JP2010037375A - Flame-retardant thermoplastic polyester resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant thermoplastic polyester resin composition and a molded article which are excellent in mechanical properties and flowability in injection molding and which generate little gases in high-temperature heating, and to provide a molded article which has high-level tracking resistance while maintaining the properties and which is useful as machine mechanism components, electrical and electronic components, or automobile components. <P>SOLUTION: The flame-retardant thermoplastic polyester resin composition includes formulating (A) 20-95 wt.% of a thermoplastic polyester resin, (B) 1-30 wt.% of a flame retardant consisting of at least one or more selected from phosphinates, diphosphinates, and polymers thereof, (C) 0.01-3 wt.% of an acid component neutralizer, and (D) 0.01-4 wt.% of a polyhydric alcohol compound containing at least one alkyleneoxide unit with three or more functional groups. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame-retardant thermoplastic polyester resin composition and a molded article which are excellent in mechanical properties and fluidity during injection molding and generate less gas during high-temperature heating.

  Thermoplastic polyester resins such as polybutylene terephthalate resins are utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of their excellent properties such as injection moldability and mechanical properties. Recently, mechanical mechanism parts, electrical / electronic parts, and automobile parts have a tendency to become more complex in shape, smaller, and thinner, with more advanced mechanical properties, fluidity during injection molding, Low gas properties are required.

  In addition, when a voltage is applied to a molded product or the like, the phenomenon that carbonization of the molded product proceeds and ignites is called tracking, but there are many molded products that are used at high voltages in thermoplastic polyester resins such as polybutylene terephthalate resin, for example, For molded products for circuit breakers, electromagnetic switches, and fixing machines of copying machines and printers, molded products having excellent flame resistance and high tracking resistance having a relative tracking index of 600 V or more are desired.

  Furthermore, thermoplastic polyester resins such as polybutylene terephthalate resins are inherently flammable, so they are generally used for industrial materials such as mechanical parts, electrical / electronic parts, and automotive parts. In addition to the balance of various characteristics, safety against flame, that is, flame retardancy is required, and high flame retardancy showing V-0 of UL-94 standard is often required.

  As a method of imparting flame retardancy to a thermoplastic polyester resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary is generally used. There was a problem that fluidity was lowered by the influence of the compound.

  In addition, due to increased environmental awareness, there is a concern about the environmental impact of halogen-based flame retardant materials. Therefore, in recent years, it has been strongly desired to use a non-halogen flame retardant containing no halogen.

  For example, Patent Document 1 and Patent Document 2 disclose that a phosphinate and a nitrogen-containing compound are blended as non-halogen flame retardants, but the molded product obtained by injection molding has mechanical properties, fluidity. There is a problem that the resistance and tracking resistance are inferior.

  Patent Document 3 discloses that an aromatic phosphate ester and melamine cyanurate are blended as a non-halogen flame retardant, but the molded product obtained by injection molding has a gas generation amount during high-temperature heating. There was a problem that there were many and poor fluidity.

Thus, in the technique proposed above, these problems cannot be solved, and the solution has been essential. Therefore, there has been a long-awaited development of a new technology that can solve the above-described problems and can satisfy the demands of recent mechanical mechanism parts, electrical / electronic parts, and automobile parts.
JP 11-60924 A JP 2004-263188 A Japanese Patent Laid-Open No. 3-281652

  An object of the present invention is to obtain a flame-retardant thermoplastic polyester resin composition and a molded article which are excellent in mechanical properties and fluidity during injection molding and generate less gas during high-temperature heating. An object of the present invention is to provide a molded article having high tracking resistance while being maintained and useful as a mechanical mechanism part, an electric / electronic part or an automobile part.

As a result of repeated studies to solve the above-described problems, the present inventors made (C) an acid component neutralizing agent and (C) an acid component neutralizing agent and ( D) The inventors have found that the above-mentioned problems can be solved by bringing a polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units within a specific range, and has reached the present invention. That is, the present invention for solving such a problem is characterized by the following configuration.
(1) (A) 20 to 95% by weight of a thermoplastic polyester resin, (B) 1 to 30% by weight of a flame retardant comprising at least one selected from phosphinates, diphosphinates and polymers thereof, (C) acid Difficulty of blending 0.01 to 4% by weight of a component neutralizing agent 0.01 to 3% by weight and (D) a polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units A flame-retardant thermoplastic polyester resin composition.
(2) The flame-retardant thermoplastic polyester resin composition according to (1), comprising 0.1 to 10% by weight of (E) a vinyl resin.
(3) The flame-retardant thermoplastic polyester resin composition according to (1) or (2), which comprises 1 to 50% by weight of (F) a flame-retardant aid.
(4) A molded article comprising the flame-retardant thermoplastic polyester resin composition according to any one of (1) to (3).
(5) A molded article having a relative tracking index of 600 V or more, comprising the flame-retardant thermoplastic polyester resin composition according to (2) or (3).

