JP6010464B2 - Molding - Google Patents

Description

  The present invention relates to a molded article. More specifically, the present invention is excellent in impact resistance, flame retardancy, heat aging resistance, light resistance, moisture and heat resistance, and has excellent moldability, and is an excellent polybutylene terephthalate system. The present invention relates to a charger connector for an electric vehicle formed by molding a resin composition, a holder for a battery capacitor, a casing for a battery capacitor, or a casing for a charging stand for an electric vehicle.

  In recent years, automobiles that include an electric motor as a power source, such as electric vehicles and plug-in hybrid vehicles, have become widespread, and it has been promoted to install a charging stand for battery charging for such vehicles, In addition, charger connectors for electric vehicles for battery charging and / or battery capacitor holders have been used.

A high degree of flame retardancy is required for a housing for constituting a charger connector for an electric vehicle, a battery capacitor holder, or a charging stand for an electric vehicle, and many metal ones are used. In addition, there is a movement to convert this into a resin, and various resins are being studied.
Among these, polybutylene terephthalate has properties suitable as engineering plastics such as excellent heat resistance, moldability, chemical resistance, and electrical insulation, so it can be used in electrical and electronic parts, automotive parts, other electrical parts, and machinery. It is used for parts, etc., and it has been studied to make it flame-retardant.

  As a method of imparting flame retardancy to polybutylene terephthalate, generally, a flame retardant using antimony trioxide (see Patent Document 1) as a halogen compound or a flame retardant aid is added to polybutylene terephthalate. Thus, the method of making it flame retardant is well known. In addition, as with other electric and electronic parts, the charger connector for electric vehicles, the battery capacitor holder, the battery capacitor case, or the charging stand housing for electric vehicles are thin and small due to the trend toward smaller and lighter devices. The molded products used for them are becoming smaller and thinner, and high flame resistance is required for thin molded products. However, the thinner the molded products, the more the flame retardant is achieved. It becomes difficult.

  In the field of electrical and electronic equipment, in addition to flame retardancy, it is necessary to have excellent tracking resistance, which is one of the electrical characteristics, in order to ensure safety against ignition against an electrical load.

Furthermore, polybutylene terephthalate has a problem that its toughness represented by impact strength is insufficient due to its excellent crystal characteristics, and in order to solve this problem, research on polymer alloys has been conducted conventionally. Various proposals have been made for flame retardant formulations.
For example, Patent Document 2 discloses a flame retardant polyester resin composition comprising a polybutylene terephthalate resin, a polycarbonate resin, a halogen flame retardant, a flame retardant assistant, and a transesterification inhibitor as constituents. 3 discloses a flame-retardant polyester resin composition comprising a polybutylene terephthalate resin, a polycarbonate resin, an elastomer, a flame retardant, and a flame retardant aid. Furthermore, Patent Document 4 discloses a polyester resin composition comprising a polyester resin, a polystyrene rubber and a flame retardant.

However, the required physical properties of electric vehicle charger connectors, battery capacitor holders, battery capacitor housings, or electric vehicle charging stand housings have become increasingly sophisticated, and it has become difficult to cope with conventional prescriptions. Yes.
Furthermore, excellent mold releasability that does not increase the mold release resistance is also required in injection molding, for example, there is no occurrence of ejector pin marks when taking out from the mold, the surface appearance is good, and warpage is not caused. There is a strong demand for something that does not exist.

JP-A-61-66746 JP 2007-314664 A JP-A-6-100713 JP 2005-112994 A

  The object of the present invention is to provide an electric vehicle charger connector having excellent impact resistance, flame retardancy, heat aging resistance, light resistance, moisture and heat resistance, excellent moldability, and comprehensively good characteristics, An object of the present invention is to provide a battery capacitor holder, a battery capacitor casing, or a housing for an electric vehicle charging station.

The present inventor has added a polycarbonate resin, a specific impact resistance improver, a flame retardant, and an antimony compound to the polybutylene terephthalate-based resin in specific amounts, respectively. The present inventors have found that a charger connector for an electric vehicle, a battery capacitor holder, a battery capacitor case, a battery capacitor case or a housing for a charging stand for an electric vehicle can be provided with excellent light resistance, moisture and heat resistance, and moldability. .
That is, according to the present invention, the following molded articles are provided.

[1] The (A) polybutylene terephthalate resin and the (B) polycarbonate resin are based on a total of 100 parts by mass of (A) and (B), (A) is 50 to 80 parts by mass, and (B) is 20 to 20 parts. 50 parts by mass, and (C) 5-20 parts by mass of elastomer, (D) 5-40 parts by mass of flame retardant, and (E) antimony compound 1 with respect to 100 parts by mass of (A) and (B) in total. A molded product formed by molding a resin composition containing ˜15 parts by mass, which is either a charger connector for an electric vehicle, a holder for a battery capacitor, a casing for a battery capacitor, or a casing for a charging stand for an electric vehicle A molded product characterized by being.
[2] The molded article according to the above [1], wherein the polycarbonate resin has a viscosity average molecular weight of 20000 or more.
[3] The molded article according to the above [1] or [2], wherein the intrinsic viscosity of the (A) polybutylene terephthalate resin is 0.9 dl / g or more.
[4] The molded article according to any one of [1] to [3], wherein the (C) elastomer is an acrylic core / shell type graft copolymer.

  The polybutylene terephthalate resin composition used in the present invention is a resin material excellent in impact resistance, flame retardancy, heat aging resistance, light resistance, moisture and heat resistance, and moldability. Suitable for battery capacitor holder, battery capacitor housing or electric vehicle charging station housing, excellent impact resistance, flame retardancy and tracking resistance, no warpage problem for electric vehicle charger connector, A battery capacitor holder, a battery capacitor housing, or a housing for an electric vehicle charging station can be provided.

