WO2022030507A1 - Composition de résine de polyester thermoplastique - Google Patents

Composition de résine de polyester thermoplastique Download PDF

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WO2022030507A1
WO2022030507A1 PCT/JP2021/028818 JP2021028818W WO2022030507A1 WO 2022030507 A1 WO2022030507 A1 WO 2022030507A1 JP 2021028818 W JP2021028818 W JP 2021028818W WO 2022030507 A1 WO2022030507 A1 WO 2022030507A1
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mass
polyester resin
thermoplastic polyester
parts
resin composition
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PCT/JP2021/028818
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English (en)
Japanese (ja)
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広一 佐子川
創貴 吉田
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三菱エンジニアリングプラスチックス株式会社
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Priority to JP2022541574A priority Critical patent/JPWO2022030507A1/ja
Publication of WO2022030507A1 publication Critical patent/WO2022030507A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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

Definitions

  • the present invention relates to a thermoplastic polyester resin composition, and more specifically, has mechanical strength, heat resistance, and dimensional stability at a high level in a well-balanced manner, and has tracking resistance, heat shock resistance, and hydrolysis resistance.
  • the present invention relates to a thermoplastic polyester resin composition having excellent fluidity during injection molding.
  • Thermoplastic polyester resin represented by polybutylene terephthalate and polyethylene terephthalate has excellent mechanical strength, chemical resistance, electrical insulation, etc., and also has excellent heat resistance, moldability, and recyclability. Therefore, it is widely used for electrical and electronic equipment parts, automobile parts and other electrical parts, mechanical parts, and the like.
  • the insulating material Since the insulating material is dried and charged by the heat generated from the device during energization, dust tends to adhere to the surface of the insulating material. Therefore, the component formed from the insulating material tends to have dust adhered to its surface while the device is stopped, and the dust absorbs the moisture in the air, and the absorbed moisture lowers the surface resistance of the material and leaks. The current increases. In general, electrical components are more or less exposed to this situation, and the tracking resistance of insulating materials is emphasized. For electrical and electronic equipment components, requirements such as the Comparative Tracking Index (CTI) of Underwriters Laboratories, Inc. of the United States must be met, and CTI meets the PLC0 level (600V ⁇ CTI) these days. Required.
  • CTI Comparative Tracking Index
  • Patent Document 1 describes a resin composition containing a thermoplastic polyester resin and an olefin-based copolymer composed of an ⁇ -olefin and a glycidyl ester of ⁇ , ⁇ -unsaturated acid.
  • the material is disclosed, and it is described that a conventional flame-retardant agent, a filler such as talc, kaolin, silica, etc., and a fibrous filler such as glass fiber may be added, if necessary, but simply.
  • Patent Document 2 describes a resin composition comprising a polybutylene terephthalate resin, a brominated flame retardant, an antimon flame retardant, an ethylene fluoride polymer, a polyolefin and a metal silicate metal salt filler, and glass fiber. ing.
  • Patent Document 3 discloses a resin composition composed of a thermoplastic polyester resin, compressed fine powder talc, and a halogenated benzyl (meth) acrylate-based flame retardant, and a fibrous reinforcing agent is added as necessary. It is stated that it may be used.
  • an object of the present invention is to have the characteristics of mechanical strength, heat resistance, and dimensional stability originally possessed by a thermoplastic polyester resin at a high level in a well-balanced manner, and to have tracking resistance, hydrolysis resistance, and hydrolysis resistance. It is an object of the present invention to provide a thermoplastic polyester resin material having excellent heat shock resistance and fluidity during injection molding.
  • the present inventor contains a maleic anhydride-modified olefin polymer, a hydrolysis inhibitor, and a reinforcing filler in a specific amount in a thermoplastic polyester resin having a specific intrinsic viscosity. By doing so, it has the characteristics of mechanical strength, heat resistance, and dimensional stability at a high level in a well-balanced manner, and is also excellent in tracking resistance, hydrolysis resistance, heat shock resistance, and fluidity during injection molding. This has led to the completion of the present invention.
  • the present invention relates to the following thermoplastic polyester resin compositions and molded articles.
  • thermoplastic polyester resin (A) having an intrinsic viscosity of 0.60 dl / g or more and less than 0.85 dl / g.
  • a thermoplastic polyester resin composition comprising no E), or even if it is contained, the content thereof is less than 9 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A).
  • thermoplastic polyester resin composition according to any one of the above [1] to [4], wherein the maleic anhydride-modified olefin polymer (B) is a maleic anhydride-modified ethylene-propylene copolymer.
  • thermoplastic polyester resin composition according to any one of the above [1] to [6] wherein the thermoplastic polyester resin (A) is a polybutylene terephthalate resin.
  • thermoplastic polyester resin composition according to any one of the above [1] to [7], wherein the hydrolysis inhibitor (C) is an epoxy compound.
  • the hydrolysis inhibitor (C) is an epoxy compound.
  • the thermoplastic polyester resin composition according to any one of the above [1] to [10] which further contains a colorant.
  • thermoplastic polyester resin composition of the present invention has mechanical strength, heat resistance, and dimensional stability in a well-balanced manner at a high level, and is excellent in tracking resistance, heat shock resistance, and hydrolysis resistance, and further. It also has excellent fluidity during injection molding. Therefore, the thermoplastic polyester resin composition of the present invention can be used as an insulating component for electrical / electronic device parts or electrical component parts, for example, a housing, a connector, a relay, a switch, a breaker, an electromagnetic switch, or a terminal of the electronic / electrical device component. It can be particularly suitably used for a table, a sensor, an actuator, a terminal switch and the like.
  • the molded product for example, it can be particularly preferably used as a fitting member having a fitting structure, an insert molded product, or the like.
