WO2021140553A1 - Flame-retardant polybutylene terephthalate resin composition - Google Patents

Flame-retardant polybutylene terephthalate resin composition Download PDF

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Publication number
WO2021140553A1
WO2021140553A1 PCT/JP2020/000111 JP2020000111W WO2021140553A1 WO 2021140553 A1 WO2021140553 A1 WO 2021140553A1 JP 2020000111 W JP2020000111 W JP 2020000111W WO 2021140553 A1 WO2021140553 A1 WO 2021140553A1
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Prior art keywords
polybutylene terephthalate
flame
terephthalate resin
resin composition
flame retardant
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PCT/JP2020/000111
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French (fr)
Japanese (ja)
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一也 五島
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ポリプラスチックス株式会社
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Priority to PCT/JP2020/000111 priority Critical patent/WO2021140553A1/en
Publication of WO2021140553A1 publication Critical patent/WO2021140553A1/en

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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
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof
    • 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 flame-retardant polybutylene terephthalate resin composition and a method for producing the same.
  • Polybutylene terephthalate resin is widely used as an engineering plastic in various applications such as automobile parts and electrical / electronic equipment parts because it has excellent mechanical properties, electrical properties, heat resistance, and other properties. Of these, in the applications of electrical and electronic equipment parts, flame retardancy is required for the materials used in order to prevent ignition due to tracking and the like. Since polybutylene terephthalate resin is insufficient in flame retardancy by itself, it is used as a flame retardant resin composition to which a flame retardant is added.
  • Halogenated benzyl acrylate-based flame retardant is one of the flame retardants added to such polybutylene terephthalate resin, and an example thereof is polypentabromobenzyl acrylate (PBBPA) as introduced in Patent Document 1.
  • PBBPA polypentabromobenzyl acrylate
  • the monomer pentabromobenzyl acrylate is polymerized in ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether, or in chlorobenzene. The method is illustrated.
  • chlorobenzene which is a halogenated aromatic compound
  • PBBPA polybutylene terephthalate resin composition
  • This chlorobenzene is generally a stable compound, but in a high temperature environment, especially when it comes into contact with a metal such as a metal oxide or an alkali metal compound, dechlorination occurs and a compound such as hydrogen chloride is generated. Sometimes. Therefore, when a composition containing this is used for a molded product that comes into contact with a metal member such as insert molding or terminal press fitting, there may be a problem that the metal member is corroded.
  • a molded product made of a polybutylene terephthalate resin composition is used as an electrically insulating member in combination with a metal member which is a conductive portion, so that the metal member may not be corroded.
  • polybutylene terephthalate resin is a resin with excellent tracking resistance by itself.
  • various additives such as a reinforcing filler and various stabilizers for adjusting various properties such as mechanical strength, or the above-mentioned flame retardant are usually used.
  • tracking resistance may be impaired depending on the type.
  • brominated flame retardants such as PBBPA can reduce tracking resistance because carbonization is likely to occur. Therefore, in order to achieve both flame retardancy and tracking resistance, for example, Patent Document 2 discloses a thermoplastic polyester resin composition to which a phosphorus-based flame retardant is added instead of a bromine-based flame retardant. May be disadvantageous in terms of cost and seepage from the article. Therefore, it is required to improve the flame retardancy while ensuring the tracking resistance of the polybutylene terephthalate resin.
  • An object of the present invention is to suppress a decrease in tracking resistance and corrosion of a metal member in contact with a molded product in a polybutylene terephthalate resin composition using a halogenated benzyl acrylate flame retardant as a flame retardant. And.
  • the present inventor uses a halogenated benzyl acrylate-based flame retardant as a flame retardant in the process of research subject to the above, and in a polybutylene terephthalate resin composition containing a specific tracking resistance improving agent, the polybutylene terephthalate resin.
  • a halogenated benzyl acrylate-based flame retardant as a flame retardant in the process of research subject to the above, and in a polybutylene terephthalate resin composition containing a specific tracking resistance improving agent, the polybutylene terephthalate resin.
  • the present invention relates to the following (1) to (8).
  • a filler for improving properties a filler for improving properties
  • a flame-retardant polybutylene terephthalate resin composition characterized in that the content of a halogenated aromatic compound other than the above is less than 0.5 ppm.
  • X is a hydrogen atom or a bromine atom, at least one X is a bromine atom, and m is a number of 10 to 2000.
  • a production method characterized in that the content of the halogenated aromatic compound in the solvent used in the step is 1000 ppm or less.
  • the poly in a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant, the poly by suppressing the amount of a halogenated aromatic compound such as chlorobenzene in the process of producing the flame retardant. It is possible to suppress the corrosion of the metal member in contact with the butylene terephthalate resin composition.
  • a to B means A or more and B or less.
  • the polybutylene terephthalate resin contains 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. It is a polybutylene terephthalate resin obtained by polycondensing with a glycol component containing glycol (1,4-butanediol) or an ester-forming derivative thereof (acetylated product, etc.).
  • the polybutylene terephthalate resin (A) is not limited to the homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of butylene terephthalate units.
  • the amount of terminal carboxyl groups of the polybutylene terephthalate resin (A) is not particularly limited as long as the object of the present invention is not impaired, but is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less.
  • the intrinsic viscosity of the polybutylene terephthalate resin (A) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 0.60 dL / g or more and 1.2 dL / g or less, and 0.65 dL / g or more and 0. More preferably, it is 9.9 dL / g or less.
  • the obtained polybutylene terephthalate resin composition is particularly excellent in moldability. It is also possible to adjust the intrinsic viscosity by blending polybutylene terephthalate resins having different intrinsic viscosities.
  • a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g can be 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 be done.
  • the intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol under the condition of a temperature of 35 ° C.
  • aromatic dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof is used as a comonomer component in the preparation of the polybutylene terephthalate resin (A), for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4, C 8-14 aromatic dicarboxylic acid such as 4'-dicarboxydiphenyl ether ; C 4-16 alcandicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid; C 5-10 such as cyclohexanedicarboxylic acid Cycloalkandicarboxylic acids; ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.) can be used. 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 and C 6-12 alkane dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid are more preferable.
  • glycol component other than 1,4-butanediol is used as the comonomer component in the preparation of the polybutylene terephthalate resin (A), for example, ethylene glycol, propylene glycol, trimethylene glycol, 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, dipropylene glycol; alicyclic type such as cyclohexanedimethanol, hydride bisphenol A, etc.
  • Diols aromatic diols such as bisphenol A, 4,4'-dihydroxybiphenyl; alkylene oxides of C 2-4 of bisphenol A such as 2 mol adducts of ethylene oxide of bisphenol A and 3 mol adducts of propylene oxide of bisphenol A.
  • Additives; or ester-forming derivatives of these glycols (acetylates, etc.) can be used. These glycol components can be used alone or in combination of two or more.
  • C 2-6 alkylene glycols such as ethylene glycol and trimethylene glycol
  • polyoxyalkylene glycols such as diethylene glycol
  • alicyclic diols such as cyclohexanedimethanol are more preferable.
  • 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.
  • the content of the polybutylene terephthalate resin (A) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 70% by mass based on the total mass of the resin composition. Is even more preferable.
  • (B) Halogenated benzyl acrylate flame retardant examples include a brominated acrylic polymer represented by the following general formula (I).
  • X in the formula is a hydrogen atom or a bromine atom, and at least one or more is bromine.
  • the number of X is 1 to 5 in one structural unit, but it is preferably 3 to 5 from the viewpoint of flame retardancy.
  • the average degree of polymerization m is 10 to 2000, preferably in the range of 15 to 1000.
  • the average degree of polymerization is lower than 10, the thermal stability is deteriorated, and if it exceeds 2000, the molding processability of the added polybutylene terephthalate resin is deteriorated.
  • the brominated acrylic polymer may be used alone or in combination of two or more.
  • the (B) halogenated benzyl acrylate-based flame retardant used in the present invention can be used as an impurity in a solvent during polymerization or a decomposition product of the bromized acrylic polymer, in addition to the above-mentioned brominated acrylic polymer which is the flame retardant itself.
  • it may contain a derived halogenated aromatic compound
  • the content of such an impurity, a halogenated aromatic compound other than the flame retardant is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 30 ppm or less. , Especially preferably 10 ppm or less.
  • the content of the halogenated aromatic compound other than the flame retardant was measured, for example, by measuring the gas generated when a sample obtained by crushing the (B) halogenated benzyl acrylate flame retardant was heat-treated in the headspace by a gas chromatograph. , Can be determined from the amount of gas generated from the halogenated aromatic compound.
  • the brominated acrylic polymer represented by the general formula (I) is obtained by polymerizing a benzyl acrylate containing bromine alone, but a benzyl methacrylate having a similar structure or the like may be copolymerized.
  • the bromine-containing benzyl acrylate include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, or a mixture thereof. Of these, pentabromobenzyl acrylate is preferable.
  • the benzyl methacrylate which is a copolymerizable component, include methacrylates corresponding to the above-mentioned acrylates.
  • acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and benzyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and benzyl methacrylate.
  • methacrylic acid esters such as styrene, acrylonitrile, fumaric acid, unsaturated carboxylic acids such as maleic acid or an anhydride thereof, vinyl acetate, vinyl chloride and the like.
  • crosslinkable vinyl-based monomers xylylene diacrylate, xylylene dimethacrylate, tetrabromxylylene diacrylate, tetrabromxylylene dimethacrylate, butadiene, isoprene, and divinylbenzene can also be used. These are used in an equimolar amount or less, preferably 0.5 times a molar amount or less, based on benzyl acrylate or benzyl methacrylate.
  • a brominated acrylic monomer is subjected to solution polymerization or bulk polymerization to a predetermined degree of polymerization.
  • a method of reacting can be mentioned.
  • the content of the halogenated aromatic compound in the solvent is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 300 ppm or less, and particularly preferably 100 ppm or less. preferable.
  • halogenated benzene or a halogenated aromatic compound such as chlorobenzene it is more preferable not to use halogenated benzene or a halogenated aromatic compound such as chlorobenzene as the solvent.
  • aprotic solvents such as ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether and dioxane are preferable.
  • the (B) halogenated benzyl acrylate flame retardant such as the above brominated acrylic polymer uses water and / or alkali (earth) metal ions in order to remove reaction by-products such as residual sodium polyacrylate. It is preferable to wash with the contained aqueous solution.
  • "containing an alkali (earth) metal ion” means containing an alkali metal ion and / or an alkaline earth metal ion.
  • An aqueous solution containing an alkali (earth) metal ion can be easily obtained by adding an alkali (earth) metal salt to water, but an alkali (earth) metal containing no chloride ion, phosphate ion, etc.
  • Certain hydroxides are optimal.
  • calcium hydroxide is used as the alkali (earth) metal salt, for example, calcium hydroxide is generally soluble in about 0.126 g in 100 g of water at 20 ° C., and the concentration of the aqueous solution is not particularly specified as long as it is up to solubility. ..
  • the method of cleaning with an aqueous solution containing water and / or an alkali (earth) metal ion is not particularly limited, and the brominated acrylic polymer contains water and / or an alkali (earth) metal ion for an appropriate time. It may be a method such as immersing in an aqueous solution.
  • the brominated acrylic polymer that has been washed with the aqueous solution containing water and / or alkaline (earth) metal ions generally has a dry solid content of 100 ppm or less in the hot water extract.
  • a simple brominated acrylic polymer is used, foreign matter is hardly generated on the surface of the molded product.
  • the content of the halogenated aromatic compound other than the flame retardant is less than 0.5 ppm, preferably 0.3 ppm or less, more preferably. Is 0.1 ppm or less.
  • the insert molded product using the polybutylene terephthalate resin composition has metal terminals. Corrosion can be suppressed.
  • the content of the halogenated aromatic compound other than the flame retardant is determined by, for example, measuring the gas generated when the sample obtained by crushing the polybutylene terephthalate resin composition is heat-treated in the headspace by a gas chromatograph. It can be obtained from the amount of gas generated from the halogenated aromatic compound.
  • an antimony-based flame-retardant aid In making the above resin flame-retardant, it is preferable to use an antimony-based flame-retardant aid together.
  • Typical flame-retardant aids include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate and the like.
  • a dripping inhibitor such as polytetrafluoroethylene together.