[Summary of Invention]
In the present invention, (A) polybutylene terephthalate resin and (B) polycarbonate resin are based on a total of 100 parts by mass of (A) and (B), and (A) is 50 to 80 parts by mass, and (B) is 20 -50 mass parts, and (C) elastomer 5-20 mass parts, (D) flame retardant 5-40 mass parts, and (E) antimony compound with respect to a total of 100 mass parts of (A) and (B) A molded product formed by molding a resin composition containing 1 to 15 parts by mass, which is either a charger connector for an electric vehicle, a holder for a battery capacitor, a casing for a battery capacitor, or a casing for a charging stand for an electric vehicle It is a molded product characterized by being.

Hereinafter, the contents of the present invention will be described in detail.
The description of each constituent element described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is interpreted to be limited to such embodiments and specific examples. It is not a thing. In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

[(A) Polybutylene terephthalate resin]
The (A) polybutylene terephthalate resin (hereinafter sometimes abbreviated as “PBT resin”), which is the main component constituting the resin composition used in the present invention, includes a terephthalic acid unit and 1,4-butanediol. A polymer having a structure in which units are ester-bonded is shown. That is, in addition to polybutylene terephthalate resin (homopolymer), polybutylene terephthalate copolymer containing other copolymer components other than terephthalic acid units and 1,4-butanediol units, and homopolymers and copolymers thereof Including the mixture.

  The PBT resin may contain dicarboxylic acid units other than terephthalic acid. Specific examples of other dicarboxylic acids include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, and 2,5-naphthalenedicarboxylic acid. 2,6-naphthalenedicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, bis (4,4′-carboxyphenyl) methane , Aromatic dicarboxylic acids such as anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid, and adipic acid , Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, dimer acid, etc. .

  The diol unit may contain other diol units in addition to 1,4-butanediol, but specific examples of other diol units include aliphatic or alicyclic diols having 2 to 20 carbon atoms. And bisphenol derivatives. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4'-dicyclohexylhydroxymethane. 4,4′-dicyclohexylhydroxypropane, bisphenol A ethylene oxide addition diol, and the like. Furthermore, triols such as glycerin and trimethylolpropane are also included.

  The PBT resin is preferably a polybutylene terephthalate homopolymer obtained by polycondensation of terephthalic acid and 1,4-butanediol. In addition, as a carboxylic acid unit, one or more dicarboxylic acids other than the terephthalic acid and / or A polybutylene terephthalate copolymer containing one or more diols other than 1,4-butanediol as the diol unit may be used. In the PBT resin, from the viewpoint of mechanical properties and heat resistance, the proportion of terephthalic acid in the dicarboxylic acid unit is preferably 70 mol% or more, more preferably 90 mol% or more. Similarly, the proportion of 1,4-butanediol in the diol unit is preferably 70 mol% or more, more preferably 90 mol% or more.

  In addition to the above-mentioned bifunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure, and fatty acids are used for molecular weight control. A small amount of a monofunctional compound can be used in combination.

The PBT resin is produced by melt-polymerizing a dicarboxylic acid component containing terephthalic acid as a main component or an ester derivative thereof and a diol component containing 1,4-butanediol as a main component in a batch or continuous manner. Can do. In addition, after producing a low molecular weight polybutylene terephthalate resin by melt polymerization, the degree of polymerization (or molecular weight) can be increased to a desired value by further solid-phase polymerization under a nitrogen stream or under reduced pressure.
The PBT resin is preferably obtained by a production method in which a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing 1,4-butanediol as a main component are continuously melt polycondensed.

  The catalyst used in performing the esterification reaction may be a conventionally known catalyst, and examples thereof include a titanium compound, a tin compound, a magnesium compound, and a calcium compound. Of these, titanium compounds are particularly preferred. Specific examples of the titanium compound as the esterification catalyst include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate.

The PBT resin may be a polybutylene terephthalate resin modified by copolymerization. As a specific preferred copolymer thereof, a polyalkylene glycol (particularly, polytetramethylene glycol (PTMG)) is copolymerized. Examples include polyester ether resins, dimer acid copolymerized polybutylene terephthalate resins, and particularly isophthalic acid copolymerized polybutylene terephthalate resins. These copolymers are those having a copolymerization amount of 1 mol% or more and less than 50 mol% in all segments of the PBT resin. Among them, the copolymerization amount is preferably 2 to 50 mol%, more preferably 3 to 40 mol%, and particularly preferably 5 to 20 mol%.
And the preferable content of these copolymers is 10-100 mass% in the total amount of 100 mass% of (A) polybutylene terephthalate resin, Furthermore, 30-100 mass%, Especially it is 50-100 mass%. is there.

  The intrinsic viscosity ([η]) of the PBT resin is preferably 0.9 dl / g or more. If the intrinsic viscosity is lower than 0.9 dl / g, the resulting resin composition tends to have a low mechanical strength such as impact resistance. The intrinsic viscosity is preferably 1.8 dl / g or less, more preferably 1.6 dl / g or less, and further preferably 1.3 dl / g or less. If it is higher than 1.8 dl / g, the fluidity of the resin composition may deteriorate and the moldability may deteriorate. The intrinsic viscosity is measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

[(B) Polycarbonate resin]
The resin composition used in the present invention contains (B) a polycarbonate resin.
The polycarbonate resin is an optionally branched thermoplastic polymer or copolymer obtained by reacting a dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester. The production method of the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by a conventionally known phosgene method (interfacial polymerization method) or a melting method (transesterification method) can be used.