  • the thermoplastic polyester resin composition of the present invention has an intrinsic maleic acid-modified olefin polymer (B) with respect to 100 parts by mass of the thermoplastic polyester resin (A) having an intrinsic viscosity of 0.60 dl / g or more and less than 0.85 dl / g. It contains 5 to 30 parts by mass, 0.2 to 4.5 parts by mass of the hydrolysis inhibitor (C), and 10 to 80 parts by mass of the reinforcing filler (D), and the water absorption rate measured by the ISO62A method is 0.28. It is characterized in that it does not contain or more than% by mass of the thermoplastic resin (E), or even if it is contained, the content thereof is less than 9 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A).
  • thermoplastic polyester resin (A) The thermoplastic polyester resin composition of the present invention contains a thermoplastic polyester resin (A).
  • the thermoplastic polyester resin (A) is a polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, polycondensation of these compounds, etc., and is either homopolyester or copolyester. There may be.
  • an aromatic dicarboxylic acid or an ester-forming derivative thereof is preferably used as the dicarboxylic acid compound constituting the thermoplastic polyester resin (A).
  • the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, and the like.
  • aromatic dicarboxylic acids Two or more kinds of these aromatic dicarboxylic acids may be mixed and used.
  • dimethyl ester or the like can be used as an ester-forming derivative in the polycondensation reaction in addition to the free acid.
  • aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecandioic acid and sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1 , 4-Cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids can be mixed and used.
  • dihydroxy compound constituting the thermoplastic polyester resin (A) examples include ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol and triethylene glycol.
  • diethylene glycol and triethylene glycol examples include aliphatic diols, alicyclic diols such as cyclohexane-1,4-dimethanol, and mixtures thereof. If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be copolymerized.
  • aromatic diols such as hydroquinone, resorcin, naphthalene diol, dihydroxydiphenyl ether, and 2,2-bis (4-hydroxyphenyl) propane can also be used.
  • trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane for introducing a branched structure, and fatty acids for adjusting the molecular weight, etc.
  • trimellitic acid trimesic acid
  • pyromellitic acid pyromellitic acid
  • pentaerythritol trimethylolpropane
  • fatty acids for adjusting the molecular weight, etc.
  • a small amount of the monofunctional compound can also be used in combination.
  • thermoplastic polyester resin (A) a resin mainly composed of a polycondensation of a dicarboxylic acid and a diol, that is, a resin in which 50% by mass, preferably 70% by mass or more of the total resin is composed of this polycondensate is used.
  • the dicarboxylic acid is preferably an aromatic carboxylic acid
  • the diol is preferably an aliphatic diol.
  • polyalkylene terephthalate in which 95 mol% or more of the acid component is terephthalic acid and 95% by mass or more of the alcohol component is an aliphatic diol is preferable.
  • Typical examples are polybutylene terephthalate and polyethylene terephthalate. It is preferable that these are close to homopolyester, that is, 95% by mass or more of the whole resin is composed of a terephthalic acid component and a 1,4-butanediol or ethylene glycol component.
  • thermoplastic polyester resin (A) a polybutylene terephthalate resin or a polyethylene terephthalate resin having a main component (that is, 50% by mass or more) is preferable, and a polybutylene terephthalate resin is particularly preferable.
  • the thermoplastic polyester resin (A) has an intrinsic viscosity of 0.60 dl / g or more and less than 0.85 dl / g, preferably 0.60 dl / g or more and less than 0.75 dl / g, and more preferably 0.65 dl / g or more. Use one that is less than 0.75 dl / g. If an intrinsic viscosity lower than 0.60 dl / g is used, the mechanical strength of the obtained resin composition may be lowered, the hydrolysis resistance may be deteriorated, or the heat shock resistance may be lowered.
  • the intrinsic viscosity is preferably 0.62 dl / g or more, particularly 0.64 dl / g or more, 0.66 dl / g or more, particularly preferably 0.67 dl / g or more, and preferably 0.83 dl / g or less, particularly 0.
  • dl / g or less 0.80 dl / g or less, 0.79 dl / g or less, 0.78 dl / g or less, 0.77 dl / g or less, 0.76 dl / g or less, 0.75 dl / g or less, 0. It is 74 dl / g or less, 0.73 dl / g or less, 0.72 dl / g or less, and particularly preferably 0.71 dl / g or less.
  • the intrinsic viscosity of the thermoplastic polyester resin shall be measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of 1,1,2,2-tetrachloroethane and phenol.
  • the amount of the terminal carboxyl group of the thermoplastic polyester resin (A) may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and 30 eq / ton or less. Is even more preferable. If it exceeds 60 eq / ton, gas is likely to be generated during melt molding of the resin composition.
  • the lower limit of the amount of the terminal carboxyl group is not particularly determined, but is usually 10 eq / ton in consideration of the productivity of manufacturing the thermoplastic polyester resin.
  • the amount of terminal carboxyl groups in the polyester resin is a value obtained by dissolving 0.5 g of a polyalkylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide.
  • a method for adjusting the amount of the terminal carboxyl group a method for adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, the depressurization method, the method for reacting the terminal blocking agent, and the like, any conventionally known method can be used. Just do it.
  • maleic anhydride-modified olefin polymer (B) As the maleic anhydride-modified olefin polymer (B), a maleic anhydride-modified olefin polymer modified, preferably graft-modified, can be used. By combining the maleic anhydride-modified olefin polymer (B) with each component, both tracking resistance and heat shock resistance can be improved.
  • graft modification is included not only when maleic anhydride is introduced as a side chain having a long chain length with respect to the skeleton of the olefin polymer, but also when it is chemically bonded to the olefin polymer. Graft modification can be performed by various conventionally known methods. The modification method is not limited, but (i) a melt modification method in which maleic anhydride is added to a molten olefin polymer to carry out graft copolymerization, and (ii) maleic anhydride is added to the olefin polymer dissolved in a solvent. Examples thereof include a solution modification method in which graft copolymerization is carried out.