  • the range of addition of the halogenated benzyl acrylate flame retardant and the antimon flame retardant to the resin is 3 to 50 parts by mass of the polymer with respect to 100 parts by mass of the polybutylene terephthalate resin, and 5 to 40 parts by mass.
  • the amount is preferably 10 to 30 parts by mass, more preferably 10 to 30 parts by mass.
  • the range of 1 to 40 parts by mass of the antimony flame retardant aid is preferable. If the amount of the brominated acrylic polymer and the antimony-based flame retardant aid added is too small, sufficient flame retardancy cannot be imparted, and if it is too large, the physical properties of the molded product may be deteriorated.
  • (C) Resin for improving tracking resistance In order to improve tracking resistance, (C) resin for improving tracking resistance is supplementarily added to the flame-retardant polybutylene terephthalate resin composition of the present invention.
  • the resin for improving the tracking resistance a resin having not only high tracking resistance but also (A) a processing temperature close to that of the polybutylene terephthalate resin and good compatibility can be used.
  • the resin for improving the tracking resistance (C) include an olefin-based elastomer, an acrylic-based core-shell type elastomer, a linear polyolefin resin, and a combination thereof.
  • olefin-based elastoma examples include an ethylene-propylene copolymer (EP copolymer), an ethylene-butene copolymer, an ethylene-octene copolymer, an ethylene-propylene-diene copolymer (EPD copolymer), and the like.
  • EP copolymer ethylene-propylene copolymer
  • EPD copolymer ethylene-propylene-diene copolymer
  • Copolymers containing at least one unit selected from ethylene-propylene-butene copolymers, ethylene-vinyl acetate copolymers, EP copolymers and EPD copolymers, olefins and (meth) acrylic monomers Copolymers with (ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, etc.) and the like are included.
  • Preferred olefin-based elastomas include EP copolymers, EPD copolymers, and copolymers of olefins and (meth) acrylic monomers, with ethylene ethyl acrylate being particularly preferred. These olefin-based elastomers can be used alone or in combination of two or more.
  • Acrylic core-shell type elastomer is a polymer in which the core layer is composed of a rubber component (soft component) and the shell layer is composed of a hard component, and acrylic rubber is used as the rubber component of the core layer.
  • the acrylic rubber used for the core layer preferably has a glass transition temperature (Tg) of less than 0 ° C. (for example, ⁇ 10 ° C. or lower), and preferably ⁇ 20 ° C. or lower (for example, ⁇ 180 ° C. or higher and ⁇ 25 ° C. or lower). Is more preferable, and it is particularly preferable that the temperature is ⁇ 30 ° C. or lower (for example, ⁇ 150 ° C. or higher and ⁇ 40 ° C. or lower).
  • the acrylic rubber used as the rubber component is preferably a polymer obtained by polymerizing an acrylic monomer such as alkyl acrylate as a main component.
  • an acrylic monomer such as alkyl acrylate as a main component.
  • the alkyl acrylate used as the monomer of the acrylic rubber the alkyl ester of acrylic acid C 1 to C 12 such as butyl acrylate is preferable, and the alkyl ester of acrylic acid C 2 to C 6 is more preferable.
  • the acrylic rubber may be a homopolymer of an acrylic monomer or a copolymer.
  • the acrylic rubber may be a copolymer of acrylic monomers or a copolymer of an acrylic monomer and another unsaturated bond-containing monomer.
  • the acrylic rubber may be a copolymer of a crosslinkable monomer.
  • a vinyl polymer is preferably used for the shell layer.
  • the vinyl-based polymer may be, for example, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, a methacrylic acid ester-based monomer, and an acrylic acid ester monomer. Obtained by polymerization or copolymerization.
  • the core layer and the shell layer of such an acrylic core-shell type elastomer may be bonded by graft copolymerization. This graft copolymerization is obtained by adding a graft crossover that reacts with the shell layer at the time of polymerization of the core layer, giving a reactive group to the core layer, and then forming the shell layer, if necessary.
  • an organosiloxane having a vinyl bond or an organosiloxane having a thiol is used, and acryloxysiloxane, methacryoxysiloxane, and vinylsiloxane are preferably used.
  • the linear polyolefin resin is preferably a polyolefin resin having substantially no side chain, such as polyethylene or polypropylene, and having a viscosity average molecular weight of 10,000 to 1,000,000 as measured by the ASTM D2857 method.
  • the amount of the resin for improving tracking resistance added is 5 to 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin, and may be 10 to 90 parts by mass or 20 to 80 parts by mass.
  • the content of the resin for improving tracking resistance is the flame-retardant polybutylene terephthalate of the present invention. It is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less with respect to the entire resin composition.
  • (D) Tracking resistance improver To the flame-retardant polybutylene terephthalate resin composition of the present invention, (D) tracking resistance improving agent is supplementarily added in order to further improve the tracking resistance. ..
  • the (D) tracking resistance improving agent examples include talc, mica, and an inorganic metal compound, and any one of these or a combination thereof can be used.
  • talc known talc can be used, and preferably talc having a volume average particle diameter of 1 to 10 ⁇ m or compressed fine powder talc having a bulk specific density of 0.4 to 1.5 can be used.
  • mica known ones can be used, and preferably mica having a volume average particle diameter of 10 to 60 ⁇ m can be used.
  • inorganic metal compound examples include metal salts of inorganic acids (inorganic acids other than phosphoric acid and silicic acid, for example, carbonic acid, boric acid, tin acid, tungsten acid, sulfuric acid, etc.) and metal oxides (magnesium oxide, iron oxide, oxidation).
  • inorganic acids organic acids other than phosphoric acid and silicic acid, for example, carbonic acid, boric acid, tin acid, tungsten acid, sulfuric acid, etc.
  • metal oxides magnesium oxide, iron oxide, oxidation
  • Titanium, zinc oxide, alumina, etc. metal hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (bemite), etc.), metal sulfides (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.) And the like, and preferred examples thereof include barium sulfate, zinc sulfide, zinc borate, calcium borate, and zinc stannate.
  • These (D) tracking resistance improvers may be surface-treated (surface-coated) with an inorganic compound and / or an organic compound
  • examples of the inorganic compound used for the surface treatment include aluminum hydroxide and alumina.
  • Preferred examples thereof include silica, zirconia, zirconium hydroxide, zirconia hydrate, cerium oxide, cerium oxide hydrate, aluminum such as cerium hydroxide, inorganic oxides such as silicon, zirconium and cerium, and hydroxides.
  • these inorganic compounds may be hydrates.
  • aluminum hydroxide and silica are preferable, and when silica is used, silica hydrate represented by SiO 2 ⁇ nH 2 O is particularly preferable.
  • an epoxy compound or an amine compound is preferable, and an epoxy compound such as bisphenol A type epoxy or novolak type epoxy and an amine compound such as monoethanolamine, diethanolamine, triethanolamine and dichlorohexylamine are preferable. Can be exemplified as a more preferable compound.
  • the amount of the (D) tracking resistance improving agent added is 0 to 100 parts by mass, and may be 0 to 90 parts by mass or 0 to 80 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin.
  • a nitrogen-based compound (E) is supplementarily added to the flame-retardant polybutylene terephthalate resin composition of the present invention in order to further improve tracking resistance.
  • Examples of the (E) nitrogen-based compound include triazine compounds, benzoguanine compounds, terephthalic acid ester compounds of tris (hydroxyalkyl) isocyanurate, allantin compounds, glycoluryl compounds, and combinations thereof.
  • triazine compound examples include cyanurate, trimethylocyanurate, triethyl cyanurate, tri (n-propyl) cyanurate, methyl cyanurate, diethyl cyanurate, isocyanurate, trimethyl cyanurate, triethyl isocyanurate, and tri (n).
  • the amount of the nitrogen-based compound added (E) is 0 to 80 parts by mass, and may be 0 to 70 parts by mass or 0 to 60 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin.
  • a filler is used in the composition of the present invention as needed.
  • Such a filler is preferably blended in order to obtain excellent performance properties such as mechanical strength, heat resistance, and dimensional stability, and is particularly effective for the purpose of increasing rigidity.
  • This is a fibrous, powdery or plate-like filler depending on the purpose, and a compound different from (C) the tracking resistance improving agent is used.
  • Fibrous fillers include circular cross-section glass fibers, flat cross-section glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, zirconia fibers, potassium titanate fibers, and stainless steel, aluminum, titanium, copper, brass, etc. Examples include metal fibrous materials. In addition, organic fibrous substances having a high melting point such as fluororesin and acrylic resin can also be used.
  • powder granular filler examples include glass beads, glass powder, quartz powder, kaolin, clay, diatomaceous earth, wollastonite, silicon carbide, silicon nitride, and various metal powders.
  • Examples of the plate-shaped inorganic filler include glass flakes and various metal foils.
  • the type of filler is not particularly limited, and one or more fillers can be added.
  • the amount of the filler added is not particularly specified, but is preferably 200 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin. When the filler is added excessively, the moldability is poor and the toughness is lowered.
  • thermoplastic resin in order to impart various desired properties to the composition of the present invention, a known substance generally added to a thermoplastic resin or the like can be added and used in combination.
  • antioxidants UV absorbers, stabilizers such as light stabilizers, antistatic agents, lubricants, mold release agents, colorants such as dyes and pigments, plasticizers, fluidity improvers, toughness improvers, hydrolysis resistance. It is possible to blend any of a property improver, a flame retardant other than the halogenated benzyl acrylate flame retardant, a resin other than the tracking resistance improving resin, and the like.
  • the colorant is not carbon black but black or dark color. It is desirable to add organic dyes and pigments.
  • a phosphorus-based flame-retardant is added as a flame-retardant other than the halogenated benzyl acrylate-based flame-retardant, an organic phosphinic acid metal salt, an organic diphosphinic acid metal salt, and a condensed phosphate ester (resorcinol phosphates, hydroquinone phosphates, biphenol) Phosphazenes, etc.), phosphazene compounds (cyclic phenoxyphosphazene, chain phenoxyphosphazene, crosslinked phenoxyphosphazene, etc.) can be used.
  • halogen-based flame retardant Aluminum methylethylphosphinate, organic phosphinic acid metal salts such as zinc diethylphosphinate are preferred.
  • a halogen-based flame retardant is added as a flame retardant other than the halogenated benzyl acrylate-based flame retardant, a halogenated epoxy-based flame retardant, a halogenated phenoxy-based flame retardant, a halogenated polyphenylene ether-based flame retardant, or a halogenated styrene-based flame retardant
  • Halogen-based flame retardants such as flame retardants, halogenated phthalimide-based flame retardants, and halogenated polycarbonate-based flame retardants can be mentioned, but in order not to reduce the tracking resistance, free bromine contained in these halogen-based flame retardants can be mentioned.
  • Free chlorine and free sulfur are preferably 0.5% by mass or less, respectively.
  • the form of the flame-retardant polybutylene terephthalate resin composition of the present invention may be a powder or granular material mixture or a melt mixture (melt kneaded product) such as pellets.
  • the method for producing a polybutylene terephthalate resin composition according to an embodiment of the present invention includes (B) a step for producing a halogenated benzyl acrylate-based flame retardant. Since the process is as described above, the description thereof is omitted here.
  • the method for producing the polybutylene terephthalate resin composition is not particularly limited, and the polybutylene terephthalate resin composition can be produced using equipment and methods known in the art.
  • the required components can be mixed and kneaded using a single-screw or twin-screw extruder or other melt-kneading device to prepare pellets for molding. Multiple extruders or other melt kneaders may be used. Further, all the components may be input from the hopper at the same time, or some components may be input from the side feed port.
  • PBT resin Polybutylene terephthalate resin (B-1) manufactured by Polyplastics Co., Ltd., having a terminal carboxyl group concentration of 20 meq / kg and an intrinsic viscosity of 0.7 dL / g.
  • B-1) PBBPA1 Using ethylene glycol monomethyl ether as a solvent.
  • PBBPA2 Polypentabromobenzyl acrylate polymerized using chlorobenzene as a solvent (content of halogenated aromatic compound other than flame retardant 150 ppm)
  • C-1 Resin for improving tracking resistance 1: Acrylic core-shell type elastomer whose core layer is an acrylic rubber and whose shell layer is a vinyl polymer (Rohm and Haas Japan Co., Ltd., Pararoid EXL2314)
  • C-2 Resin for improving tracking resistance 2: Ethylene-glycidyl methacrylate copolymer (olefin elastomer, manufactured by Sumitomo Chemical Co., Ltd., BONDFAST 7M)
  • D Talc: Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd.