  As the raw material dihydroxy compound, an aromatic dihydroxy compound is preferable, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, Hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc. are mentioned, Preferably bisphenol A is mentioned. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  As the polycarbonate resin, among the above-mentioned, aromatic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy Aromatic polycarbonate copolymers derived from the compounds are preferred. Further, it may be a copolymer mainly composed of an aromatic polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure. Furthermore, you may mix and use 2 or more types of the polycarbonate resin mentioned above.

  In order to adjust the molecular weight of the polycarbonate resin, a monovalent aromatic hydroxy compound may be used. For example, m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p-long chain And alkyl-substituted phenols.

  The viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 20000 or more, more preferably 23000 or more and 25000 or more. When a resin having a viscosity average molecular weight lower than 20000 is used, the resulting resin composition tends to have a low mechanical strength such as impact resistance. Moreover, it is preferable that it is 60000 or less, It is more preferable that it is 40000 or less, It is further more preferable that it is 35000 or less. If it is higher than 60000, the fluidity of the resin composition may deteriorate and the moldability may deteriorate.

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin is determined by measuring the viscosity of the methylene chloride solution of the polycarbonate resin at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity ([η]). The value calculated from the following Schnell viscosity equation is shown.
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

  The method for producing the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can also be used. Moreover, the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method is also preferable.

  The content of (B) polycarbonate resin is based on a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin, and (B) polycarbonate resin is 20 to 50 parts by mass, preferably 25 parts by mass. Part or more, more preferably 30 parts by weight or more, preferably 45 parts by weight or less, more preferably 40 parts by weight or less. Below the lower limit, the effect of improving the impact resistance and toughness of the polybutylene terephthalate resin composition of the present invention is small, and the dimensional stability is lowered. Moreover, when it exceeds the said upper limit, fluidity | liquidity will worsen and a moldability will deteriorate.

[(C) Elastomer]
As the (C) elastomer used in the present invention, a thermoplastic elastomer used for improving impact resistance by blending with a polyester resin or polycarbonate resin may be used. For example, a rubber polymer or rubber heavy polymer may be used. A compound obtained by copolymerizing a compound that reacts with the compound is used. (C) The glass transition temperature of the elastomer is preferably 0 ° C. or lower, particularly preferably −20 ° C. or lower.

Specific examples of (C) elastomers include, for example, polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, acrylic / butadiene rubber, etc.), ethylene and carbon atoms of 3 or more. Copolymers with α-olefins (ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / octene copolymers, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (ethylene / methacrylate copolymer) Copolymers, ethylene / butyl acrylate copolymers, etc.), copolymers of ethylene and aliphatic vinyl compounds, terpolymers of ethylene, propylene and non-conjugated dienes, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl acrylate)) , Butyl acrylate, 2-ethylhexyl urea Relate copolymers), silicone rubber (a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkyl (meth) IPN type composite rubber consisting of acrylate rubber), and the like. These may be used alone or in combination of two or more.
In the present invention, (meth) acrylate means acrylate and methacrylate, and (meth) acrylic acid means acrylic acid and methacrylic acid.

  Another example of the elastomer (C) is a copolymer obtained by polymerizing a monomer compound with a rubber polymer. Examples of the monomer compound include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. In addition, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β- such as maleic acid, phthalic acid and itaconic acid Examples thereof also include unsaturated carboxylic acid compounds and anhydrides thereof (for example, maleic anhydride). These monomer compounds can be used alone or in combination of two or more.

(C) The elastomer is preferably an elastomer containing an acrylic and / or butadiene component, and is preferably a copolymer obtained by copolymerizing a butadiene-based and / or acrylic rubbery polymer with a monomer compound that reacts therewith.
Specific examples of the impact modifier containing an acrylic and / or butadiene component include, for example, acrylonitrile-butadiene copolymer, acrylic-butadiene rubber, and a copolymer obtained by polymerizing a monomer compound with these rubbery polymers. Coalescence is mentioned. Examples of the monomer compound include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. In addition, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β- such as maleic acid, phthalic acid and itaconic acid Examples thereof also include unsaturated carboxylic acid compounds and anhydrides thereof (for example, maleic anhydride). These monomer compounds can be used alone or in combination of two or more.

  The elastomer containing the acrylic and / or butadiene component is preferably of the core / shell type graft copolymer type from the viewpoint of improving impact resistance, and the butadiene component-containing rubber and / or the acrylic component-containing rubber polymer is used as the core. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing a monomer selected from an acrylic ester, a methacrylic ester and an aromatic vinyl compound around the layer is particularly preferred.

  Examples of the core / shell type graft copolymer include butyl acrylate-methyl methacrylate copolymer, butadiene-methyl methacrylate / styrene copolymer, silicone / acryl-methyl methacrylate copolymer, methyl methacrylate-butadiene-styrene polymer. (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl methacrylate-acryl-butadiene rubber copolymer, methyl methacrylate-acryl-butadiene rubber-styrene copolymer Examples include coalescence. These rubbery polymers may be used alone or in combination of two or more. Among these, an acrylic core / shell type elastomer in which both the core and the shell are acrylic acid esters is preferable from the viewpoint of impact resistance, heat aging resistance, and light resistance.

  The content of the acrylic and / or butadiene component in the elastomer containing the acrylic and / or butadiene component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 70 to 85% by mass. If the content of the acrylic and / or butadiene component is less than 50% by mass, the impact resistance tends to be inferior, and if it exceeds 90% by mass, the flame retardancy and weather resistance tend to deteriorate, such being undesirable.