  • melt modification method that does not require the use of a solvent is preferable, and graft modification using an extruder is more preferable.
  • graft modification using an extruder is more preferable.
  • ⁇ -olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, and octene-1 are used alone. Examples thereof include polymers and copolymers, and these can be used by mixing two or more kinds.
  • a maleic anhydride-modified olefin copolymer is preferable, and in particular, a maleic anhydride-modified ethylene-propylene copolymer, a maleic anhydride-modified ethylene-butene copolymer, and maleic anhydride are used. Acid-modified ethylene-hexene copolymers and maleic anhydride-modified ethylene-octene copolymers are preferable, and maleic anhydride-modified ethylene-propylene copolymers are particularly preferable.
  • the acid modification rate (content) of the maleic anhydride-modified olefin polymer (B) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass.
  • the melt flow rate (MFR) of the maleic anhydride-modified olefin polymer (B) is not particularly limited, but is preferably 0.05 to 10 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes, 0. The one of 1 to 3 g / 10 minutes is preferable.
  • the MFR means a value at 190 ° C. and a load of 2.16 kg.
  • the content of the maleic anhydride-modified olefin polymer (B) is 5 to 30 parts by mass, preferably 5 to 25 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). By containing such an amount in combination with other components, it is possible to achieve a high degree of tracking resistance, specifically, 0 level (CTI: 600 V or more) in PLC. If the content exceeds 30 parts by mass, the elastic modulus of the resin composition will decrease.
  • the content is preferably 6 parts by mass or more, more preferably 7 parts by mass or more, preferably 25 parts by mass or less, more preferably 23 parts by mass or less, still more preferably, with respect to 100 parts by mass of the thermoplastic polyester resin (A). Is 20 mass or less.
  • Hydrolysis inhibitor (C) a compound having reactivity with a carboxylic acid which is a terminal functional group of the thermoplastic polyester resin (A) and a hydroxyl group, for example, an epoxy compound, a carbodiimide compound, an isoanate compound, an oxazoline compound and the like can be applied. be. Of these, epoxy compounds are preferred.
  • the epoxy compound may be any compound having one or more epoxy groups in one molecule, and is usually a glycidyl compound which is a reaction product of epichlorohydrin with an alcohol, a phenol, a carboxylic acid, or the like, or an olefinic compound.
  • a compound having an epoxidized double bond may be used.
  • the epoxy compound include novolak type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, alicyclic epoxy compounds, glycidyl ethers, glycidyl esters, epoxidized butadiene polymers, resorcin type epoxy compounds and the like. Can be mentioned.
  • Examples of the novolak type epoxy compound include phenol novolac type epoxy compounds and cresol novolak type epoxy compounds.
  • Examples of the bisphenol A type epoxy compound include bisphenol A-diglycidyl ether and hydrogenated bisphenol A-diglycidyl ether
  • examples of the bisphenol F type epoxy compound include bisphenol F-diglycidyl ether and hydrogenated bisphenol F-diglycidyl. Examples include ether.
  • alicyclic epoxy compounds include vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, and vinylcyclohexenedi. Examples thereof include epoxides and 3,4-epoxycyclohexene glycidyl ethers.
  • glycidyl ethers include monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butyl phenyl glycidyl ether and allyl glycidyl ether;
  • diglycidyl ethers such as pentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether.
  • glycidyl esters examples include monoglycidyl esters such as benzoic acid glycidyl ester and sorbic acid glycidyl ester; diglycidyl esters such as adipic acid diglycidyl ester, terephthalic acid diglycidyl ester, and orthophthalic acid diglycidyl ester.
  • Examples of the epoxidized butadiene polymer include epoxidized polybutadiene, epoxidized styrene-butadiene polymer, and epoxidized hydride styrene-butadiene polymer.
  • Examples of the resorcin type epoxy compound include resorcin diglycidyl ether and the like.
  • the epoxy compound may be a copolymer containing a glycidyl group-containing compound as one component.
  • examples thereof include a polymer of a glycidyl ester of ⁇ , ⁇ -unsaturated acid and one or more kinds of monomers selected from the group consisting of ⁇ -olefin, acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester. Be done.
  • an epoxy compound having an epoxy equivalent of 100 to 2000 g / eq is preferable. If the epoxy equivalent is less than 100 g / eq, the amount of epoxy groups is too large and the viscosity of the resin composition becomes high. On the contrary, if the epoxy equivalent exceeds 2000 g / eq, the amount of epoxy groups is small. It tends to be difficult to sufficiently exhibit the effects of improving the alkali resistance, heat shock resistance, and hydrolysis resistance of the resin composition.
  • the epoxy equivalent is more preferably 100 to 1500 g / eq.
  • the molecular weight of the epoxy compound is preferably 8000 or less in terms of weight average molecular weight.
  • the weight average molecular weight exceeds 8000, the compatibility with the thermoplastic polyester resin (A) tends to decrease, and the mechanical strength of the molded product tends to decrease.
  • the weight average molecular weight is more preferably 7,000 or less, still more preferably 6000 or less.
  • the epoxy compound a bisphenol A type epoxy compound or a novolak type epoxy compound obtained from the reaction of bisphenol A or novolak with epichlorohydrin is preferable.
  • the novolak type epoxy compound is particularly preferable in terms of alkali resistance, hydrolysis resistance, heat shock resistance, and surface appearance of the molded product.