  • Nitrogen compound Melamine cyanurate (BASF, Melapur MC50) Glass fiber: ECS03T-127 manufactured by Nippon Electric Glass Co., Ltd. (Circular cross-section glass fiber with an average fiber diameter of 13 ⁇ m and an average fiber length of 3 mm) Antimony trioxide: manufactured by Nihon Seiko Co., Ltd., PATOX-M Anti-dripping agent: Polytetrafluoroethylene

Abstract

[Problem] To improve the tracking resistance of a polybutylene terephthalate resin composition in which a halogenated benzyl acrylate flame retardant is used as a flame retardant, and to suppress the corrosion of a metal member in contact with a molded article composed of said resin composition. [Solution] The problem is solved with a polybutylene terephthalate resin composition that uses a halogenated benzyl acrylate flame retardant as a flame retardant, wherein the amount of a halogenated aromatic compound such as chlorobenzene is suppressed in the flame retardant production process.

Description

難燃性ポリブチレンテレフタレート樹脂組成物Flame-retardant polybutylene terephthalate resin composition
　本発明は、難燃性ポリブチレンテレフタレート樹脂組成物、及びその製造方法に関する。 The present invention relates to a flame-retardant polybutylene terephthalate resin composition and a method for producing the same.
　ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、機械的特性、電気的特性、耐熱性など各種特性に優れるため、エンジニアリングプラスチックとして自動車部品や電気・電子機器部品など種々の用途に広く利用されている。これらのうち、電気・電子機器部品用途では、トラッキング等による発火を防ぐため、使用される材料には難燃性が要求されている。ポリブチレンテレフタレート樹脂は、それ自体では難燃性が不足するため、難燃剤を添加した難燃性樹脂組成物として使用されている。 Polybutylene terephthalate resin (PBT resin) is widely used as an engineering plastic in various applications such as automobile parts and electrical / electronic equipment parts because it has excellent mechanical properties, electrical properties, heat resistance, and other properties. Of these, in the applications of electrical and electronic equipment parts, flame retardancy is required for the materials used in order to prevent ignition due to tracking and the like. Since polybutylene terephthalate resin is insufficient in flame retardancy by itself, it is used as a flame retardant resin composition to which a flame retardant is added.
　このようなポリブチレンテレフタレート樹脂に添加される難燃剤の一種としてハロゲン化ベンジルアクリレート系難燃剤があり、その例としては特許文献１に紹介されているようなポリペンタブロモベンジルアクリレート（ＰＢＢＰＡ）がある。この難燃剤を製造する方法として特許文献１の段落［0004］には、モノマーであるペンタブロモベンジルアクリレートを、エチレングリコールモノメチルエーテルや、メチルエチルケトン、エチレングリコールジメチルエーテル中で重合する方法やクロロベンゼン中で重合する方法が例示されている。 Halogenated benzyl acrylate-based flame retardant is one of the flame retardants added to such polybutylene terephthalate resin, and an example thereof is polypentabromobenzyl acrylate (PBBPA) as introduced in Patent Document 1. .. As a method for producing this flame retardant, in paragraph [0004] of Patent Document 1, the monomer pentabromobenzyl acrylate is polymerized in ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether, or in chlorobenzene. The method is illustrated.
　これらのうち、ハロゲン化芳香族化合物であるクロロベンゼンを溶媒として重合した場合、最終的にＰＢＢＰＡ中に不純物として微量のクロロベンゼンが存在することになる。そして、これを添加して難燃化したポリブチレンテレフタレート樹脂組成物もクロロベンゼンを含有することとなる。 Of these, when chlorobenzene, which is a halogenated aromatic compound, is polymerized as a solvent, a trace amount of chlorobenzene will eventually be present as an impurity in PBBPA. Then, the polybutylene terephthalate resin composition to which this is added to make it flame-retardant also contains chlorobenzene.
　このクロロベンゼンは一般的には安定した化合物であるが、高温環境下において、特に金属酸化物やアルカリ金属系化合物などの金属と接触した場合、脱塩素化が起こり、塩化水素等の化合物が発生することがある。そのため、これを含む組成物をインサート成形や端子圧入など金属部材と接触する成形品に用いると、当該金属部材の腐蝕が生じるといった問題が起こる場合がある。ここで、前述した電気・電子部品用途においては、ポリブチレンテレフタレート樹脂組成物からなる成形品が電気絶縁部材として、導電部である金属部材と組み合わせて用いられるため、その金属部材を腐蝕させないことが要求される。また、成形品が金属部材と組み合わせて用いられる場合のみに限らず、成形品自体を成形する過程において、成形機のスクリュやシリンダ、あるいは金型といった金属部材の腐蝕の観点からも、これを抑制することが求められる。 This chlorobenzene is generally a stable compound, but in a high temperature environment, especially when it comes into contact with a metal such as a metal oxide or an alkali metal compound, dechlorination occurs and a compound such as hydrogen chloride is generated. Sometimes. Therefore, when a composition containing this is used for a molded product that comes into contact with a metal member such as insert molding or terminal press fitting, there may be a problem that the metal member is corroded. Here, in the above-mentioned electric / electronic component applications, a molded product made of a polybutylene terephthalate resin composition is used as an electrically insulating member in combination with a metal member which is a conductive portion, so that the metal member may not be corroded. Required. Further, not only when the molded product is used in combination with the metal member, but also from the viewpoint of corrosion of the metal member such as the screw, cylinder, or mold of the molding machine in the process of molding the molded product itself, this is suppressed. Is required to do.
　ところでポリブチレンテレフタレート樹脂は、それのみであれば耐トラッキング性に優れる樹脂である。しかし、ポリブチレンテレフタレート樹脂には、機械的強度等の各種特性を調整するための強化用充填剤や各種安定化剤、あるいは上述の難燃剤等の種々の添加剤が使用されるのが通常であり、その種類によっては耐トラッキング性が損なわれる場合がある。特にＰＢＢＰＡなどの臭素系難燃剤は、炭化が起こりやすいことから耐トラッキング性を低下させうる。そこで、難燃性と耐トラッキング性を両立するため、例えば特許文献２では、臭素系難燃剤ではなくリン系難燃剤を添加した熱可塑性ポリエステル樹脂組成物が開示されているが、リン系難燃剤はコストや成形品からの浸み出しといった点で不利となる場合がある。そこで、ポリブチレンテレフタレート樹脂の耐トラッキング性を確保しつつ難燃性を向上することが求められている。 By the way, polybutylene terephthalate resin is a resin with excellent tracking resistance by itself. However, in polybutylene terephthalate resin, various additives such as a reinforcing filler and various stabilizers for adjusting various properties such as mechanical strength, or the above-mentioned flame retardant are usually used. Yes, tracking resistance may be impaired depending on the type. In particular, brominated flame retardants such as PBBPA can reduce tracking resistance because carbonization is likely to occur. Therefore, in order to achieve both flame retardancy and tracking resistance, for example, Patent Document 2 discloses a thermoplastic polyester resin composition to which a phosphorus-based flame retardant is added instead of a bromine-based flame retardant. May be disadvantageous in terms of cost and seepage from the article. Therefore, it is required to improve the flame retardancy while ensuring the tracking resistance of the polybutylene terephthalate resin.
特表２０１５－５３２３５０号公報Special Table 2015-532350 国際公開２０１４／０２１１０１号パンフレットInternational Publication 2014/021101 Pamphlet
　本発明は、難燃剤としてハロゲン化ベンジルアクリレート系難燃剤を用いるポリブチレンテレフタレート樹脂組成物において、耐トラッキング性の低下を抑制するとともに、当該成形品と接触する金属部材の腐蝕を抑制することを課題とする。 An object of the present invention is to suppress a decrease in tracking resistance and corrosion of a metal member in contact with a molded product in a polybutylene terephthalate resin composition using a halogenated benzyl acrylate flame retardant as a flame retardant. And.
　本発明者は、上記を課題とする研究の過程で、難燃剤としてハロゲン化ベンジルアクリレート系難燃剤を用い、特定の耐トラッキング性向上剤を含むポリブチレンテレフタレート樹脂組成物において、当該ポリブチレンテレフタレート樹脂組成物に含有される、クロロベンゼンなどのハロゲン化芳香族化合物の量を抑える、特に当該難燃剤の製造工程に由来するハロゲン化芳香族化合物の量を抑えることで、上記の課題を解決できることを見出し、本発明を完成させるに至った。 The present inventor uses a halogenated benzyl acrylate-based flame retardant as a flame retardant in the process of research subject to the above, and in a polybutylene terephthalate resin composition containing a specific tracking resistance improving agent, the polybutylene terephthalate resin. We have found that the above problems can be solved by suppressing the amount of halogenated aromatic compounds such as chlorobenzene contained in the composition, particularly by suppressing the amount of halogenated aromatic compounds derived from the manufacturing process of the flame retardant. , The present invention has been completed.
すなわち、本発明は以下の（１）～（８）に関する。
（１）（Ａ）ポリブチレンテレフタレート樹脂１００質量部と、（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤３～５０質量部と、（Ｃ）オレフィン系エラストマ、アクリル系コアシェル型エラストマ、直鎖状ポリオレフィン樹脂、及びこれらの組み合わせから選択される１種以上の耐トラッキング性向上用樹脂５～１００質量部と、（Ｄ）タルク、マイカ、無機金属化合物、及びこれらの組み合わせから選ばれる１種以上の耐トラッキング性向上用充填剤０～１００質量部と、（Ｅ）トリアジン化合物、ベンゾグアニン化合物、トリス（ヒドロキシアルキル）イソシアヌレートのテレフタル酸エステル化合物、アラントイン化合物、グリコールウリル化合物、及びこれらの組み合わせから選択される１種以上の窒素系化合物０～８０質量部とを含有する難燃性ポリブチレンテレフタレート樹脂組成物であって、ヘッドスペースガスクロマトグラフ法（１５０℃、１時間加熱）により測定される、前記難燃剤以外のハロゲン化芳香族化合物の含有量が０．５ｐｐｍ未満であることを特徴とする、難燃性ポリブチレンテレフタレート樹脂組成物。
（２）（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤が、一般式（Ｉ）で表されるブロム化アクリル重合体を含有する、（１）に記載の難燃性ポリブチレンテレフタレート樹脂組成物。
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｘは、水素原子または臭素原子であり、少なくとも１つ以上のＸは臭素原子であり、ｍは１０～２０００の数である。）
（３）（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤が、ポリペンタブロモベンジルアクリレートを含有する、（１）または（２）に記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（４）前記難燃剤以外のハロゲン化芳香族化合物が、ハロゲン化ベンゼンを含有する、（１）から（３）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（５）前記難燃剤以外のハロゲン化芳香族化合物が、クロロベンゼンを含有する、（１）から（４）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物。
（６）（１）から（５）のいずれかに記載の難燃性ポリブチレンテレフタレート樹脂組成物の製造方法であって、（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程を有し、該工程で用いる溶媒中のハロゲン化芳香族化合物の含有量が１０００ｐｐｍ以下であることを特徴とする、製造方法。
（７）（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程において、溶媒としてハロゲン化芳香族化合物を用いない、（６）に記載の製造方法。
（８）（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程において、溶媒としてエチレングリコールモノメチルエーテル、メチルエチルケトン、エチレングリコールジメチルエーテルおよびジオキサンからなる群から選択される一以上の溶媒を用いる、（６）又は（７）に記載の製造方法。 That is, the present invention relates to the following (1) to (8).
(1) 100 parts by mass of (A) polybutylene terephthalate resin, (B) 3 to 50 parts by mass of halogenated benzyl acrylate-based flame retardant, (C) olefin-based elastoma, acrylic core-shell type elastoma, linear polyolefin resin , And one or more types of tracking resistance improving resin selected from 5 to 100 parts by mass, and (D) talc, mica, inorganic metal compound, and one or more types of tracking resistance selected from these combinations. It is selected from 0 to 100 parts by mass of a filler for improving properties, (E) a triazine compound, a benzoguanine compound, a terephthalate ester compound of tris (hydroxyalkyl) isocyanurate, an allantin compound, a glycoluril compound, and a combination thereof. A flame-retardant polybutylene terephthalate resin composition containing 0 to 80 parts by mass of one or more nitrogen-based compounds, which is measured by a headspace gas chromatograph method (heating at 150 ° C. for 1 hour). A flame-retardant polybutylene terephthalate resin composition, characterized in that the content of a halogenated aromatic compound other than the above is less than 0.5 ppm.