  (C) The average particle size of the elastomer is preferably 3 μm or less, more preferably 2 μm or less, further preferably 1 μm or less, and particularly preferably 800 nm or less. The lower limit is usually 50 nm, preferably 100 nm, and more preferably 150 nm. It is preferable to use an elastomer having such a particle diameter because the moldability such as impact resistance such as surface impact, moisture and heat resistance and releasability tends to be improved.

  The content of (C) elastomer is 5 to 20 parts by mass with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. When the content of the elastomer (C) is less than 5 parts by mass, the effect of improving the impact resistance is small, and when it exceeds 20 parts by mass, the heat aging resistance and rigidity, as well as the fluidity and flame retardancy are reduced. The content of the preferred (C) impact modifier is 7 parts by mass or more, 16 parts by mass or less, and further 13 parts by mass or less.

[(D) Flame retardant]
The resin composition used in the present invention contains (D) a flame retardant.
(D) As a flame retardant, known plastic flame retardants can be used. Specifically, halogen flame retardants, phosphorus flame retardants (melamine polyphosphate, etc.), nitrogen flame retardants (melamine cyanurate, etc.) ), Metal hydroxides (magnesium hydroxide, etc.).
As the halogen-based flame retardant, a brominated flame retardant is more preferable.

Bromine-based flame retardant As the brominated flame retardant, any conventionally known brominated flame retardant used in thermoplastic resins can be used. Such brominated flame retardants include aromatic compounds, specifically, for example, polybrominated benzyl (meth) acrylates such as pentabromobenzyl polyacrylate, polybromophenylene ether, brominated polystyrene, Examples thereof include brominated epoxy compounds such as tetrabromobisphenol A epoxy oligomer, brominated imide compounds such as N, N′-ethylenebis (tetrabromophthalimide) (EBTPI), and brominated polycarbonate.

  Of these, brominated epoxy compounds such as polybrominated benzyl (meth) acrylates such as pentabromobenzyl polyacrylate, epoxy oligomers such as tetrabromobisphenol A, brominated polystyrene, and brominated polycarbonate are preferred from the viewpoint of good thermal stability. Is preferably brominated polycarbonate or brominated polystyrene, and brominated polycarbonate is particularly preferred from the viewpoint of impact resistance and flame retardancy.

  As a polybrominated benzyl (meth) acrylate, a polymer obtained by polymerizing benzyl (meth) acrylate containing a bromine atom alone, copolymerizing two or more kinds, or copolymerizing with other vinyl monomers It is preferable that the bromine atom is added to the benzene ring, and the number of addition is preferably 1 to 5, more preferably 4 to 5 per benzene ring.

  Examples of the benzyl acrylate containing a bromine atom include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, and mixtures thereof. Examples of benzyl methacrylate containing a bromine atom include methacrylates corresponding to the acrylates described above.

  Specific examples of other vinyl monomers used for copolymerization with benzyl (meth) acrylates containing bromine atoms include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and benzyl acrylate. Acrylic acid esters; Methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate; Unsaturated carboxylic acids such as styrene, acrylonitrile, fumaric acid, maleic acid or anhydrides thereof; Vinyl acetate , Vinyl chloride, and the like.

  These are usually preferably used in an equimolar amount or less, particularly 0.5 times the molar amount or less with respect to the benzyl (meth) acrylate containing a bromine atom.

  In addition, xylene diacrylate, xylene dimethacrylate, tetrabromoxylene diacrylate, tetrabromoxylene dimethacrylate, butadiene, isoprene, divinylbenzene, etc. can be used as vinyl monomers, and these usually contain bromine atoms. 0.5 mol or less of benzyl acrylate or benzyl methacrylate can be used.

  As the polybrominated benzyl (meth) acrylate, pentabromobenzyl polyacrylate is preferable from the viewpoint of high bromine content and high electrical insulation characteristics (tracking resistance).

  Specific examples of brominated epoxy compounds include bisphenol A brominated epoxy compounds represented by tetrabromobisphenol A epoxy compounds.

The molecular weight of the brominated epoxy compound is arbitrary and may be appropriately selected and determined. Preferably, the weight average molecular weight (Mw) is 3000 to 100,000, and among them, the higher molecular weight is preferable, specifically Mw. 15000 to 80000, particularly 18000 to 78000 (Mw), more preferably 20000 to 75000 (Mw), particularly 22000 to 70000, and those having a high molecular weight are also preferable within this range.
The epoxy equivalent of the brominated epoxy compound is preferably 3000 to 40000 g / eq, more preferably 4000 to 35000 g / eq, and particularly preferably 10,000 to 30000 g / eq.

  Moreover, a brominated epoxy oligomer can also be used together as a brominated epoxy compound flame retardant. In this case, for example, by using about 0 to 50% by mass of an oligomer having Mw of 5000 or less, flame retardancy, mold release property and fluidity can be appropriately adjusted. Although the bromine atom content in the brominated epoxy compound is arbitrary, it is usually 10% by mass or more, preferably 20% by mass or more, particularly preferably 30% by mass or more, in order to impart sufficient flame retardancy. The upper limit is 60% by mass, preferably 55% by mass or less.

  Specifically, the brominated polycarbonate flame retardant is preferably a brominated polycarbonate obtained from, for example, brominated bisphenol A, particularly tetrabromobisphenol A. Examples of the terminal structure include a phenyl group, 4-t-butylphenyl group, 2,4,6-tribromophenyl group, etc., and particularly those having a 2,4,6-tribromophenyl group in the terminal group structure. Is preferred.