  • the content of the hydrolysis inhibitor (C) is 0.2 to 4.5 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). Within such a range, the hydrolysis resistance of the resin composition is improved, the decrease in mechanical strength and the like is suppressed, and the synergistic effect with the maleic anhydride-modified olefin polymer (B) is promoted. Alkali resistance and heat shock resistance can be further improved. If the content of the hydrolysis inhibitor (C) is less than 0.2 parts by mass, the alkali resistance and the hydrolysis resistance are likely to be lowered, and if it is more than 4.5 parts by mass, cross-linking proceeds and during molding. Liquidity tends to deteriorate.
  • the content of the hydrolysis inhibitor (C) is preferably 0.3 parts by mass or more, more preferably 0.4 parts by mass or more, further preferably 0.5 parts by mass or more, and preferably 4 parts by mass or less. It is more preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, and particularly preferably 2 parts by mass or less.
  • the ratio (B) / (C) of the contents of the maleic anhydride-modified olefin polymer (B) and the hydrolysis inhibitor (C) is preferably 99 to 80/1 to 20.
  • (B) / (C) are in such a range, hydrolysis resistance and moldability can be compatible in a well-balanced manner.
  • the amount of the hydrolysis inhibitor (C) is smaller than this range, the hydrolysis resistance tends to deteriorate, and when the amount exceeds this range, the viscosity increases during molding and the moldability tends to become unstable.
  • (B) / (C) is more preferably 98 to 80/2 to 20, still more preferably 97 to 90/3 to 10.
  • the thermoplastic polyester resin composition of the present invention contains a reinforced filler (D).
  • the reinforced filler refers to a material that is contained in a resin component to improve strength and rigidity, and may be in any form such as fibrous, plate-like, granular, or amorphous.
  • the form of the reinforcing filler (D) is fibrous, it may be either inorganic or organic.
  • inorganic or organic For example, glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, metal fiber, inorganic fiber such as wallastnite, fluororesin fiber, organic fiber such as aramid fiber. Contains fiber.
  • the reinforcing filler (D) is fibrous, inorganic fibers are preferable, and glass fibers are particularly preferable.
  • the reinforcing filler (D) may be one kind or a mixture of two kinds.
  • the average fiber diameter is preferably selected in the range of, for example, 1 to 100 ⁇ m, and the average fiber.
  • the length is preferably selected in the range of, for example, 0.1 to 20 mm.
  • the average fiber diameter is more preferably 1 to 50 ⁇ m, more preferably about 5 to 20 ⁇ m.
  • the average fiber length is preferably about 0.12 to 10 mm.
  • the flatness is preferably 1.4 to 10, more preferably 2 to 6. 5 to 5 are more preferable. It is preferable to use the glass fiber having such a deformed cross section because the dimensional stability such as the warp of the molded product and the anisotropy of the shrinkage ratio can be easily improved.
  • the plate-shaped inorganic filler exhibits a function of reducing anisotropy and warpage, and examples thereof include glass flakes, talc, mica, mica, and kaolin.
  • glass flakes are preferable.
  • Examples of other granular or amorphous fillers include ceramic beads, asbestos, clay, zeolite, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide and the like.
  • the surface of the reinforcing filler (D) is preferable to treat the surface of the reinforcing filler (D) with a surface treatment agent such as a sizing agent.
  • a surface treatment agent such as a sizing agent.
  • the surface treatment agent include functional compounds such as epoxy resins, acrylic resins, urethane resins, isocyanate compounds, silane compounds, and titanate compounds.
  • an epoxy resin for the surface treatment.
  • the epoxy resin a novolak type epoxy compound such as phenol novolac type and cresol novolak type, and a bisphenol A type epoxy resin are preferable.
  • the novolak type epoxy compound and the bisphenol A type epoxy resin in combination, and the combined use of the phenol novolac type epoxy compound and the bisphenol A type epoxy resin is from the viewpoint of alkali resistance, hydrolysis resistance and mechanical properties. preferable.
  • silane coupling agents such as aminosilane-based, epoxysilane-based, allylsilane-based, and vinylsilane-based compounds are preferable, and aminosilane-based compounds are particularly preferable.
  • aminosilane compound ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane are preferable, and among them, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane is preferable.
  • ⁇ -Aminopropyltriethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane are preferred.
  • the present invention it is possible to use a novolak type epoxy resin and a bisphenol type epoxy resin as a so-called sizing agent, and to use a reinforced filler surface-treated with an aminosilane compound as a coupling agent for alkali resistance and hydrolysis resistance. It is particularly preferable from the viewpoint of sex.
  • the inorganic functional group of the aminosilane compound is highly reactive with the surface of the reinforcing filler (D), and the organic functional group of aminosilane is highly reactive with the glycidyl group of the epoxy resin.
  • the glycidyl group of the epoxy resin reacts appropriately with the thermoplastic polyester resin (A), thereby improving the interfacial adhesion between the reinforced filler (D) and the epoxy resin.
  • the alkali resistance, hydrolysis resistance, and mechanical properties of the resin composition of the present invention can be easily improved.
  • urethane resin, acrylic resin, antistatic agent, lubricant, water repellent and the like can be included in the surface treatment agent within the range not deviating from the gist of the present invention, and when these other components are included, It is preferable to use urethane resin.
  • the surface treatment of the reinforced filler (D) can be treated by a conventionally known method.
  • the surface treatment may be performed in advance with the above-mentioned surface treatment agent, and the surface treatment has not been performed when preparing the resin composition of the present invention.
  • a surface treatment agent may be added separately from the reinforced filler (D) for surface treatment.
  • the amount of the surface treatment agent adhered to the reinforcing filler (D) is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass. When it is 0.01% by mass or more, the mechanical strength tends to be improved more effectively, and when it is 5% by mass or less, a necessary and sufficient effect can be obtained, and a resin composition is produced. Is preferable because it tends to be easy.
  • the content of the reinforced filler (D) is 10 to 80 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). Within such a range, the strength and rigidity can be improved.
