test piece was measured at 9 points on the test piece shown in FIG. 1 using a CNC image measuring machine (product name: QVBHU404-PRO1F, manufactured by Mitutoyo Corporation).
  • the evaluation criteria are as follows. 2mm or less; 2-5mm; ⁇ 5-8mm; ⁇ 8 mm or more; ⁇
  • CTI Comparative tracking index
  • the comparative tracking index (CTI) of the test piece for evaluation was measured using a 0.1% ammonium chloride aqueous solution and a platinum electrode. Moreover, the comparative tracking index was ranked based on the following evaluation criteria. 250-400V; 2 400-600V; 1 Over 600V; 0
  • the polybutylene terephthalate resin (A) is blended with (B) a modified polyethylene terephthalate, a flame retardant containing no halogen atom (C), and a thermoplastic polyester elastomer (D). It was confirmed that a molded article having tracking resistance and flame retardancy, suppressing warpage, and having a good appearance can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Casings For Electric Apparatus (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'objet de la présente invention est de fournir un étui pour les appareils électroniques, qui offre un bon équilibre entre résistance à l'impact et ininflammabilité, tout en ayant un excellent aspect. L'invention concerne un étui pour les appareils électroniques qui est configuré par une composition de résine de polybutylène-téréphtalate qui contient (A) une résine de polybutylène-téréphtalate, (B) une résine de polyéthylène-téréphtalate modifiée, (C) un agent ignifuge ne contenant pas d'atome d'halogène et (D) un élastomère de polyester thermoplastique. La valeur de résilience Charpy de la composition de résine de polybutylène-téréphtalate, telle que déterminée selon la norme ISO-179 est de 7 kJ/m² ou plus, et la composition de résine de polybutylène-téréphtalate est conforme à la norme 5VA par un test selon la norme UL-94.
PCT/JP2013/062673 2012-05-01 2013-04-30 Etui pour appareils électroniques WO2013165007A1 (fr)

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WO2017089293A1 (fr) 2015-11-26 2017-06-01 Clariant International Ltd Mélanges ignifuges polymères
JP2018502971A (ja) * 2014-10-10 2018-02-01 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ デオキシベンゾイン含有難燃性ポリマー組成物

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CN109721970A (zh) * 2019-01-15 2019-05-07 胡敏悫 一种壳体及其制备方法
JP7259455B2 (ja) * 2019-03-22 2023-04-18 株式会社オートネットワーク技術研究所 コネクタ付きケース、コネクタ付きワイヤーハーネス、及びエンジンコントロールユニット
US20230094235A1 (en) * 2020-02-19 2023-03-30 Toyobo Co., Ltd. Flame retardant polyester resin composition and molded article comprising same

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