(2) The flame-retardant polybutylene terephthalate resin composition according to (1), wherein the halogenated benzyl acrylate-based flame retardant contains a brominated acrylic polymer represented by the general formula (I).
Figure JPOXMLDOC01-appb-C000002
 (In the formula, X is a hydrogen atom or a bromine atom, at least one X is a bromine atom, and m is a number of 10 to 2000.)
(3) The flame-retardant polybutylene terephthalate resin composition according to (1) or (2), wherein the halogenated benzyl acrylate-based flame retardant contains polypentabromobenzyl acrylate.
(4) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (3), wherein the halogenated aromatic compound other than the flame retardant contains benzene halide.
(5) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (4), wherein the halogenated aromatic compound other than the flame retardant contains chlorobenzene.
(6) The method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (5), which comprises (B) a step for producing a halogenated benzyl acrylate-based flame retardant. A production method, characterized in that the content of the halogenated aromatic compound in the solvent used in the step is 1000 ppm or less.
(7) The production method according to (6), wherein the halogenated aromatic compound is not used as a solvent in the production process of the halogenated benzyl acrylate flame retardant.
(8) In the process of producing the halogenated benzyl acrylate flame retardant, one or more solvents selected from the group consisting of ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether and dioxane are used as the solvent, (6) or The manufacturing method according to (7).
　本発明によれば、難燃剤としてハロゲン化ベンジルアクリレート系難燃剤を用いるポリブチレンテレフタレート樹脂組成物において、当該難燃剤の製造工程におけるクロロベンゼンなどのハロゲン化芳香族化合物の量を抑えることで、当該ポリブチレンテレフタレート樹脂組成物と接する金属部材の腐蝕を抑制することができる。 According to the present invention, in a polybutylene terephthalate resin composition using a halogenated benzyl acrylate-based flame retardant as a flame retardant, the poly by suppressing the amount of a halogenated aromatic compound such as chlorobenzene in the process of producing the flame retardant. It is possible to suppress the corrosion of the metal member in contact with the butylene terephthalate resin composition.
　以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。なお、本発明においてＡ～Ｂとは、Ａ以上Ｂ以下であることを意味している。 Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired. In the present invention, A to B means A or more and B or less.
［難燃性ポリブチレンテレフタレート樹脂組成物］
　以下、本実施形態の難燃性ポリブチレンテレフタレート樹脂組成物の各成分の詳細を例を挙げて説明する。 [Flame-retardant polybutylene terephthalate resin composition]
Hereinafter, details of each component of the flame-retardant polybutylene terephthalate resin composition of the present embodiment will be described with reference to examples.
（（Ａ）ポリブチレンテレフタレート樹脂）
　（Ａ）ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１－６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも炭素原子数４のアルキレングリコール（１，４－ブタンジオール）又はそのエステル形成性誘導体（アセチル化物等）を含むグリコール成分とを重縮合して得られるポリブチレンテレフタレート樹脂である。本実施形態において、（Ａ）ポリブチレンテレフタレート樹脂はホモポリブチレンテレフタレート樹脂に限らず、ブチレンテレフタレート単位を６０モル％以上含有する共重合体であってもよい。 ((A) Polybutylene terephthalate resin)
The polybutylene terephthalate resin (PBT resin) contains 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. It is a polybutylene terephthalate resin obtained by polycondensing with a glycol component containing glycol (1,4-butanediol) or an ester-forming derivative thereof (acetylated product, etc.). In the present embodiment, the polybutylene terephthalate resin (A) is not limited to the homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of butylene terephthalate units.
　（Ａ）ポリブチレンテレフタレート樹脂の末端カルボキシル基量は、本発明の目的を阻害しない限り特に限定されないが、３０ｍｅｑ／ｋｇ以下が好ましく、２５ｍｅｑ／ｋｇ以下がより好ましい。 The amount of terminal carboxyl groups of the polybutylene terephthalate resin (A) is not particularly limited as long as the object of the present invention is not impaired, but is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less.
　（Ａ）ポリブチレンテレフタレート樹脂の固有粘度は本発明の目的を阻害しない範囲で特に制限されないが、０．６０ｄＬ／ｇ以上１．２ｄＬ／ｇ以下であるのが好ましく、０．６５ｄＬ／ｇ以上０．９ｄＬ／ｇ以下であるのがより好ましい。このような範囲の固有粘度のポリブチレンテレフタレート樹脂を用いる場合には、得られるポリブチレンテレフタレート樹脂組成物が特に成形性に優れたものとなる。また、異なる固有粘度を有するポリブチレンテレフタレート樹脂をブレンドして、固有粘度を調整することもできる。例えば、固有粘度１．０ｄＬ／ｇのポリブチレンテレフタレート樹脂と固有粘度０．７ｄＬ／ｇのポリブチレンテレフタレート樹脂とをブレンドすることにより、固有粘度０．９ｄＬ／ｇのポリブチレンテレフタレート樹脂を調製することができる。ポリブチレンテレフタレート樹脂の固有粘度は、例えば、ｏ－クロロフェノール中で温度３５℃の条件で測定することができる。 The intrinsic viscosity of the polybutylene terephthalate resin (A) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 0.60 dL / g or more and 1.2 dL / g or less, and 0.65 dL / g or more and 0. More preferably, it is 9.9 dL / g or less. When a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, the obtained polybutylene terephthalate resin composition is particularly excellent in moldability. It is also possible to adjust the intrinsic viscosity by blending polybutylene terephthalate resins having different intrinsic viscosities. For example, a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g can be 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 be done. The intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol under the condition of a temperature of 35 ° C.
　（Ａ）ポリブチレンテレフタレート樹脂の調製において、コモノマー成分としてテレフタル酸以外の芳香族ジカルボン酸又はそのエステル形成性誘導体を用いる場合、例えば、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジカルボキシジフェニルエーテル等のＣ８－１４の芳香族ジカルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸等のＣ４－１６のアルカンジカルボン酸；シクロヘキサンジカルボン酸等のＣ５－１０のシクロアルカンジカルボン酸；これらのジカルボン酸成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体や酸ハロゲン化物等）を用いることができる。これらのジカルボン酸成分は、単独で又は２種以上を組み合わせて使用できる。 When an aromatic dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof is used as a comonomer component in the preparation of the polybutylene terephthalate resin (A), for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4, C 8-14 aromatic dicarboxylic acid such as 4'-dicarboxydiphenyl ether ; C 4-16 alcandicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid; C 5-10 such as cyclohexanedicarboxylic acid Cycloalkandicarboxylic acids; ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.) can be used. These dicarboxylic acid components can be used alone or in combination of two or more.
　これらのジカルボン酸成分の中では、イソフタル酸等のＣ８－１２の芳香族ジカルボン酸、及び、アジピン酸、アゼライン酸、セバシン酸等のＣ６－１２のアルカンジカルボン酸がより好ましい。 Among these dicarboxylic acid components, C 8-12 aromatic dicarboxylic acids such as isophthalic acid and C 6-12 alkane dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid are more preferable.
　（Ａ）ポリブチレンテレフタレート樹脂の調製において、コモノマー成分として１，４－ブタンジオール以外のグリコール成分を用いる場合、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、１，３－オクタンジオール等のＣ２－１０のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等のポリオキシアルキレングリコール；シクロヘキサンジメタノール、水素化ビスフェノールＡ等の脂環式ジオール；ビスフェノールＡ、４，４’－ジヒドロキシビフェニル等の芳香族ジオール；ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等の、ビスフェノールＡのＣ２－４のアルキレンオキサイド付加体；又はこれらのグリコールのエステル形成性誘導体（アセチル化物等）を用いることができる。これらのグリコール成分は、単独で又は２種以上を組み合わせて使用できる。 When a glycol component other than 1,4-butanediol is used as the comonomer component in the preparation of the polybutylene terephthalate resin (A), for example, ethylene glycol, propylene glycol, trimethylene glycol, 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, dipropylene glycol; alicyclic type such as cyclohexanedimethanol, hydride bisphenol A, etc. Diols; aromatic diols such as bisphenol A, 4,4'-dihydroxybiphenyl; alkylene oxides of C 2-4 of bisphenol A such as 2 mol adducts of ethylene oxide of bisphenol A and 3 mol adducts of propylene oxide of bisphenol A. Additives; or ester-forming derivatives of these glycols (acetylates, etc.) can be used. These glycol components can be used alone or in combination of two or more.
　これらのグリコール成分の中では、エチレングリコール、トリメチレングリコール等のＣ２－６のアルキレングリコール、ジエチレングリコール等のポリオキシアルキレングリコール、又は、シクロヘキサンジメタノール等の脂環式ジオール等がより好ましい。 Among these glycol components, C 2-6 alkylene glycols such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycols such as diethylene glycol, and alicyclic diols such as cyclohexanedimethanol are more preferable.
　ジカルボン酸成分及びグリコール成分の他に使用できるコモノマー成分としては、例えば、４－ヒドロキシ安息香酸、３－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４－カルボキシ－４’－ヒドロキシビフェニル等の芳香族ヒドロキシカルボン酸；グリコール酸、ヒドロキシカプロン酸等の脂肪族ヒドロキシカルボン酸；プロピオラクトン、ブチロラクトン、バレロラクトン、カプロラクトン（ε－カプロラクトン等）等のＣ３－１２ラクトン；これらのコモノマー成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体、酸ハロゲン化物、アセチル化物等）が挙げられる。 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. Aromatic hydroxycarboxylic acids; aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C 3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (ε-caprolactone, etc.); esters of these comonomer components Examples thereof include formable derivatives (C 1-6 alkyl ester derivatives, acid halides, acetylates, etc.).
　（Ａ）ポリブチレンテレフタレート樹脂の含有量は、樹脂組成物の全質量の１０～９０質量％であることが好ましく、２０～８０質量％であることがより好ましく、３０～７０質量％であることがさらに好ましい。 The content of the polybutylene terephthalate resin (A) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 70% by mass based on the total mass of the resin composition. Is even more preferable.
（（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤）
本発明に用いられる（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤としては、下記一般式（Ｉ）で示されるブロム化アクリル重合体が挙げられる。
Figure JPOXMLDOC01-appb-C000003
  式中のＸは、水素原子または臭素原子であり、少なくとも１つ以上が臭素である。Ｘの数は、一構成単位中１～５であるが、難燃化の効果から３～５であることが好ましい。平均重合度ｍは１０～２０００であり、好ましくは１５～１０００の範囲である。平均重合度が１０より低いものは、熱安定性が悪化し、２０００を超えると添加したポリブチレンテレフタレート樹脂の成形加工性を悪化させる。また、上記ブロム化アクリル重合体は１種又は２種以上混合使用してもよい。 ((B) Halogenated benzyl acrylate flame retardant)
Examples of the (B) halogenated benzyl acrylate-based flame retardant used in the present invention include a brominated acrylic polymer represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000003
 X in the formula is a hydrogen atom or a bromine atom, and at least one or more is bromine. The number of X is 1 to 5 in one structural unit, but it is preferably 3 to 5 from the viewpoint of flame retardancy. The average degree of polymerization m is 10 to 2000, preferably in the range of 15 to 1000. If the average degree of polymerization is lower than 10, the thermal stability is deteriorated, and if it exceeds 2000, the molding processability of the added polybutylene terephthalate resin is deteriorated. Further, the brominated acrylic polymer may be used alone or in combination of two or more.