  • the content is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, preferably 75 parts by mass or less, and more preferably 70 parts by mass or less.
  • thermoplastic resin (E) having a water absorption rate of 0.28% by mass or more The thermoplastic polyester resin composition of the present invention does not contain the thermoplastic resin (E) having a water absorption rate of 0.28% by mass or more as measured by the ISO62A method, or even if it does, the content thereof is the thermoplastic polyester. It is less than 9 parts by mass with respect to 100 parts by mass of the resin (A). If the thermoplastic resin (E) is not contained in addition to the thermoplastic resin (E), or even if it is contained, the amount is less than the above amount, so that a significant dimensional change due to water absorption can be suppressed.
  • the water absorption rate of the thermoplastic resin (E) is preferably 0.25% by mass or more, more preferably 0.20% by mass or more.
  • the upper limit of the water absorption rate of the thermoplastic resin (E) is not limited, but is usually 7% by mass or less, preferably 6% by mass or less, and more preferably 5% by mass or less.
  • the water absorption rate of the resin is a value obtained by measuring the water content after being immersed in water at 23 ° C. for 24 hours in accordance with the ISO62A method, and is a flat plate test having a length and width of 60 mm and a thickness of 3.0 mm. It is performed using a piece, and is the mass% obtained from the ratio% of the mass increase before and after water absorption with respect to the original mass (100%) of the test piece.
  • the water supply rate of the thermoplastic resin is, for example, polyamide resin: 0.4 to 4%, polyimide resin: 0.3%, polyamide-imide resin: 0.28%, polymethylmethacrylate resin: 0.3%, ABS resin. : 0.3%.
  • the polycarbonate resin is 0.24%, and the polyoxymethylene resin is 0.25%.
  • the water absorption rate of the polybutylene terephthalate resin is about 0.09%, and that of the polyethylene terephthalate resin is about 0.10%.
  • the thermoplastic resin (E) a polyamide resin is preferable.
  • thermoplastic resin having a water supply rate of less than 0.28% other than the thermoplastic polyester resin (A) is preferable because the polycarbonate resin can suppress warpage during molding.
  • a thermoplastic resin having a water absorption rate of less than 0.28% other than the thermoplastic polyester resin (A) is contained, the content thereof shall be less than 9 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). Is preferable. Even when the polycarbonate resin is contained, the content thereof is preferably less than 9 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A).
  • the resin composition of the present invention preferably contains carbon black (F) for the purpose of imparting black coloring and enhancing weather resistance (light) such as ultraviolet resistance.
  • the average particle size of carbon black is preferably 30 to 300 nm, more preferably 50 nm or more, further preferably 80 nm or more, particularly preferably 100 nm or more, still more preferably 200 nm or less, further preferably 170 nm or less, and particularly preferably 150 nm or less. It is preferably 140 nm or less, and most preferably 140 nm or less.
  • the average particle size of carbon black is obtained by acquiring an aggregate enlarged image according to the procedure described in ASTM D3849, measuring the particle size of 3,000 particles as unit constituent particles from this aggregate image, and arithmetically averaging them. The value.
  • the DBP oil absorption of carbon black is preferably less than 100 ml / 100 g, more preferably less than 70 ml / 100 g, and even more preferably less than 50 ml / 100 g. It is preferable that the amount of DBP oil absorbed is less than 100 ml / 100 g because the fluidity of the resin composition tends to be improved.
  • the lower limit is usually 5 ml / 100 g, preferably 10 ml / 100 g.
  • the DBP oil absorption amount is a value measured in accordance with JIS K6217-4: 2008.
  • the iodine adsorption amount (mg / g) per unit mass of carbon black is preferably less than 60 mg / g, and more preferably less than 40 mg / g.
  • the lower limit is usually 1 mg / g, preferably 3 mg / g. It is preferable that the iodine adsorption amount is less than 60 mg / g because the fluidity of the resin composition tends to be improved.
  • the iodine adsorption amount is a value measured in accordance with JIS K6217-1: 2008.
  • the nitrogen adsorption specific surface area of carbon black is usually preferably less than 100 m 2 / g, particularly preferably 80 m 2 / g or less, particularly preferably 50 m 2 / g or less, and particularly preferably 30 m 2 / g or less. It is preferable that the nitrogen adsorption specific surface area is less than 100 m 2 / g because the fluidity of the resin composition tends to be improved.
  • the lower limit is usually 1 m 2 / g, preferably 3 m 2 / g.
  • the nitrogen adsorption specific surface area is a value measured in accordance with JIS K6217-2: 2001.
  • the pH of carbon black is not particularly limited, but is usually 2 to 10, preferably 3 to 9, and even more preferably 4 to 8.
  • the content of carbon black (F) is preferably 0.01 to 0.5 parts by mass, more preferably 0.05 parts by mass or more, and 0.1 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is more preferably parts by mass or more, more preferably 0.4 parts by mass or less, and further preferably 0.3 parts by mass or less.
  • Carbon black (F) is preferably blended as a masterbatch.
  • the handling property of the thermoplastic polyester resin composition at the time of melt-kneading and the dispersibility in the resin composition are improved, and the resin composition having excellent tracking resistance can be obtained.
  • a carbon black masterbatch having a carbon black concentration of 30 to 80% by mass is preferable.
  • a carbon black masterbatch based on a polyolefin resin is preferable.
  • a masterbatch that has been melt-kneaded at a high concentration in a polyolefin resin base the handling property of the thermoplastic polyester resin composition during melt-kneading and the dispersibility in the resin composition are improved, and the tracking resistance is excellent. It can be a resin composition.