  The average number of carbonate repeating units in the brominated polycarbonate flame retardant may be appropriately selected and determined, but is usually 2 to 30. If the average number of carbonate repeating units is small, the molecular weight of the (A) polybutylene terephthalate resin may be lowered during melting. On the other hand, if it is too large, the melt viscosity of the (B) polycarbonate resin is increased, causing a dispersion failure in the molded body, which may deteriorate the appearance of the molded body, particularly the glossiness. Therefore, the average number of repeating units is preferably 3 to 15, particularly 3 to 10.

  The molecular weight of the brominated polycarbonate-based flame retardant is arbitrary and may be appropriately selected and determined. Preferably, the viscosity average molecular weight is 1000 to 20000, and preferably 2000 to 10,000. In addition, the viscosity average molecular weight of a brominated polycarbonate flame retardant can be calculated | required by the method similar to the measurement of the viscosity average molecular weight of (B) polycarbonate resin.

  The brominated polycarbonate flame retardant obtained from the brominated bisphenol A can be obtained by, for example, a usual method of reacting brominated bisphenol and phosgene. Examples of the end-capping agent include aromatic monohydroxy compounds, which may be substituted with a halogen or an organic group.

  The content of the flame retardant (D) is 5 to 40 parts by mass, preferably 7 parts by mass or more, based on a total of 100 parts by mass of the (A) polybutylene terephthalate resin and the (B) polycarbonate resin. Preferably it is 10 mass parts or more, Preferably it is 30 mass parts or less, More preferably, it is 25 mass parts or less, More preferably, it is 20 mass parts or less. (D) If the content of the flame retardant is too small, the flame retardancy of the resin composition used in the present invention will be insufficient. Conversely, if the content is too large, the mechanical properties and release properties will deteriorate, and the flame retardant bleed out. Problems arise.

[(E) Antimony compound]
The resin composition used in the present invention contains (E) an antimony compound.
Preferred examples of the antimony compound include antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), and sodium antimonate. Among these, antimony trioxide is preferable from the viewpoint of impact resistance.

  (E) When using a brominated flame retardant as the flame retardant, the antimony compound has a total mass concentration of 3 bromine atoms derived from the brominated flame retardant and antimony atoms derived from the antimony compound in the resin composition. It is preferably ˜25% by mass, more preferably 4 to 22% by mass, and even more preferably 10 to 20% by mass. If it is less than 3% by mass, the flame retardancy tends to decrease, and if it exceeds 20% by mass, the mechanical strength tends to decrease. The mass ratio (Br / Sb) of bromine atoms and antimony atoms is preferably 0.3 to 5, and more preferably 0.3 to 4. By setting it as such a range, it exists in the tendency for a flame retardance to express easily, and it is preferable.

  The content of the (E) antimony compound is 1 to 15 parts by mass, preferably 2 parts by mass or more, more preferably with respect to 100 parts by mass in total of the (A) polybutylene terephthalate resin and the (B) polycarbonate resin. It is 3 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, further preferably 6 parts by mass or less, and particularly preferably 5 parts by mass or less. If it falls below the lower limit, the flame retardancy is lowered. On the other hand, when the above upper limit is exceeded, the crystallization temperature is lowered and the releasability is deteriorated, and mechanical properties such as impact resistance are lowered.

[(F) Anti-drip agent]
The resin composition used in the present invention preferably contains (F) an anti-drip agent.
(F) As the anti-drip agent, a fluoropolymer is preferable.
As the fluoropolymer, a known polymer having fluorine can be arbitrarily selected and used, and among these, a fluoroolefin resin is preferable.
As fluoroolefin resin, the polymer and copolymer containing a fluoroethylene structure are mentioned, for example. Specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. As this fluoroethylene resin, a fluoroethylene resin having a fibril forming ability is preferable.
Examples of the fluoroethylene resin having a fibril-forming ability include Mitsui DuPont Fluorochemical Co., Ltd., Teflon (registered trademark) 6J, Daikin Chemical Industries, Ltd., Polyflon (registered trademark) F201L, and Polyflon F103.

  Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Fullon D-1 manufactured by Daikin Industries, Ltd., and TF1750 manufactured by Sumitomo 3M Limited. Furthermore, a fluoroethylene polymer having a multilayer structure formed by polymerizing vinyl monomers can also be used as the fluoropolymer. Specific examples thereof include METABRENE (registered trademark) A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

  The content of the (D) anti-drip agent is preferably 0.05 to 1 part by mass, more preferably 0 with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. 0.1 part by mass or more, more preferably 0.12 part by mass or more, particularly preferably 0.15 part by mass or more, more preferably 0.6 part by mass or less, still more preferably 0.45 part by mass or less, particularly preferably Is 0.35 parts by mass or less. (F) If the content of the anti-drip agent is too small, the flame retardancy of the resin composition used in the present invention may be insufficient. Conversely, if it is too much, the molded product of the resin composition used in the present invention. There is a possibility that a poor appearance or a decrease in mechanical strength may occur.

[Other ingredients]
The resin composition used in the present invention may contain various additives as long as the effects of the present invention are not impaired. Such additives include stabilizers, mold release agents (lubricants), reinforcing fillers, UV absorbers, nucleating agents, antistatic agents, antifogging agents, antiblocking agents, plasticizers, dispersing agents, antibacterial agents, etc. Is mentioned.

<Stabilizer>
It is preferable that the resin composition used in the present invention further contains a stabilizer because it has effects of improving thermal stability and preventing deterioration of mechanical strength, transparency and hue. As the stabilizer, a phosphorus stabilizer, a sulfur stabilizer and a phenol stabilizer are preferable.

  Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphite ester, and phosphate ester. Among them, organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds are preferable.

The organic phosphate compound is preferably the following general formula:
(R ¹ O) _3-n P (═O) OH _n
(In the formula, R ¹ is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2.)
It is a compound represented by these. More preferably, R ¹ is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group, etc. are mentioned.