本発明に用いられる（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤は、当該難燃剤自体である上記のブロム化アクリル重合体以外に、不純物として、重合時の溶媒やブロム化アクリル重合体の分解物に由来するハロゲン化芳香族化合物を含有しうるが、そのような不純物である、難燃剤以外のハロゲン化芳香族化合物の含有量は、好ましくは１００ｐｐｍ以下、より好ましくは５０ｐｐｍ以下、さらに好ましくは３０ｐｐｍ以下、特に好ましくは１０ｐｐｍ以下である。難燃剤以外のハロゲン化芳香族化合物の含有量は、例えば、（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤を粉砕した試料を、ヘッドスペース中で加熱処理した際の発生ガスを、ガスクロマトグラフにより測定し、ハロゲン化芳香族化合物に由来するガス発生量から求めることができる。 The (B) halogenated benzyl acrylate-based flame retardant used in the present invention can be used as an impurity in a solvent during polymerization or a decomposition product of the bromized acrylic polymer, in addition to the above-mentioned brominated acrylic polymer which is the flame retardant itself. Although it may contain a derived halogenated aromatic compound, the content of such an impurity, a halogenated aromatic compound other than the flame retardant, is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 30 ppm or less. , Especially preferably 10 ppm or less. The content of the halogenated aromatic compound other than the flame retardant was measured, for example, by measuring the gas generated when a sample obtained by crushing the (B) halogenated benzyl acrylate flame retardant was heat-treated in the headspace by a gas chromatograph. , Can be determined from the amount of gas generated from the halogenated aromatic compound.
  一般式（Ｉ）で表されるブロム化アクリル重合体は臭素を含有するベンジルアクリレートを単独で重合することによって得られるが、類似構造のベンジルメタクリレート等を共重合させてもよい。臭素含有ベンジルアクリレートとしては、ペンタブロモベンジルアクリレート、テトラブロモベンジルアクリレート、トリブロモベンジルアクリレート、又はその混合物が挙げられる。中でも、ペンタブロモベンジルアクリレートが好ましい。また、共重合可能な成分であるベンジルメタクリレートとしては、上記したアクリレートに対応するメタクリレートが挙げられる。さらにはビニル系モノマーとの共重合も可能であり、アクリル酸、メチルアクリレート、エチルアクリレート、ブチルアクリレート、ベンジルアクリレートのようなアクリル酸エステル類、メタクリル酸、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、ベンジルメタクリレートのようなメタクリル酸エステル類、スチレン、アクリロニトリル、フマル酸、マレイン酸のような不飽和カルボン酸又はその無水物、酢酸ビニル、塩化ビニルなどが挙げられる。また、架橋性のビニル系モノマー、キシリレンジアクリレート、キシリレンジメタクリレート、テトラブロムキシリレンジアクリレート、テトラブロムキシリレンジメタクリレート、ブタジエン、イソプレン、ジビニルベンゼンも使用できる。これらはベンジルアクリレートやベンジルメタクリレートに対し等モル量以下、好ましくは０．５倍モル量以下が使用される。 The brominated acrylic polymer represented by the general formula (I) is obtained by polymerizing a benzyl acrylate containing bromine alone, but a benzyl methacrylate having a similar structure or the like may be copolymerized. Examples of the bromine-containing benzyl acrylate include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, or a mixture thereof. Of these, pentabromobenzyl acrylate is preferable. Examples of the benzyl methacrylate, which is a copolymerizable component, include methacrylates corresponding to the above-mentioned acrylates. Furthermore, copolymerization with vinyl-based monomers is also possible, and acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and benzyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and benzyl methacrylate. Examples thereof include methacrylic acid esters such as styrene, acrylonitrile, fumaric acid, unsaturated carboxylic acids such as maleic acid or an anhydride thereof, vinyl acetate, vinyl chloride and the like. Further, crosslinkable vinyl-based monomers, xylylene diacrylate, xylylene dimethacrylate, tetrabromxylylene diacrylate, tetrabromxylylene dimethacrylate, butadiene, isoprene, and divinylbenzene can also be used. These are used in an equimolar amount or less, preferably 0.5 times a molar amount or less, based on benzyl acrylate or benzyl methacrylate.
　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造方法として、上記のブロム化アクリル重合体の製造法の一例を示すと、ブロム化アクリルのモノマーを溶液重合あるいは、塊状重合にて所定の重合度に反応させる方法が挙げられる。溶液重合の場合、溶媒中のハロゲン化芳香族化合物の含有量が１０００ｐｐｍ以下であることが好ましく、５００ｐｐｍ以下であることがより好ましく、３００ｐｐｍ以下であることがさらに好ましく、１００ｐｐｍ以下であることが特に好ましい。溶媒としてハロゲン化ベンゼンや、クロロベンゼンなどのハロゲン化芳香族化合物を用いないことがより好ましい。また、溶液重合の際の溶媒としては、エチレングリコールモノメチルエーテルや、メチルエチルケトン、エチレングリコールジメチルエーテルおよびジオキサンなどの非プロトン性溶媒が好ましい。 (B) As an example of the above-mentioned method for producing a brominated acrylic polymer as a method for producing a halogenated benzyl acrylate-based flame retardant, a brominated acrylic monomer is subjected to solution polymerization or bulk polymerization to a predetermined degree of polymerization. A method of reacting can be mentioned. In the case of solution polymerization, the content of the halogenated aromatic compound in the solvent is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 300 ppm or less, and particularly preferably 100 ppm or less. preferable. It is more preferable not to use halogenated benzene or a halogenated aromatic compound such as chlorobenzene as the solvent. Further, as the solvent for solution polymerization, aprotic solvents such as ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether and dioxane are preferable.
　上記のブロム化アクリル重合体等の（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤は、残留ポリアクリル酸ナトリウム等の反応副生成物を除去するために、水及び／又はアルカリ（土類）金属イオンを含有する水溶液にて洗浄されることが好ましい。なお、本明細書において、「アルカリ（土類）金属イオンを含有する」とは、アルカリ金属イオン及び／又はアルカリ土類金属イオンを含有することを意味している。アルカリ（土類）金属イオンを含有する水溶液はアルカリ（土類）金属塩を水に投入することで容易に得られるが、塩化物イオン、リン酸イオン等を含まないアルカリ（土類）金属である水酸化物（例えば水酸化カルシウム）が最適である。アルカリ（土類）金属塩として、例えば水酸化カルシウムを用いる場合、水酸化カルシウムは一般に２０℃において１００ｇの水中に０．１２６ｇ程度可溶であり、水溶液濃度は溶解度までであれば特に規定はない。また、水及び／又はアルカリ（土類）金属イオンを含有する水溶液による洗浄の手法も特に限定されず、ブロム化アクリル重合体を適当な時間、水及び／又はアルカリ（土類）金属イオンを含有する水溶液に浸漬させる等の手法で良い。上記、水及び／又はアルカリ（土類）金属イオンを含有する水溶液による洗浄処理を終えたブロム化アクリル重合体は、一般的に温水抽出分中の乾固分が１００ｐｐｍ以下のものとなり、このようなブロム化アクリル重合体を用いる場合、その成形品表面に異物を発生させることが殆どなくなる。 The (B) halogenated benzyl acrylate flame retardant such as the above brominated acrylic polymer uses water and / or alkali (earth) metal ions in order to remove reaction by-products such as residual sodium polyacrylate. It is preferable to wash with the contained aqueous solution. In addition, in this specification, "containing an alkali (earth) metal ion" means containing an alkali metal ion and / or an alkaline earth metal ion. An aqueous solution containing an alkali (earth) metal ion can be easily obtained by adding an alkali (earth) metal salt to water, but an alkali (earth) metal containing no chloride ion, phosphate ion, etc. Certain hydroxides (eg calcium hydroxide) are optimal. When calcium hydroxide is used as the alkali (earth) metal salt, for example, calcium hydroxide is generally soluble in about 0.126 g in 100 g of water at 20 ° C., and the concentration of the aqueous solution is not particularly specified as long as it is up to solubility. .. Further, the method of cleaning with an aqueous solution containing water and / or an alkali (earth) metal ion is not particularly limited, and the brominated acrylic polymer contains water and / or an alkali (earth) metal ion for an appropriate time. It may be a method such as immersing in an aqueous solution. The brominated acrylic polymer that has been washed with the aqueous solution containing water and / or alkaline (earth) metal ions generally has a dry solid content of 100 ppm or less in the hot water extract. When a simple brominated acrylic polymer is used, foreign matter is hardly generated on the surface of the molded product.
　本発明の難燃性ポリブチレンテレフタレート樹脂組成物は、前述の不純物である、難燃剤以外のハロゲン化芳香族化合物の含有量が、０．５ｐｐｍ未満であり、好ましくは０．３ｐｐｍ以下、より好ましくは０．１ｐｐｍ以下である。難燃性ポリブチレンテレフタレート樹脂組成物中の、難燃剤以外のハロゲン化芳香族化合物の含有量が上記範囲であることにより、当該ポリブチレンテレフタレート樹脂組成物を用いたインサート成形品において、金属端子の腐蝕を抑制することができる。このような難燃剤以外のハロゲン化芳香族化合物の含有量は、例えば、ポリブチレンテレフタレート樹脂組成物を粉砕した試料を、ヘッドスペース中で加熱処理した際の発生ガスを、ガスクロマトグラフにより測定し、ハロゲン化芳香族化合物に由来するガス発生量から求めることができる。 In the flame-retardant polybutylene terephthalate resin composition of the present invention, the content of the halogenated aromatic compound other than the flame retardant, which is the above-mentioned impurity, is less than 0.5 ppm, preferably 0.3 ppm or less, more preferably. Is 0.1 ppm or less. When the content of the halogenated aromatic compound other than the flame retardant in the flame-retardant polybutylene terephthalate resin composition is within the above range, the insert molded product using the polybutylene terephthalate resin composition has metal terminals. Corrosion can be suppressed. The content of the halogenated aromatic compound other than the flame retardant is determined by, for example, measuring the gas generated when the sample obtained by crushing the polybutylene terephthalate resin composition is heat-treated in the headspace by a gas chromatograph. It can be obtained from the amount of gas generated from the halogenated aromatic compound.
　上記樹脂の難燃化において、アンチモン系の難燃助剤をあわせて使用することが好ましい。難燃助剤の代表的なものとしては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、ピロアンチモン酸ナトリウム等が挙げられる。さらに、燃焼した樹脂が滴下することによる延焼を防ぐ目的で、ポリテトラフルオロエチレン等の滴下防止剤をあわせて使用することも好ましい。 In making the above resin flame-retardant, it is preferable to use an antimony-based flame-retardant aid together. Typical flame-retardant aids include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate and the like. Further, for the purpose of preventing the spread of fire due to the dripping of the burned resin, it is also preferable to use a dripping inhibitor such as polytetrafluoroethylene together.
　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤及びアンチモン系難燃助剤の樹脂に対する添加の範囲は、ポリブチレンテレフタレート樹脂１００質量部に対して前記重合体３～５０質量部であり、５～４０質量部であることが好ましく、１０～３０質量部であることがより好ましい。アンチモン系難燃助剤１～４０質量部の範囲が好ましい。ブロム化アクリル重合体及びアンチモン系難燃助剤の添加量が過少であると十分な難燃性を付与することができず、過大であると成形品としての物性を悪化させることがある。 (B) The range of addition of the halogenated benzyl acrylate flame retardant and the antimon flame retardant to the resin is 3 to 50 parts by mass of the polymer with respect to 100 parts by mass of the polybutylene terephthalate resin, and 5 to 40 parts by mass. The amount is preferably 10 to 30 parts by mass, more preferably 10 to 30 parts by mass. The range of 1 to 40 parts by mass of the antimony flame retardant aid is preferable. If the amount of the brominated acrylic polymer and the antimony-based flame retardant aid added is too small, sufficient flame retardancy cannot be imparted, and if it is too large, the physical properties of the molded product may be deteriorated.
（（Ｃ）耐トラッキング性向上用樹脂）　本発明の難燃性ポリブチレンテレフタレート樹脂組成物には、耐トラッキング性を向上させるために、（Ｃ）耐トラッキング性向上用樹脂が補助的に添加される。 ((C) Resin for improving tracking resistance) In order to improve tracking resistance, (C) resin for improving tracking resistance is supplementarily added to the flame-retardant polybutylene terephthalate resin composition of the present invention. To.
　（Ｃ）耐トラッキング性向上用樹脂としては、耐トラッキング性が高いのみならず、（Ａ）ポリブチレンテレフタレート樹脂との加工温度が近く、相溶性の良い樹脂を用いることができる。このような（Ｃ）耐トラッキング性向上用樹脂としては、オレフィン系エラストマ、アクリル系コアシェル型エラストマ、直鎖状ポリオレフィン樹脂、及びこれらの組み合わせを挙げることができる。 As the resin for improving the tracking resistance, a resin having not only high tracking resistance but also (A) a processing temperature close to that of the polybutylene terephthalate resin and good compatibility can be used. Examples of the resin for improving the tracking resistance (C) include an olefin-based elastomer, an acrylic-based core-shell type elastomer, a linear polyolefin resin, and a combination thereof.