  • polyolefin resin As the polyolefin resin as the base resin of the masterbatch, a homopolymer or a copolymer composed of at least one ⁇ -olefin having 2 to 8 carbon atoms, a copolymer thereof, or a modified product thereof is preferable, and among them, a polyethylene resin or a polypropylene resin is preferable. Etc. are preferable.
  • a resin such as polybutylene terephthalate resin can be considered, but when polybutylene terephthalate resin is used, for example, the effect of improving the tracking resistance tends to be inferior to that of the polyolefin resin. ..
  • polyethylene resin As the polyolefin resin, polyethylene resin is particularly preferable.
  • the content of carbon black in the masterbatch is preferably 30 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 35 to 65% by mass. If the content of carbon black in the masterbatch is less than 30% by mass, the amount added to the masterbatch is large in order to obtain a sufficient blackness, and a good black appearance may not be obtained. Further, if it exceeds 80% by mass, poor dispersion of carbon black may occur, which is not preferable.
  • the content of the carbon black masterbatch is preferably 0.2 to 4.5 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If it exceeds 4.5 parts by mass, the tracking resistance tends to deteriorate.
  • the content is more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, further preferably 4 parts by mass or less, and further preferably 3.5 parts by mass or less.
  • the polyester resin composition of the present invention contains a flame retardant.
  • a flame retardant for example, a halogen-based flame retardant, a phosphorus-based flame retardant, and a silicone-based flame retardant can be contained, and among them, a halogen-based flame retardant or a phosphorus-based flame retardant is preferably contained.
  • Preferred specific examples of the halogen-based flame retardant include brominated polycarbonate resin, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, glycidyl brominated bisphenol A, and pentabromo.
  • brominated flame retardant examples thereof include benzyl polyacrylate and brominated imide (bromineed phthalimide, etc.).
  • brominated flame retardant is preferable, and brominated polycarbonate resin, brominated polystyrene resin, glycidyl brominated bisphenol A, pentabromobenzyl polyacrylate, etc. are used. It tends to suppress the decrease in impact resistance, which is more preferable.
  • Examples of the phosphorus-based flame retardant include (di) phosphinic acid metal salts such as aluminum ethylphosphinate, aluminum diethylphosphinate, aluminum ethylmethylphosphinate, and zinc diethylphosphinate, and melamine and phosphorus typified by melamine polyphosphate.
  • phosphinic acid metal salts such as aluminum ethylphosphinate, aluminum diethylphosphinate, aluminum ethylmethylphosphinate, and zinc diethylphosphinate
  • melamine and phosphorus typified by melamine polyphosphate.
  • examples thereof include acid reaction products, phosphoric acid esters, cyclic phenoxyphosphazene, chain phenoxyphosphazene, phosphazene such as crosslinked phenoxyphosphazene, and among them,
  • phosphinic acid metal salt, polyphosphate melamine, and phosphazene are thermal
  • the content of the flame retardant is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If the flame retardant is less than 5 parts by mass, it is difficult to obtain sufficient flame retardancy, and if it exceeds 100 parts by mass, the tracking resistance may not be improved.
  • the more preferable content of the flame retardant is 10 parts by mass or more, more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is 80 parts by mass or less, more preferably 70 parts by mass or less, particularly 60 parts by mass or less, and particularly preferably 50 parts by mass or less.
  • the polyester resin composition of the present invention preferably contains a flame retardant aid together with the flame retardant.
  • the flame retardant aid include antimony compounds, zinc borate, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, zirconium oxide, tin oxide, iron oxide, titanium oxide, aluminum oxide and the like, and two or more of them are used in combination. You may. Among these, antimony compounds and zinc borate are preferable because they are more excellent in flame retardancy.
  • the antimony compound include antimony trioxide (Sb 2 O 3 ), antimony pentoxide (Sb 2 O 5 ), sodium antimonate and the like.
  • the mass concentrations of the halogen atom derived from the halogen-based flame retardant and the antimony atom derived from the antimony compound in the polyester resin composition are 5 to 16% by mass in total. It is preferably present, and more preferably 6 to 15% by mass. If it is less than 5% by mass, the flame retardancy tends to decrease, and if it exceeds 16% by mass, the mechanical strength and the tracking resistance may decrease.
  • the mass ratio of the halogen atom to the antimony atom is preferably 0.3 to 5, and more preferably 0.3 to 4.
  • the content of the flame retardant aid is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and further preferably 10 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). ..
  • the polyester resin composition of the present invention may contain a colorant.
  • a colorant By including a colorant, the molded product can be given a color.
  • the colorant may be a chromatic colorant or an achromatic colorant.
  • the colorant may be a pigment or a dye.
  • chromatic colorant examples include a red colorant, a blue colorant, a yellow colorant, a green colorant, and an orange colorant.
  • a red colorant composition or the like may be obtained by mixing two or more kinds of colorants to make them red.
  • the colorant preferably contains an orange colorant and / or an orange colorant composition.
  • the content thereof is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A). .. By setting the value to the lower limit or more, the coloring property tends to be further improved.
  • the upper limit of the content of the chromatic colorant is preferably 1 part by mass or less, and more preferably 0.8 part by mass or less with respect to 100 parts by mass of the thermoplastic polyester resin (A). .. By setting the value to the upper limit or less, the mechanical strength tends to be further improved.
  • thermoplastic polyester resin composition of the present invention preferably contains a mold release agent.
  • a mold release agent known release agents usually used for polyester resins can be used, but among them, polyolefin-based compounds and fatty acid ester-based compounds are preferable in terms of good alkali resistance, and especially polyolefin-based ones. Compounds are preferred.
  • polyolefin compound examples include paraffin wax, Fischer-Tropsch wax, polyethylene wax and the like, and among them, those having a weight average molecular weight of 700 to 10000 and further preferably 900 to 8000 are preferable.