  Examples of the long-chain alkyl acid phosphate include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate Acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, geo Chill acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and a bis-nonylphenyl acid phosphate, or the like. Among these, octadecyl acid phosphate is preferable, and this is marketed under the trade name “ADEKA STAB AX-71” of ADEKA.

As the organic phosphite compound, preferably, the following general formula:
^{R 2 O-P (OR 3} ) (OR 4)
Wherein R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ² , R ³ and R ⁴ At least one of them is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phosphite, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like. Among these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable.

The organic phosphonite compound is preferably the following general formula:
R ⁵ -P (OR ⁶ ) (OR ⁷ )
(In the formula, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ⁵ , R ⁶ and R ⁷ , At least one of them is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2, -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6- And di-tert-butylphenyl) -3,3′-biphenylenediphosphonite.

  As the sulfur stabilizer, any conventionally known sulfur atom-containing compound can be used, and among these, thioethers are preferred. Specifically, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis (N-phenyl-β-naphthylamine) ), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite. Among these, pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable.

  Examples of the phenol-based stabilizer include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like. Among these, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred.

  One type of stabilizer may be contained, or two or more types may be contained in any combination and ratio.

  The content of the stabilizer is preferably 0.001 to 1 part by mass with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect an improvement in the thermal stability and compatibility of the resin composition, and a decrease in molecular weight and a deterioration in hue during molding are likely to occur. When it exceeds, it will become excess amount and there exists a tendency for generation | occurrence | production of silver and a hue deterioration to occur further easily. The content of the stabilizer is more preferably 0.001 to 0.7 parts by mass, and still more preferably 0.005 to 0.6 parts by mass.

<Ultraviolet absorber>
The resin composition in the present invention preferably further contains an ultraviolet absorber from the viewpoint of having an effect of improving light resistance. In particular, when used in combination with the above-described phosphorus stabilizer and / or phenol stabilizer, the light resistance tends to be more improved.
Examples of the ultraviolet absorber include organic ultraviolet absorbers such as a benzotriazole compound, a benzophenone compound, a salicylate compound, a cyanoacrylate compound, a triazine compound, an oxanilide compound, a malonic ester compound, and a hindered amine compound. Of these, benzotriazole-based UV absorbers, triazine-based UV absorbers or malonic ester-based UV absorbers are more preferable, and benzotriazole-based UV absorbers are particularly preferable.

  Specific examples of the benzotriazole ultraviolet absorber include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α -Dimethylbenzyl) phenyl] -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'- Hydroxy-3 ′, 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotria Sol, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], among others, 2- (2 '-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) Phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred.

  Specific examples of the triazine-based UV absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy -4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6 (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) 1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4) -Butoxyethoxyphenyl) -1,3,5-triazine and the like.

  Specific examples of the malonic acid ester ultraviolet absorber include 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters, and such malonic acid ester ultraviolet absorbers. Specific examples include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by BASF, and the like.

  The content of the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. In addition, it is preferably 1 part by mass or less, more preferably 0.8 part by mass or less, and further preferably 0.6 part by mass or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the light resistance improvement effect may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, the mold Debogit etc. may occur and cause mold contamination.

<Pigment>
The resin composition in the present invention preferably further contains a pigment from the viewpoint of having an effect of improving light resistance. Examples of the pigment include inorganic pigments (black pigments such as carbon black (for example, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black), red pigments such as iron oxide red, molybdate orange, etc. Examples include orange pigments such as titanium pigments, white pigments such as titanium oxide, organic pigments (yellow pigments, orange pigments, red pigments, blue pigments, green pigments, etc.) Among these, carbon black, Titanium oxide is preferred.

  The content of the pigment is preferably 0.05 to 5 parts by mass with respect to a total of 100 parts by mass of (A) the polybutylene terephthalate resin and (B) the polycarbonate resin. If it is less than 0.05 parts by mass, the light resistance improving effect may not be sufficient, and if it exceeds 5 parts by mass, the mechanical properties may deteriorate. The content of the pigment is preferably 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass.

<Release agent>
The resin composition in the present invention preferably contains a release agent from the viewpoint of further improving the releasability from the mold. As the release agent, known release agents that are usually used for polybutylene terephthalate resins can be used, but among them, it is difficult to bleed out and express high release properties, and it is difficult to inhibit metal film adhesion. In this respect, one or more mold release agents selected from polyolefin-based compounds, fatty acid ester-based compounds, and silicone-based compounds are preferable.

Examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax. Among them, polyethylene having a mass average molecular weight of 700 to 10000, more preferably 900 to 8000, from the viewpoint of good dispersion of the polyolefin compound. Wax is preferred.
Polyolefin compounds include carboxyl groups (carboxylic acid (anhydride) groups, that is, carboxylic acid groups and / or carboxylic anhydride groups; the same shall apply hereinafter), haloformyl groups, ester groups, carboxylate metal bases, hydroxyl groups. It is preferable to add a functional group having an affinity for polybutylene terephthalate, such as an alkoxyl group, an epoxy group, an amino group, or an amide group. This concentration is preferably more than 5 mgKOH / g and less than 50 mgKOH / g, more preferably 10 to 40 mgKOH / g, more preferably 15 to 30 mgKOH / g, and particularly preferably 20 to 28 mgKOH / g as the acid value of the polyolefin compound. preferable.
In addition, an oxidized polyethylene wax is preferable as the polyolefin-based compound since it has a small amount of volatile matter and at the same time has a remarkable effect of improving the releasability.
The acid value can be measured according to a potentiometric titration method (ASTM D1386) using a 0.5 mol KOH ethanol solution.