　オレフィン系エラストマとしては、例えば、エチレン－プロピレン共重合体（ＥＰ共重合体）、エチレン－ブテン共重合体、エチレン－オクテン共重合体、エチレン－プロピレン－ジエン共重合体（ＥＰＤ共重合体）、エチレン－プロピレン－ブテン共重合体、エチレン－酢酸ビニル共重合体、ＥＰ共重合体およびＥＰＤ共重合体から選択された少なくとも一種の単位を含む共重合体、オレフィンと（メタ）アクリル系単量体との共重合体（エチレン－エチルアクリレート共重合体、エチレン－グリシジルメタクリレート共重合体等）などが含まれる。好ましいオレフィン系エラストマには、ＥＰ共重合体、ＥＰＤ共重合体、オレフィンと（メタ）アクリル系単量体との共重合体が含まれ、特にエチレンエチルアクリレートが好ましい。これらのオレフィン系エラストマは単独でまたは二種以上組み合わせて使用することができる。 Examples of the olefin-based elastoma include an ethylene-propylene copolymer (EP copolymer), an ethylene-butene copolymer, an ethylene-octene copolymer, an ethylene-propylene-diene copolymer (EPD copolymer), and the like. Copolymers containing at least one unit selected from ethylene-propylene-butene copolymers, ethylene-vinyl acetate copolymers, EP copolymers and EPD copolymers, olefins and (meth) acrylic monomers Copolymers with (ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, etc.) and the like are included. Preferred olefin-based elastomas include EP copolymers, EPD copolymers, and copolymers of olefins and (meth) acrylic monomers, with ethylene ethyl acrylate being particularly preferred. These olefin-based elastomers can be used alone or in combination of two or more.
　アクリル系コアシェル型エラストマは、コア層がゴム成分（軟質成分）、シェル層が硬質成分で構成されるポリマーであり、コア層のゴム成分にアクリル系ゴムを用いるものである。コア層に用いるアクリル系ゴムは、ガラス転移温度（Ｔｇ）が０℃未満（例えば－１０℃以下）であるのが好ましく、－２０℃以下（例えば－１８０℃以上－２５℃以下）であるのがより好ましく、－３０℃以下（例えば－１５０℃以上－４０℃以下）であるのが特に好ましい。 Acrylic core-shell type elastomer is a polymer in which the core layer is composed of a rubber component (soft component) and the shell layer is composed of a hard component, and acrylic rubber is used as the rubber component of the core layer. The acrylic rubber used for the core layer preferably has a glass transition temperature (Tg) of less than 0 ° C. (for example, −10 ° C. or lower), and preferably −20 ° C. or lower (for example, −180 ° C. or higher and −25 ° C. or lower). Is more preferable, and it is particularly preferable that the temperature is −30 ° C. or lower (for example, −150 ° C. or higher and −40 ° C. or lower).
　ゴム成分として用いるアクリル系ゴムは、アルキルアクリレート等のアクリル系モノマーを主成分として重合して得られる重合体が好ましい。アクリル系ゴムのモノマーとして用いるアルキルアクリレートは、ブチルアクリレート等のアクリル酸のＣ１～Ｃ１２のアルキルエステルが好ましく、アクリル酸のＣ２～Ｃ６のアルキルエステルがより好ましい。 The acrylic rubber used as the rubber component is preferably a polymer obtained by polymerizing an acrylic monomer such as alkyl acrylate as a main component. As the alkyl acrylate used as the monomer of the acrylic rubber, the alkyl ester of acrylic acid C 1 to C 12 such as butyl acrylate is preferable, and the alkyl ester of acrylic acid C 2 to C 6 is more preferable.
　アクリル系ゴムは、アクリル系モノマーの単独重合体でもよく、共重合体でもよい。アクリル系ゴムがアクリル系モノマーの共重合体である場合、アクリル系モノマー同士の共重合体でも、アクリル系モノマーと他の不飽和結合含有モノマーとの共重合体であってもよい。アクリル系ゴムが共重合体である場合、アクリル系ゴムは架橋性モノマーを共重合したものであってもよい。 The acrylic rubber may be a homopolymer of an acrylic monomer or a copolymer. When the acrylic rubber is a copolymer of an acrylic monomer, it may be a copolymer of acrylic monomers or a copolymer of an acrylic monomer and another unsaturated bond-containing monomer. When the acrylic rubber is a copolymer, the acrylic rubber may be a copolymer of a crosslinkable monomer.
　シェル層には、ビニル系重合体が好ましく用いられる。ビニル系重合体は、例えば、芳香族ビニル単量体、シアン化ビニル単量体、メタクリル酸エステル系単量体、及びアクリル酸エステル単量体の中から選ばれた少なくとも一種の単量体を重合あるいは共重合させて得られる。かかるアクリル系コアシェル型エラストマのコア層とシェル層は、グラフト共重合によって結合されていてもよい。このグラフト共重合化は、必要な場合には、コア層の重合時にシェル層と反応するグラフト交差剤を添加し、コア層に反応基を与えた後、シェル層を形成させることによって得られる。グラフト交差剤として、シリコーン系ゴムを使用する場合は、ビニル結合を有したオルガノシロキサンあるいはチオールを有したオルガノシロキサンが用いられ、好ましくはアクリロキシシロキサン、メタクリロキシシロキサン、ビニルシロキサンが使用される。 A vinyl polymer is preferably used for the shell layer. The vinyl-based polymer may be, for example, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, a methacrylic acid ester-based monomer, and an acrylic acid ester monomer. Obtained by polymerization or copolymerization. The core layer and the shell layer of such an acrylic core-shell type elastomer may be bonded by graft copolymerization. This graft copolymerization is obtained by adding a graft crossover that reacts with the shell layer at the time of polymerization of the core layer, giving a reactive group to the core layer, and then forming the shell layer, if necessary. When a silicone-based rubber is used as the graft crossing agent, an organosiloxane having a vinyl bond or an organosiloxane having a thiol is used, and acryloxysiloxane, methacryoxysiloxane, and vinylsiloxane are preferably used.
　直鎖状ポリオレフィン樹脂としては、ポリエチレンやポリプロピレン等、実質的に側鎖を有しないポリオレフィン樹脂であって、ＡＳＴＭ　Ｄ２８５７法で測定した粘度平均分子量が１万～１００万であるものが好ましい。 The linear polyolefin resin is preferably a polyolefin resin having substantially no side chain, such as polyethylene or polypropylene, and having a viscosity average molecular weight of 10,000 to 1,000,000 as measured by the ASTM D2857 method.
　（Ｃ）耐トラッキング性向上用樹脂の添加量は、ポリブチレンテレフタレート樹脂１００質量部に対し、５～１００質量部であり、１０～９０質量部または２０～８０質量部であっても良い。ただし、難燃性の低い樹脂では、多量に添加することで組成物としての燃焼性を悪化させるおそれがあるため、耐トラッキング性向上用樹脂の含有量は、本発明の難燃性ポリブチレンテレフタレート樹脂組成物全体に対し、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましい。 (C) The amount of the resin for improving tracking resistance added is 5 to 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin, and may be 10 to 90 parts by mass or 20 to 80 parts by mass. However, since a resin having low flame retardancy may deteriorate the flammability of the composition by adding a large amount, the content of the resin for improving tracking resistance is the flame-retardant polybutylene terephthalate of the present invention. It is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less with respect to the entire resin composition.
（（Ｄ）耐トラッキング性向上剤）　本発明の難燃性ポリブチレンテレフタレート樹脂組成物には、耐トラッキング性をさらに向上させるために、（Ｄ）耐トラッキング性向上剤が補助的に添加される。 ((D) Tracking resistance improver) To the flame-retardant polybutylene terephthalate resin composition of the present invention, (D) tracking resistance improving agent is supplementarily added in order to further improve the tracking resistance. ..
　（Ｄ）耐トラッキング性向上剤の具体例としては、タルク、マイカ、無機金属化合物が挙げられ、これらのいずれか、またはこれらのいずれかを組み合わせたものを用いることができる。 Specific examples of the (D) tracking resistance improving agent include talc, mica, and an inorganic metal compound, and any one of these or a combination thereof can be used.
　タルクとしては、公知のものを使用することができ、好ましくは体積平均粒子径が１～１０μｍのタルク、または嵩比重が０．４～１．５の圧縮微粉タルクを用いることができる。 As the talc, known talc can be used, and preferably talc having a volume average particle diameter of 1 to 10 μm or compressed fine powder talc having a bulk specific density of 0.4 to 1.5 can be used.
　マイカとしては、公知のものを使用することができ、好ましくは体積平均粒子径が１０～６０μｍのマイカを用いることができる。 As the mica, known ones can be used, and preferably mica having a volume average particle diameter of 10 to 60 μm can be used.
　無機金属化合物としては、無機酸（リン酸及びケイ酸以外の無機酸、例えば、炭酸、ホウ酸、スズ酸、タングステン酸、硫酸など）の金属塩、金属酸化物（酸化マグネシウム、酸化鉄、酸化チタン、酸化亜鉛、アルミナなど）、金属水酸化物（水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、アルミナ水和物（ベーマイト）など）、金属硫化物（硫化亜鉛、硫化モリブデン、硫化タングステンなど）等を挙げることができ、好ましいものとして、硫酸バリウム、硫化亜鉛、ホウ酸亜鉛、ホウ酸カルシウム、スズ酸亜鉛が挙げられる。 Examples of the inorganic metal compound include metal salts of inorganic acids (inorganic acids other than phosphoric acid and silicic acid, for example, carbonic acid, boric acid, tin acid, tungsten acid, sulfuric acid, etc.) and metal oxides (magnesium oxide, iron oxide, oxidation). Titanium, zinc oxide, alumina, etc.), metal hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (bemite), etc.), metal sulfides (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.) And the like, and preferred examples thereof include barium sulfate, zinc sulfide, zinc borate, calcium borate, and zinc stannate.
　これらの（Ｄ）耐トラッキング性向上剤は、無機化合物および／または有機化合物で表面処理（表面被覆）されていてもよく、表面処理に用いられる無機化合物としては、例えば、水酸化アルミニウム、アルミナ、シリカ、ジルコニア、水酸化ジルコニウム、ジルコニア水和物、酸化セリウム、酸化セリウム水和物、水酸化セリウム等のアルミニウム、ケイ素、ジルコニウム、セリウム等の無機酸化物、水酸化物が好ましく挙げられる。また、これらの無機化合物は水和物であってもよい。これらの中でも、水酸化アルミニウム、シリカが好ましく、シリカを用いる場合は、ＳｉＯ２・ｎＨ２Ｏで表されるシリカ水和物であることが特に好ましい。また、表面処理に用いられる有機化合物としては、エポキシ化合物やアミン化合物が好ましく、ビスフェノールＡ型エポキシ、ノボラック型エポキシ等のエポキシ化合物およびモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジクロルヘキシルアミン等のアミン化合物がより好ましい化合物として例示することができる。 These (D) tracking resistance improvers may be surface-treated (surface-coated) with an inorganic compound and / or an organic compound, and examples of the inorganic compound used for the surface treatment include aluminum hydroxide and alumina. Preferred examples thereof include silica, zirconia, zirconium hydroxide, zirconia hydrate, cerium oxide, cerium oxide hydrate, aluminum such as cerium hydroxide, inorganic oxides such as silicon, zirconium and cerium, and hydroxides. Moreover, these inorganic compounds may be hydrates. Among these, aluminum hydroxide and silica are preferable, and when silica is used, silica hydrate represented by SiO 2 · nH 2 O is particularly preferable. Further, as the organic compound used for the surface treatment, an epoxy compound or an amine compound is preferable, and an epoxy compound such as bisphenol A type epoxy or novolak type epoxy and an amine compound such as monoethanolamine, diethanolamine, triethanolamine and dichlorohexylamine are preferable. Can be exemplified as a more preferable compound.
　（Ｄ）耐トラッキング性向上剤の添加量は、ポリブチレンテレフタレート樹脂１００質量部に対し、０～１００質量部であり、０～９０質量部または０～８０質量部であっても良い。 The amount of the (D) tracking resistance improving agent added is 0 to 100 parts by mass, and may be 0 to 90 parts by mass or 0 to 80 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin.