  • fatty acid ester-based compound examples include saturated or unsaturated monovalent or divalent aliphatic carboxylic acid esters, glycerin fatty acid esters, sorbitan fatty acid esters and other fatty acid esters, and partially saponified products thereof.
  • mono or difatty acid esters composed of fatty acids having 11 to 28 carbon atoms, preferably 17 to 21 carbon atoms and alcohols are preferable.
  • fatty acids examples include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, cerotic acid, melicic acid, tetrariacontanic acid, montanic acid, adipic acid, azelaic acid and the like. Be done. Further, the fatty acid may be an alicyclic type.
  • the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group.
  • monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable.
  • the aliphatic term also contains an alicyclic compound.
  • specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like.
  • the above ester compound may contain an aliphatic carboxylic acid and / or an alcohol as an impurity, or may be a mixture of a plurality of compounds.
  • fatty acid ester compound examples include glycerin monostearate, glycerin monobehenate, glycerin dibehenate, glycerin-12-hydroxymonostearate, sorbitan monostearate, pentaerythritol monostearate, and pentaeristoldi.
  • examples thereof include stearate, stearyl stearate, and ethylene glycol montanic acid ester.
  • the content of the release agent is preferably 0.1 to 3 parts by mass, but more preferably 0.2 to 2.5 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). , More preferably 0.3 to 2 parts by mass. If it is less than 0.1 part by mass, the surface property is likely to be deteriorated due to poor mold release during melt molding, while if it is more than 3 parts by mass, the kneading workability of the resin composition is likely to be deteriorated, and the molded product is formed. The surface tends to be cloudy.
  • the thermoplastic polyester resin composition of the present invention contains a stabilizer because it has an effect of improving thermal stability and preventing deterioration of mechanical strength, transparency and hue.
  • a sulfur-based stabilizer and a phenol-based stabilizer are preferable.
  • any conventionally known sulfur atom-containing compound can be used, and among them, thioethers are preferable.
  • thioethers are preferable.
  • 2-Mercaptobenzothiazole 2-mercaptobenzimidazole, tetramethylthium monosulfide, tetramethylthiuram disulfide, nickeldibutyldithiocarbamate, nickelisopropylxanthate, trilauryltrithiophosphite.
  • pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable.
  • phenolic stabilizer examples include pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and octadecyl-3- (3,5-di-tert-butyl-4).
  • -Hydroxyphenyl) propionate thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like.
  • pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
  • octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
  • one type may be contained, or two or more types may be contained in any combination and ratio.
  • the content of the stabilizer is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect improvement in thermal stability and compatibility of the resin composition, and a decrease in molecular weight and deterioration of hue during molding are likely to occur, and 2 parts by mass is used. If it exceeds the amount, the amount becomes excessive and the generation of silver and the deterioration of hue tend to occur more easily.
  • the content of the stabilizer is more preferably 0.01 to 1.5 parts by mass, still more preferably 0.1 to 1 part by mass.
  • the thermoplastic polyester resin composition of the present invention may contain a thermoplastic resin other than the above-mentioned thermoplastic polyester resin (A) and the thermoplastic resin (E) as long as the effect of the present invention is not impaired. can.
  • the content shall be 20 parts by mass or less with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, particularly preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.
  • thermoplastic polyester resin composition of the present invention may contain various additives other than those described above, and examples of such additives include antistatic agents (fluororesin and the like), ultraviolet absorbers, and the like. Examples thereof include antistatic agents, antifogging agents, antiblocking agents, plasticizers, dispersants, antibacterial agents and the like.
  • the plasticizer include various plasticizers, for example, ester-based plasticizers (aromatic polyvalent carboxylic acid ester, alicyclic polyvalent carboxylic acid ester, polyester, sucrose fatty acid ester, etc.), phosphoric acid ester-based plasticizer.
  • plasticizers examples thereof include agents (tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.), acrylic polymers, and the like.
  • plasticizers can be used alone or in combination of two or more.
  • a plasticizer having a high boiling point for example, a plasticizer having a boiling point of 250 to 400 ° C., preferably 270 to 400 ° C., more preferably about 300 to 400 ° C.
  • an effect such as improvement of fluidity can be obtained.
  • thermoplastic polyester resin composition of the present invention can be produced according to a conventional method for preparing a resin composition. That is, the above-mentioned essential components and other components and additives added as desired are mixed well, and then melt-kneaded by a uniaxial or twin-screw extruder. Further, it is also possible to prepare a resin composition without mixing each component in advance or by mixing only a part thereof in advance and supplying it to an extruder by using a feeder to melt-knead it. Further, a masterbatch of a part thereof may be blended and melt-kneaded.
  • the reinforcing filler (D) is preferably side-fed by a side feeder. Further, it is also possible to supply a mixture in which each component is mixed in advance to a molding machine such as an injection molding machine as it is without melt-kneading to manufacture various molded products.
  • the method for producing a molded product using the thermoplastic polyester resin composition of the present invention is not particularly limited, and a molding method generally adopted for the thermoplastic polyester resin composition can be arbitrarily adopted.
  • a molding method generally adopted for the thermoplastic polyester resin composition can be arbitrarily adopted.
  • examples include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas assist, molding methods using heat insulating molds, molding methods using rapid heating molds, and foaming.
  • injection molding and insert molding are preferable because the effects of the present invention are remarkable, such as good productivity and surface properties of the obtained molded product.
  • the obtained molded product has mechanical strength, heat resistance, and dimensional stability in a well-balanced manner at a high level, and is excellent in tracking resistance, heat shock resistance, and hydrolysis resistance.
  • Particularly suitable for use as insulating members for electrical and electronic equipment parts and electrical components that are strictly required for example, housings, connectors, relays, switches, circuit breakers, electromagnetic switches, terminal blocks, sensors, actuators, terminal switches, etc. can do.