  Examples of the fatty acid ester compounds include fatty acid esters such as glycerin fatty acid esters and sorbitan fatty acid esters, and partially saponified products thereof. Among them, the fatty acid ester compounds are composed of fatty acids having 11 to 28 carbon atoms, preferably 17 to 21 carbon atoms. Preferred are mono- or di-fatty acid esters. Specific examples include glycerin monostearate, glycerin monobehenate, glycerin dibehenate, glycerin-12-hydroxy monostearate, sorbitan monobehenate, pentaerythritol monostearate, pentaerythritol distearate and the like. It is done.

  Moreover, as a silicone type compound, the compound modified | denatured from points, such as compatibility with polybutylene terephthalate, is preferable. Examples of the modified silicone oil include silicone oil in which an organic group is introduced into the side chain of polysiloxane, silicone oil in which an organic group is introduced into both ends and / or one end of polysiloxane, and the like. Examples of the organic group to be introduced include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenol group, and preferably an epoxy group. As the modified silicone oil, a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane is particularly preferable.

  The content of the release agent is preferably 0.05 to 2 parts by mass with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. If it is less than 0.05 parts by mass, the surface appearance tends to be reduced due to defective mold release at the time of melt molding. On the other hand, if it exceeds 2 parts by mass, the kneading workability of the resin composition is reduced, and molding is also performed. The surface of the product may be cloudy. The content of the release agent is preferably 0.07 to 1.5 parts by mass, more preferably 0.1 to 1.2 parts by mass.

<Reinforcing filler>
The resin composition used in the present invention may contain a reinforcing filler as long as the effects of the present invention are not impaired. However, when high impact resistance is required, it is preferable not to contain a reinforcing filler. When the reinforcing filler is contained, a reinforcing filler having an effect of improving the mechanical properties of the resin composition obtained by blending with the resin is preferable, and a conventional inorganic filler for plastics can be used. Preferably, fibrous fillers such as glass fiber, carbon fiber, basalt fiber, wollastonite and potassium titanate fiber can be used. In addition, granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clays, organic clays, glass beads, etc .; plate-like fillers such as talc; scale-like fillings such as glass flakes, mica and graphite A material can also be used. Among these, glass fibers are preferably used from the viewpoint of mechanical strength, rigidity, and heat resistance.
In addition, when using a filler such as talc as a nucleating agent for the purpose of improving the crystallization speed, 1% by mass or less with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin, Preferably, you may mix | blend in the quantity of 0.6 mass part or less.

  More preferably, the reinforcing filler is surface-treated with a surface treatment agent such as a coupling agent. The glass fiber to which the surface treatment agent is attached is preferable because it is excellent in durability, heat and humidity resistance, hydrolysis resistance, and heat shock resistance.

As the surface treatment agent, any conventionally known one can be used. Specifically, for example, silane coupling agents such as amino silane, epoxy silane, allyl silane, and vinyl silane are preferable.
Among these, aminosilane-based surface treatment agents are preferable, and specifically, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable. Take as an example.

Moreover, as a surface treating agent, epoxy resins, such as a novolac type, a bisphenol A type epoxy resin, etc. are mentioned preferably. Among these, novolac type epoxy resins are preferable.
The silane-based surface treatment agent and the epoxy resin may be used alone or in combination, and it is also preferable to use both in combination.

  The content of the reinforcing filler is preferably 0 to 100 parts by mass with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. When the content of the reinforcing filler exceeds 100 parts by mass, the fluidity is lowered, which is not preferable. The more preferable content of the reinforcing filler is 5 to 90 parts by mass, of which 15 to 80 parts by mass, more preferably 30 to 80 parts by mass, and particularly 40 to 70 parts by mass.

  The resin composition used in the present invention can contain (A) a polybutylene terephthalate resin and (B) a thermoplastic resin other than the polycarbonate resin as long as the effects of the present invention are not impaired. . Specific examples of the other thermoplastic resins include polyethylene terephthalate, polyamide, polyphenylene oxide, polystyrene resin, polyphenylene sulfide ethylene, polysulfone, polyether sulfone, polyether imide, and polyether ketone.

[Method for Producing Resin Composition]
As a manufacturing method of the resin composition used for this invention, it can carry out in accordance with the conventional method of resin composition preparation. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Moreover, it is also possible to prepare the resin composition used in the present invention without mixing each component in advance, or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Furthermore, (A) a polybutylene terephthalate-based resin or (B) a polycarbonate resin partly blended with a part of other components is melt-kneaded to prepare a masterbatch, and then the remaining other ingredients May be blended and melt-kneaded.
In addition, when using fibrous reinforcement fillers, such as glass fiber, it is also preferable to supply from the side feeder in the middle of the cylinder of an extruder.

  The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. In order to suppress decomposition during kneading or molding in the subsequent process, it is desirable to use an antioxidant or a heat stabilizer.

[Molding]
The molded article of the present invention is a charger connector for an electric vehicle, a battery capacitor holder, a battery capacitor casing, or a casing for a charging stand for an electric vehicle, in which the above-described resin composition is molded.
The charger connector for an electric vehicle is a contact type connector for the charger for an electric vehicle used in the facility, which is charged in the facility provided with the charger when the amount of stored electricity decreases. The battery capacitor holder is a holder for holding a large-capacity capacitor as an emergency auxiliary power source separately from the charger (battery). The battery capacitor casing is a casing constituting the capacitor. The electric vehicle charging stand housing is a housing constituting a stand for charging the battery of the electric vehicle from a 100V or 200V AC power supply.
The shape, size, thickness and the like of these molded products are arbitrary.