（（Ｅ）窒素系化合物）
　本発明の難燃性ポリブチレンテレフタレート樹脂組成物には、耐トラッキング性をさらに向上させるために、（Ｅ）窒素系化合物が補助的に添加される。 ((E) Nitrogen compound)
A nitrogen-based compound (E) is supplementarily added to the flame-retardant polybutylene terephthalate resin composition of the present invention in order to further improve tracking resistance.
　（Ｅ）窒素系化合物としては、トリアジン化合物、ベンゾグアニン化合物、トリス（ヒドロキシアルキル）イソシアヌレートのテレフタル酸エステル化合物、アラントイン化合物、グリコールウリル化合物、及びこれらの組み合わせが挙げられる。 Examples of the (E) nitrogen-based compound include triazine compounds, benzoguanine compounds, terephthalic acid ester compounds of tris (hydroxyalkyl) isocyanurate, allantin compounds, glycoluryl compounds, and combinations thereof.
　トリアジン化合物の具体例としては、シアヌル酸、トリメチルシアヌレート、トリエチルシアヌレート、トリ（ｎ－プロピル）シアヌレート、メチルシアヌレート、ジエチルシアヌレート、イソシアヌル酸、トリメチルイソシアヌネート、トリエチルイソシアヌレート、トリ（ｎ－プロピル）イソシアヌレート、ジエチルイソシアヌネート、メチルイソシアヌレート、メラミン、メラミンシアヌレート、メラミンホスフェート化合物、ジメラミンホスフェート化合物、メラミンポリホスフェート化合物、ビスメラミンジンコホスフェート、ビスメラミンアルミノトリホスフェート、硫酸メラミン、アンメリド、アンメリン、ホルモグアナミン、グアニルメラミン、シアノメラミン、アリールグアナミン、メラム、メレム、メロンなどが挙げられる。 Specific examples of the triazine compound include cyanurate, trimethylocyanurate, triethyl cyanurate, tri (n-propyl) cyanurate, methyl cyanurate, diethyl cyanurate, isocyanurate, trimethyl cyanurate, triethyl isocyanurate, and tri (n). -Propyl) isocyanurate, diethyl isocyanurate, methyl cyanurate, melamine, melamine cyanurate, melamine phosphate compound, dimelamine phosphate compound, melamine polyphosphate compound, bismelamine discophosphate, bismelamine aluminotriphosphate, melamine sulfate, ammeride , Ammerin, formoguanamine, guanylmelamine, cyanomelamine, arylguanamine, melamine, melem, melon and the like.
　（Ｅ）窒素系化合物の添加量は、ポリブチレンテレフタレート樹脂１００質量部に対し、０～８０質量部であり、０～７０質量部または０～６０質量部であっても良い。 The amount of the nitrogen-based compound added (E) is 0 to 80 parts by mass, and may be 0 to 70 parts by mass or 0 to 60 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin.
（充填剤）　本発明の組成物には必要に応じて充填剤が使用される。このような充填剤は、機械的強度、耐熱性、寸法安定性等の性能に優れた性質を得るためには配合することが好ましく、特に剛性を高める目的で有効である。これは目的に応じて繊維状、粉粒状又は板状の充填剤であり、（Ｃ）耐トラッキング性向上剤とは異なる化合物が用いられる。 (Filler) A filler is used in the composition of the present invention as needed. Such a filler is preferably blended in order to obtain excellent performance properties such as mechanical strength, heat resistance, and dimensional stability, and is particularly effective for the purpose of increasing rigidity. This is a fibrous, powdery or plate-like filler depending on the purpose, and a compound different from (C) the tracking resistance improving agent is used.
　繊維状充填剤としては、円形断面ガラス繊維、扁平断面ガラス繊維、アスベスト繊維、カーボン繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、チタン酸カリウム繊維、更にステンレス、アルミニウム、チタン、銅、真鍮等の金属の繊維状物などが挙げられる。なお、フッ素樹脂、アクリル樹脂などの高融点の有機質繊維状物質も使用することができる。 Fibrous fillers include circular cross-section glass fibers, flat cross-section glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, zirconia fibers, potassium titanate fibers, and stainless steel, aluminum, titanium, copper, brass, etc. Examples include metal fibrous materials. In addition, organic fibrous substances having a high melting point such as fluororesin and acrylic resin can also be used.
　粉粒状充填剤としては、ガラスビーズ、ガラス粉、石英粉末、カオリン、クレー、珪藻土、ウォラストナイト、その他、炭化珪素、窒化珪素、各種金属粉末等が挙げられる。 Examples of the powder granular filler include glass beads, glass powder, quartz powder, kaolin, clay, diatomaceous earth, wollastonite, silicon carbide, silicon nitride, and various metal powders.
　また、板状無機充填剤としては、ガラスフレーク、各種金属箔等が挙げられる。 Examples of the plate-shaped inorganic filler include glass flakes and various metal foils.
　充填剤の種類は特に限定されず、１種又は複数種以上の充填剤を添加することができる。特に、円形断面ガラス繊維、扁平断面ガラス繊維、チタン酸カリウム繊維、ウォラストナイトを使用することが好ましい。 The type of filler is not particularly limited, and one or more fillers can be added. In particular, it is preferable to use circular cross-section glass fiber, flat cross-section glass fiber, potassium titanate fiber, and wollastonite.
　充填剤の添加量は特に規定されるものではないが、ポリブチレンテレフタレート樹脂１００質量部に対して２００質量部以下が好ましい。充填剤を過剰に添加した場合は成形性に劣り靭性の低下が見られる。 The amount of the filler added is not particularly specified, but is preferably 200 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin. When the filler is added excessively, the moldability is poor and the toughness is lowered.
（添加剤）
　さらに本発明の組成物には、その目的に応じ、種々の所望の特性を付与するために、一般に熱可塑性樹脂等に添加される公知の物質を添加併用することができる。例えば酸化防止剤、紫外線吸収剤、光安定剤等の安定剤、帯電防止剤、滑剤、離型剤、染料や顔料等の着色剤、可塑剤、流動性向上剤、靱性向上剤、耐加水分解性向上剤、ハロゲン化ベンジルアクリレート系難燃剤以外の難燃剤、耐トラッキング性向上用樹脂以外の樹脂等いずれも配合することが可能である。 (Additive)
Further, in order to impart various desired properties to the composition of the present invention, a known substance generally added to a thermoplastic resin or the like can be added and used in combination. For example, antioxidants, UV absorbers, stabilizers such as light stabilizers, antistatic agents, lubricants, mold release agents, colorants such as dyes and pigments, plasticizers, fluidity improvers, toughness improvers, hydrolysis resistance. It is possible to blend any of a property improver, a flame retardant other than the halogenated benzyl acrylate flame retardant, a resin other than the tracking resistance improving resin, and the like.
　なお、意匠性等の要求から、本発明の組成物を着色して用いる場合、特に暗色系の着色においては、耐トラッキング性の観点から、着色剤としてはカーボンブラックではなく、黒色あるいは暗色系の有機染料や有機顔料を添加することが望ましい。 In addition, when the composition of the present invention is colored and used from the viewpoint of designability and the like, particularly in the case of dark color coloring, from the viewpoint of tracking resistance, the colorant is not carbon black but black or dark color. It is desirable to add organic dyes and pigments.
　また、ハロゲン化ベンジルアクリレート系難燃剤以外の難燃剤としてリン系難燃剤を添加する場合は、有機ホスフィン酸金属塩、有機ジホスフィン酸金属塩、縮合リン酸エステル（レゾルシノールホスフェート類、ハイドロキノンホスフェート類、ビフェノールホスフェート類等）、ホスファゼン化合物（環状フェノキシホスファゼン、鎖状フェノキシホスファゼン、架橋フェノキシホスファゼン等）などを用いることができ、成形品からの浸み出しの観点からは、エチルホスフィン酸アルミニウム、ジエチルホスフィン酸アルミニウム、メチルエチルホスフィン酸アルミニウム、ジエチルホスフィン酸亜鉛などの有機ホスフィン酸金属塩が好ましい。また、ハロゲン化ベンジルアクリレート系難燃剤以外の難燃剤としてハロゲン系難燃剤を添加する場合は、ハロゲン化エポキシ系難燃剤、ハロゲン化フェノキシ系難燃剤、ハロゲン化ポリフェニレンエーテル系難燃剤、ハロゲン化スチレン系難燃剤、ハロゲン化フタルイミド系難燃剤、ハロゲン化ポリカーボネート系難燃剤等のハロゲン系難燃剤を挙げることができるが、耐トラッキング性を低下させないためには、これらハロゲン系難燃剤中に含まれる遊離臭素、遊離塩素、遊離硫黄の含有量がそれぞれ０．５質量％以下のものであることが好ましい。 When a phosphorus-based flame-retardant is added as a flame-retardant other than the halogenated benzyl acrylate-based flame-retardant, an organic phosphinic acid metal salt, an organic diphosphinic acid metal salt, and a condensed phosphate ester (resorcinol phosphates, hydroquinone phosphates, biphenol) Phosphazenes, etc.), phosphazene compounds (cyclic phenoxyphosphazene, chain phenoxyphosphazene, crosslinked phenoxyphosphazene, etc.) can be used. , Aluminum methylethylphosphinate, organic phosphinic acid metal salts such as zinc diethylphosphinate are preferred. When a halogen-based flame retardant is added as a flame retardant other than the halogenated benzyl acrylate-based flame retardant, a halogenated epoxy-based flame retardant, a halogenated phenoxy-based flame retardant, a halogenated polyphenylene ether-based flame retardant, or a halogenated styrene-based flame retardant Halogen-based flame retardants such as flame retardants, halogenated phthalimide-based flame retardants, and halogenated polycarbonate-based flame retardants can be mentioned, but in order not to reduce the tracking resistance, free bromine contained in these halogen-based flame retardants can be mentioned. , Free chlorine and free sulfur are preferably 0.5% by mass or less, respectively.
［難燃性ポリブチレンテレフタレート樹脂組成物の製造方法］
　本発明の難燃性ポリブチレンテレフタレート樹脂組成物の形態は、粉粒体混合物であってもよいし、ペレット等の溶融混合物（溶融混練物）であってもよい。本発明の一実施形態のポリブチレンテレフタレート樹脂組成物の製造方法は、（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程を有している。当該工程については上記のとおりであるからここでは記載を省略する。
　ポリブチレンテレフタレート樹脂組成物の製造方法は特に限定されるものではなく、当該技術分野で知られている設備及び方法を用いて製造することができる。例えば、必要な成分を混合し、１軸又は２軸の押出機又はその他の溶融混練装置を使用して混練し、成形用ペレットとして調製することができる。押出機又はその他の溶融混練装置は複数使用してもよい。また、全ての成分をホッパから同時に投入してもよいし、一部の成分はサイドフィード口から投入してもよい。 [Manufacturing method of flame-retardant polybutylene terephthalate resin composition]
The form of the flame-retardant polybutylene terephthalate resin composition of the present invention may be a powder or granular material mixture or a melt mixture (melt kneaded product) such as pellets. The method for producing a polybutylene terephthalate resin composition according to an embodiment of the present invention includes (B) a step for producing a halogenated benzyl acrylate-based flame retardant. Since the process is as described above, the description thereof is omitted here.
The method for producing the polybutylene terephthalate resin composition is not particularly limited, and the polybutylene terephthalate resin composition can be produced using equipment and methods known in the art. For example, the required components can be mixed and kneaded using a single-screw or twin-screw extruder or other melt-kneading device to prepare pellets for molding. Multiple extruders or other melt kneaders may be used. Further, all the components may be input from the hopper at the same time, or some components may be input from the side feed port.
　以下、実施例により本発明を具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、特性評価は以下の方法により行った。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The characteristic evaluation was performed by the following method.