  • the molded product for example, it can be particularly preferably used as a fitting member having a fitting structure, an insert molded product, or the like.
  • ⁇ Tracking resistance CTI: V>
  • the pellets obtained above are dried at 120 ° C. for 6 hours until just before, and then using an injection molding machine (“NEX-80” manufactured by Nissei Resin Industry Co., Ltd.) at a cylinder temperature of 260 ° C. and a thickness of 3.0 mm, 1
  • NEX-80 manufactured by Nissei Resin Industry Co., Ltd.
  • a square flat plate-shaped test piece having a side of 100 mm was formed, a tracking resistance test specified in the test method UL746A, paragraph 23 was performed, and the measurement was performed in accordance with ASTM D3638.
  • An electrolytic solution (0.1% ammonium chloride aqueous solution, resistance 385 ⁇ ⁇ cm at 23 ° C.) is dropped from the nozzle of the device at intervals of 30 seconds, and a voltage of 600 V or less (25 V step) is applied between both platinum electrodes for tracking.
  • the CTI is preferably 400 V or higher, more preferably 450 V or higher, and most preferably 600 V or higher.
  • injection molding peak pressure MPa
  • the peak pressure during injection molding was measured as follows. After the pellets obtained by the above manufacturing method are dried at 120 ° C. for 5 hours, the cylinder temperature is 260 ° C. and the mold temperature is 80 ° C. using an injection molding machine (“NEX-80” manufactured by Nissei Resin Industry Co., Ltd.). Under the conditions, the injection molding peak pressure (unit: MPa) when molding a 100 ⁇ 100 ⁇ 2 mmt test piece was measured. The peak pressure during molding is preferably 55 MPa or less.
  • the ISO multipurpose test piece (thickness 4.0 mm) was treated with a pressure cooker tester (manufactured by Hirayama Seisakusho Co., Ltd.) at a temperature of 121 ° C., a relative humidity of 100%, and a pressure of 2 atm for 100 hours.
  • the tensile strength (unit: MPa after wet heat treatment) was measured. From the following formula, the strength retention rate (%) after the wet heat treatment was determined.
  • the strength retention after the wet heat treatment is preferably 50% or more.
  • ⁇ Tension modulus (MPa)> Using the ISO multipurpose test piece (4 mm thick) obtained above, the tensile elastic modulus (unit: MPa) was measured according to ISO527.
  • the tensile elastic modulus is preferably 7500 MPa or more.
  • the total score was calculated by assuming that the score was 0. As a comprehensive evaluation, the judgment was made according to the following criteria based on the total score. A (best): 18 points B (very good): 14 points or more C (good): 12 points or more D (bad): 10 points or more E (very bad): less than 10 points.
  • E very bad
  • thermoplastic polyester resin composition of the present invention has mechanical strength, heat resistance, and dimensional stability in a well-balanced manner at a high level, and is excellent in tracking resistance, heat shock resistance, and hydrolysis resistance, and further. Since it is a polyester resin material having excellent fluidity during injection molding, it can be particularly preferably used as an insulating member for electrical and electronic equipment parts and electrical components.

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Abstract

Une composition de résine de polyester thermoplastique selon la présente invention est caractérisée en ce qu'elle comprend 100 parties en masse d'une résine de polyester thermoplastique (A) ayant une viscosité intrinsèque de 0,60 dl/g ou plus, mais inférieure à 0,85 dl/g, 5 à 30 parties en masse d'un polymère d'oléfine modifié par un anhydride maléique (B), 0,2 à 4,5 parties en masse d'un inhibiteur d'hydrolyse (C), et de 10 à 80 parties en masse d'une charge de renforcement (D) et soit ne contenant pas de résine thermoplastique (E) qui a une absorption d'eau, telle que déterminée par la méthode ISO 62A, de 0,28 % en masse ou plus soit contenant la résine thermoplastique (E) en une quantité inférieure à 9 parties en masse pour 100 parties en masse de la résine de polyester thermoplastique (A).
PCT/JP2021/028818 2020-08-06 2021-08-03 Composition de résine de polyester thermoplastique WO2022030507A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000038497A (ja) * 1998-07-22 2000-02-08 Mitsubishi Engineering Plastics Corp 黒色ポリエステル樹脂組成物及びその成形体
JP2009173876A (ja) * 2007-12-27 2009-08-06 Mitsubishi Engineering Plastics Corp サニタリー部品用ポリアルキレンテレフタレート樹脂組成物
WO2014168169A1 (fr) * 2013-04-09 2014-10-16 株式会社カネカ Composition de résine à base de téréphtalate de polybutylène ignifuge
JP2017197676A (ja) * 2016-04-28 2017-11-02 東洋紡株式会社 ポリブチレンテレフタレート樹脂組成物
JP2020076023A (ja) * 2018-11-09 2020-05-21 東レ株式会社 ポリブチレンテレフタレート樹脂組成物およびそれからなる高電圧部品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000038497A (ja) * 1998-07-22 2000-02-08 Mitsubishi Engineering Plastics Corp 黒色ポリエステル樹脂組成物及びその成形体
JP2009173876A (ja) * 2007-12-27 2009-08-06 Mitsubishi Engineering Plastics Corp サニタリー部品用ポリアルキレンテレフタレート樹脂組成物
WO2014168169A1 (fr) * 2013-04-09 2014-10-16 株式会社カネカ Composition de résine à base de téréphtalate de polybutylène ignifuge
JP2017197676A (ja) * 2016-04-28 2017-11-02 東洋紡株式会社 ポリブチレンテレフタレート樹脂組成物
JP2020076023A (ja) * 2018-11-09 2020-05-21 東レ株式会社 ポリブチレンテレフタレート樹脂組成物およびそれからなる高電圧部品

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