  The method for producing the molded product using the resin composition is not particularly limited, and a molding method generally employed for the polyester resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. Of these, injection molding is preferred.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
In the following Examples and Comparative Examples, the components used are as shown in Table 1 below.

(Examples 1 to 5 , 7 to 9, 13 to 17, Reference Examples 6, 10 to 12 , Comparative Examples 1 and 2)
Each component shown in Table 1 was uniformly mixed with a tumbler mixer in the proportions (parts by mass) shown in Tables 2 to 4, and then a twin screw extruder (“TEX-30α” manufactured by Nippon Steel Works, L / D). = 52), the resin composition melt-kneaded under the conditions of a barrel set temperature of 250 ° C. and a screw speed of 200 rpm is rapidly cooled in a water tank, pelletized using a pelletizer, and pellets of a polybutylene terephthalate resin composition Got. The characteristics of the obtained pellets were cooled except for the evaluation of mold release property in the following (3) using an injection molding machine (Nissei Plastic Industry Co., Ltd., NEX80-9E) with a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. Evaluation of releasability at a time of 15 seconds and (3) was performed on a test piece injection molded under the condition of a cooling time of 20 seconds. In molding, the resin composition was dried at 120 ° C. for 6 to 8 hours until immediately before the molding.

(1) Impact resistance Charpy impact strength:
An ISO test piece (thickness: 4.0 mm) is injection-molded, and a 4.0 mm-thick notched test piece is produced from the test piece in accordance with the ISO 179 standard, and a notched Charpy impact strength (unit: kJ / m ^2). ) Was measured.
Surface impact strength:
A box-shaped molded product with a size of 150 x 80 x 40 mm (thickness 1.5 mmt) is molded, and a 2.975 kg steel ball is dropped from a predetermined height, and the height at which the molded product is completely destroyed is obtained. It was. It can be said that the higher the height at the time of complete destruction, the better the surface impact.

(2) Flame retardance A test piece for UL94 test (125 mm × 12.5 mm × 1.5 mmt) was molded, and V-0, V-1, and V-2 were determined in accordance with UL94 standards.
Also, a test piece for UL94 5V Bar test (125 mm × 12.5 mm × 3.0 mmt) and a test piece for 5V Plate test (150 mm × 150 mm × 3.0 mmt) were formed, and 5 VA, according to UL94 5V test, A determination of 5 VB was made.

(3) Formability Flowability (molding peak pressure):
The molding peak pressure when the ISO test piece was injection molded was measured.
Release properties:
The releasability at the time of injection-molding a box-shaped product (wall thickness: 1.5 mmt) having a size of 150 mm × 80 mm × 40 mm was evaluated. The molded product without the ejector pin mark was marked with “◯”, the molded product with the ejector pin mark marked with “Δ”, and the molded product with the ejector pin penetrating and cracked with “X”.

(4) Tensile strength ISO test pieces were injection-molded, and the tensile strength before and after the wet heat resistance test was measured under conditions of a tensile speed of 50 mm / min in accordance with the ISO 527 standard.
(5) Color difference The test pieces before and after the heat aging resistance test and the light resistance test were subjected to color difference measurement using “CE-7000A” (light source: D65, field of view: 10 °, method: SCI) manufactured by GretagMacbeth, and ΔE ^* Asked.

(6) Heat aging resistance test A plate molded product having a size of 100 mm x 100 mm x 3 mmt was injection-molded and left in a hot air oven at a temperature of 160 ° C for 100 hours.

(7) Light Resistance Test A molded product having a size of 100 mm × 100 mm × 3 mmt was injection-molded and subjected to light resistance treatment under the following conditions using a xenon weather tester.
Equipment used: Atlas Ci4000
Filter / Inner; Quartz Filter / Outer; Type S borosilicate Black panel temperature; 63 ° C
Irradiance: 0.55 W / m ² (at 340 nm)
Processing time: 1000 hours No rain Humidity; 50%

(8) Moisture and heat resistance test An ISO test piece was injection-molded and allowed to stand in a pressure cooker tester at a temperature of 121 ° C, a humidity of 100%, and a pressure of 2 atm for 50 hours.
The above evaluation results are shown in Tables 2 to 4 below.

  The molded article of the present invention includes a charger connector for an electric vehicle, a battery capacitor holder, a battery, and a molded resin composition having excellent impact resistance, flame resistance, heat aging resistance, light resistance, moisture and heat resistance, and moldability. It is a casing for a capacitor or a casing for a charging stand for an electric vehicle, and has a very high industrial applicability.

Claims (4)

(A) Polybutylene terephthalate-based resin and (B) polycarbonate resin based on a total of 100 parts by mass of (A) and (B), (A) being 50 to 80 parts by mass, and (B) being 20 to 50 parts by mass And (C) elastomer 5-20 parts by mass, (D) flame retardant 5-40 parts by mass, and (E) antimony compound 1-15 parts by mass, with respect to 100 parts by mass in total of (A) and (B). A resin composition that is an acrylic core / shell type graft copolymer that is an acrylic acid ester that contains an acrylic ester having an average particle size of 1 μm or less and containing neither silicone nor core. A molded product formed by molding, and is either a charger connector for an electric vehicle, a holder for a battery capacitor, a casing for a battery capacitor, or a casing for a charging stand for an electric vehicle. Molded article and features.   (B) The molded article according to claim 1, wherein the polycarbonate resin has a viscosity average molecular weight of 20000 or more.   (A) The intrinsic viscosity of polybutylene terephthalate resin is 0.9 dl / g or more, The molded article according to claim 1 or 2 characterized by things.   The molded product according to any one of claims 1 to 3, further comprising a polyolefin-based release agent.