（１）ハロゲン化芳香族化合物含有量
　表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリュを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレットを粉砕したものを試料とした。試料を５ｇとり、２０ｍｌのヘッドスペース中に１５０℃で１時間放置した後、装置：横河ヒューレット・パッカード社製ＨＰ５８９０Ａ、カラム：ＨＲ－１７０１（０．３２ｍｍ径×３０ｍ）を用い、５０℃で１分間保持後、５℃／ｍｉｎで昇温させ、ガスクロマトグラフにより、ハロゲン化芳香族化合物に由来するガス発生量を測定し、ハロゲン化芳香族化合物の含有量をｐｐｍで示した。結果を表１に示す。 (1) Halogenated Aromatic Compound Content The material dry-blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ. A sample obtained by crushing pellets of the obtained polybutylene terephthalate resin composition obtained by melt-kneading at 260 ° C. was used as a sample. After taking 5 g of a sample and leaving it in a head space of 20 ml at 150 ° C. for 1 hour, the apparatus: HP5890A manufactured by Yokogawa Hulett Packard Co., Ltd., column: HR-1701 (0.32 mm diameter × 30 m) was used at 50 ° C. After holding for 1 minute, the temperature was raised at 5 ° C./min, the amount of gas generated from the halogenated aromatic compound was measured by a gas chromatograph, and the content of the halogenated aromatic compound was shown in ppm. The results are shown in Table 1.
（２）金属腐蝕性
　表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリュを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレット５０ｇを、１ｃｍ×１ｃｍの銀板とともに３００ｍｌのガラス製共栓ビンに入れ栓をして、１５０℃のギアオーブン中で５００時間静置した後、銀板の表面を目視にて確認し、腐蝕が発生していないものを○、腐蝕が発生していたものを×として評価した。結果を表１に示す。 (2) Metal Corrosiveness The material dry-blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ and melted at 260 ° C. 50 g of pellets of the polybutylene terephthalate resin composition obtained after kneading was placed in a 300 ml glass stopper bottle together with a 1 cm × 1 cm silver plate, stoppered, and allowed to stand in a gear oven at 150 ° C. for 500 hours. After that, the surface of the silver plate was visually confirmed, and the one without corrosion was evaluated as ◯, and the one with corrosion was evaluated as ×. The results are shown in Table 1.
（３）難燃性
　表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリュを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物のペレットを、１４０℃で３時間乾燥させた後、シリンダ温度２５０℃、金型温度７０℃にて射出成形し、ＵＬ９４に準拠し、厚さ１／３２インチの試験片を作製して燃焼性を評価した。結果を表１に示す。 (3) Flame retardancy The material dry-blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ and melted at 260 ° C. The pellets of the polybutylene terephthalate resin composition obtained by kneading were dried at 140 ° C. for 3 hours, and then injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C., conforming to UL94, and having a thickness of 1 A / 32 inch test piece was prepared and flammability was evaluated. The results are shown in Table 1.
（４）耐トラッキング性
　表１に示す成分、組成（質量部）でドライブレンドした材料を、３０ｍｍφのスクリュを有する２軸押出機（（株）日本製鋼所製）に供給して２６０℃で溶融混練し、得られたポリブチレンテレフタレート樹脂組成物について、ＵＬ７４６Ａに準拠して、比較トラッキング指数（ＣＴＩ）のＰＬＣ（Ｐｅｒｆｏｒｍａｎｃｅ　Ｌｅｖｅｌ　Ｃａｔｅｇｏｒｙ）等級を判定した。ＰＬＣ等級が最高ランクの「０」である場合は「○」、そうでない場合は「×」と評価した。結果を表１に示す。 (4) Tracking resistance The material dry-blended with the components and composition (parts by mass) shown in Table 1 is supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw of 30 mmφ and melted at 260 ° C. The polybutylene terephthalate resin composition obtained by kneading was determined to have a PLC (Performance Level Category) grade of Comparative Tracking Index (CTI) according to UL746A. When the PLC grade was the highest rank "0", it was evaluated as "○", and when it was not, it was evaluated as "x". The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000004
 　表中のＮ．Ｄ．は検出限界（０．１ｐｐｍ）以下であることを示す。
　含有量の単位は、質量部である。
Figure JPOXMLDOC01-appb-T000004
 N. in the table. D. Indicates that it is below the detection limit (0.1 ppm).
The unit of content is parts by mass.
　表１に記載の各成分の詳細は下記の通りである。
（Ａ）ＰＢＴ樹脂：ポリプラスチックス株式会社製、末端カルボキシル基濃度２０ｍｅｑ／ｋｇ、固有粘度０．７ｄＬ／ｇのポリブチレンテレフタレート樹脂
（Ｂ－１）ＰＢＢＰＡ１：溶媒にエチレングリコールモノメチルエーテルを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量８ｐｐｍ）
（Ｂ－２）ＰＢＢＰＡ２：溶媒にクロロベンゼンを使用して重合したポリペンタブロモベンジルアクリレート（難燃剤以外のハロゲン化芳香族化合物含有量１５０ｐｐｍ）
（Ｃ－１）耐トラッキング性向上用樹脂１：コア層がアクリル系ゴム、シェル層がビニル系重合体のアクリル系コアシェル型エラストマ（ローム・アンド・ハース・ジャパン社製、パラロイドＥＸＬ２３１４）
（Ｃ－２）耐トラッキング性向上用樹脂２：エチレン－グリシジルメタクリレート共重合体（オレフィン系エラストマ、住友化学工業社製、ＢＯＮＤＦＡＳＴ　７Ｍ）
（Ｄ）タルク：松村産業社製、クラウンタルクＰＰ
（Ｅ）窒素系化合物：メラミンシアヌレート（ＢＡＳＦ社製、Ｍｅｌａｐｕｒ　ＭＣ５０）
ガラス繊維：日本電気硝子社製、ＥＣＳ０３Ｔ－１２７（平均繊維径１３μｍ、平均繊維長３ｍｍの円形断面ガラス繊維）
三酸化アンチモン：日本精鉱社製、ＰＡＴＯＸ－Ｍ
滴下防止剤：ポリテトラフルオロエチレン
  Details of each component shown in Table 1 are as follows.
(A) PBT resin: Polybutylene terephthalate resin (B-1) manufactured by Polyplastics Co., Ltd., having a terminal carboxyl group concentration of 20 meq / kg and an intrinsic viscosity of 0.7 dL / g. (B-1) PBBPA1: Using ethylene glycol monomethyl ether as a solvent. Polymerized polypentabromobenzyl acrylate (content of halogenated aromatic compound other than flame retardant 8 ppm)
(B-2) PBBPA2: Polypentabromobenzyl acrylate polymerized using chlorobenzene as a solvent (content of halogenated aromatic compound other than flame retardant 150 ppm)
(C-1) Resin for improving tracking resistance 1: Acrylic core-shell type elastomer whose core layer is an acrylic rubber and whose shell layer is a vinyl polymer (Rohm and Haas Japan Co., Ltd., Pararoid EXL2314)
(C-2) Resin for improving tracking resistance 2: Ethylene-glycidyl methacrylate copolymer (olefin elastomer, manufactured by Sumitomo Chemical Co., Ltd., BONDFAST 7M)
(D) Talc: Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd.
(E) Nitrogen compound: Melamine cyanurate (BASF, Melapur MC50)
Glass fiber: ECS03T-127 manufactured by Nippon Electric Glass Co., Ltd. (Circular cross-section glass fiber with an average fiber diameter of 13 μm and an average fiber length of 3 mm)
Antimony trioxide: manufactured by Nihon Seiko Co., Ltd., PATOX-M
Anti-dripping agent: Polytetrafluoroethylene

Claims (8)

  1. 　（Ａ）ポリブチレンテレフタレート樹脂１００質量部と、
    　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤３～５０質量部と、
    　（Ｃ）オレフィン系エラストマ、アクリル系コアシェル型エラストマ、直鎖状ポリオレフィン樹脂、及びこれらの組み合わせから選択される１種以上の耐トラッキング性向上用樹脂５～１００質量部と、
    　（Ｄ）タルク、マイカ、無機金属化合物、及びこれらの組み合わせから選ばれる１種以上の耐トラッキング性向上用充填剤０～１００質量部と、
    　（Ｅ）トリアジン化合物、ベンゾグアニン化合物、トリス（ヒドロキシアルキル）イソシアヌレートのテレフタル酸エステル化合物、アラントイン化合物、グリコールウリル化合物、及びこれらの組み合わせから選択される１種以上の窒素系化合物０～８０質量部とを含有する難燃性ポリブチレンテレフタレート樹脂組成物であって、
    　ヘッドスペースガスクロマトグラフ法（１５０℃、１時間加熱）により測定される、前記難燃剤以外のハロゲン化芳香族化合物の含有量が０．５ｐｐｍ未満であることを特徴とする、難燃性ポリブチレンテレフタレート樹脂組成物。     (A) 100 parts by mass of polybutylene terephthalate resin and
    (B) Halogenated benzyl acrylate flame retardant 3 to 50 parts by mass and
    (C) 5 to 100 parts by mass of one or more kinds of resins for improving tracking resistance selected from an olefin-based elastomer, an acrylic-based core-shell type elastomer, a linear polyolefin resin, and a combination thereof.
    (D) 0 to 100 parts by mass of one or more tracking resistance improving fillers selected from talc, mica, inorganic metal compounds, and combinations thereof.
    (E) Triazine compound, benzoguanine compound, terephthalic acid ester compound of tris (hydroxyalkyl) isocyanurate, allantin compound, glycoluril compound, and one or more nitrogen-based compounds selected from these combinations, 0 to 80 parts by mass. A flame-retardant polybutylene terephthalate resin composition containing
    A flame-retardant polybutylene terephthalate, which is measured by a headspace gas chromatograph method (heating at 150 ° C. for 1 hour) and has a content of a halogenated aromatic compound other than the flame retardant of less than 0.5 ppm. Resin composition.
  2. 　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤が、一般式（Ｉ）で表されるブロム化アクリル重合体を含有する、請求項１に記載の難燃性ポリブチレンテレフタレート樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｘは、水素原子または臭素原子であり、少なくとも１つ以上のＸは臭素原子であり、ｍは１０～２０００の数である。）     (B) The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the halogenated benzyl acrylate-based flame retardant contains a brominated acrylic polymer represented by the general formula (I).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, X is a hydrogen atom or a bromine atom, at least one X is a bromine atom, and m is a number of 10 to 2000.)
  3. 　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤が、ポリペンタブロモベンジルアクリレートを含有する、請求項１または２に記載の難燃性ポリブチレンテレフタレート樹脂組成物。 (B) The flame-retardant polybutylene terephthalate resin composition according to claim 1 or 2, wherein the halogenated benzyl acrylate-based flame retardant contains polypentabromobenzyl acrylate.
  4. 　前記難燃剤以外のハロゲン化芳香族化合物が、ハロゲン化ベンゼンを含有する、請求項１から３のいずれか一項に記載の難燃性ポリブチレンテレフタレート樹脂組成物。 The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 3, wherein the halogenated aromatic compound other than the flame retardant contains benzene halide.
  5. 　前記難燃剤以外のハロゲン化芳香族化合物が、クロロベンゼンを含有する、請求項１から４のいずれか一項に記載の難燃性ポリブチレンテレフタレート樹脂組成物。 The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4, wherein the halogenated aromatic compound other than the flame retardant contains chlorobenzene.
  6. 　請求項１から５のいずれか一項に記載の難燃性ポリブチレンテレフタレート樹脂組成物の製造方法であって、
    　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程を有し、該工程で用いる溶媒中のハロゲン化芳香族化合物の含有量が１０００ｐｐｍ以下であることを特徴とする、製造方法。     The method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5.
    (B) A production method comprising a production step of a halogenated benzyl acrylate-based flame retardant, wherein the content of the halogenated aromatic compound in the solvent used in the step is 1000 ppm or less.
  7. 　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程において、溶媒としてハロゲン化芳香族化合物を用いない、請求項６に記載の製造方法。 (B) The production method according to claim 6, wherein a halogenated aromatic compound is not used as a solvent in the production process of the halogenated benzyl acrylate flame retardant.
  8. 　（Ｂ）ハロゲン化ベンジルアクリレート系難燃剤の製造工程において、溶媒としてエチレングリコールモノメチルエーテル、メチルエチルケトン、エチレングリコールジメチルエーテルおよびジオキサンからなる群から選択される一以上の溶媒を用いる、請求項６又は７に記載の製造方法。
          (B) The invention according to claim 6 or 7, wherein in the process for producing the halogenated benzyl acrylate flame retardant, one or more solvents selected from the group consisting of ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol dimethyl ether and dioxane are used as the solvent. Manufacturing method.
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