The various characteristics that are the effects of the present invention vary greatly depending on (C) the acid component neutralizing agent and (D) the polyhydric alcohol compound having one or more alkylene oxide units having three or more functional groups. Significant property improvements are seen when using compositions having (C) and (D) within the range.

  Hereinafter, the present invention will be described in detail.

  The (A) thermoplastic polyester resin of the present invention includes (a) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, and (c) a lactone. A polymer or copolymer having one or more selected from the above as a main structural unit.

Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.
Examples of the diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Group dioxy compounds, ie, 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and these Examples thereof include ester-forming derivatives.

  Polymers or copolymers containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as structural units include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene terephthalate. , Polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / Terephthalate, polybutylene isophthalate / terephthalate, poly Tylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfo Isophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / polytetramethylene glycol, polypropylene Terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol , Polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, poly Fragrances such as butylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate Group polyester resin, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, Polypropylene Sebakei , Polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, aliphatic polyester resins such as polybutylene succinate / adipate and the like.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Examples of the polymer or copolymer having these as a structural unit include polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyyoshide. Aliphatic polyester resins such as herbic acid can be mentioned.

  Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Examples of the polymer or copolymer having these as structural units include polycaprolactone. , Polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone, and the like.

  Among these, a polymer or copolymer having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative is preferable, and aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol. Alternatively, a polymer or copolymer having an ester-forming derivative as a main structural unit is more preferable, and an aliphatic diol selected from terephthalic acid or an ester-forming derivative thereof and ethylene glycol, propylene glycol, or butanediol or an ester-forming property thereof. A polymer or copolymer having a derivative as a main structural unit is more preferable, among which polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate. , Aromatic polyester resins such as polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate Is particularly preferable, and is most preferably one kind of aromatic polyester resin selected from polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene terephthalate, and two or more kinds of aromatic polyester resins can be mixed in any amount. It can also be used.

  In the present invention, the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer or copolymer having the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit is It is preferably 30 mol% or more, and more preferably 40 mol% or more.

In the present invention, a liquid crystalline polyester capable of forming anisotropy when melted may be used as the thermoplastic polyester resin. Examples of the structural unit of the liquid crystalline polyester include aromatic oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylenedioxy units, and aromatic iminooxy units. ) The blending amount of the thermoplastic polyester resin is 20 to 95% by weight, preferably 25 to 90% by weight, and more preferably 30 to 85% by weight. Sufficient moldability is obtained at 20% by weight or more, and good moldability and mechanical properties are obtained at 95% by weight or less.

  The carboxyl end group amount of the thermoplastic polyester resin (A) used in the present invention is preferably 50 eq / t or less, and preferably 30 eq / t or less, in terms of fluidity, hydrolysis resistance and heat resistance. More preferably, it is 20 eq / t or less, more preferably 10 eq / t or less. The lower limit is 0 eq / t.

In the present invention, the carboxyl end group amount of (A) thermoplastic resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.
The amount of hydroxyl terminal groups of the thermoplastic polyester resin (A) used in the present invention is preferably 50 eq / t or more, more preferably 80 eq / t or more, in terms of moldability and fluidity, and 100 eq / t is more preferably t or more, and particularly preferably 120 eq / t or more. The upper limit is 180 eq / t.

  The viscosity of the thermoplastic polyester resin (A) used in the present invention is in the range of 0.36 to 1.60 dl / g in terms of moldability when the o-chlorophenol solution is measured at 25 ° C. Is more preferable, and the range of 0.50 to 1.50 dl / g is more preferable.

  The molecular weight of the thermoplastic polyester resin (A) used in the present invention is preferably in the range of more than 8,000 and less than 500,000 in weight average molecular weight (Mw) in terms of heat resistance, and more than 8,000 and less than 300,000. Is more preferable, and more preferably in the range of more than 8000 and 250,000 or less. In the present invention, Mw of the polyester resin is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The method for producing the thermoplastic polyester resin (A) used in the present invention can be produced by a known polycondensation method or ring-opening polymerization method, and may be either batch polymerization or continuous polymerization. Although any of the reactions by direct polymerization can be applied, continuous polymerization is preferable in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased, and direct polymerization is performed in terms of cost. Is preferred.

  When (A) the thermoplastic polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof Can be produced by subjecting a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative to an esterification reaction or a transesterification reaction, followed by a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, Dibutyltin oxide, Methylphenyltin oxide, Tetraethyltin, Hexaethylditin oxide, Cyclohexahexylditin oxide, Didodecyltin oxide, Triethyltin hydroxide, Triphenyl Hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid Tin compounds such as alkylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide and antimony acetate, etc. Among these, organic titanium compounds and tin compounds are preferred, Furthermore, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are preferred, and titanic acid is preferred. Tetra -n- butyl ester are particularly preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin in terms of mechanical properties, moldability, and color tone, The range of -0.2 weight part is more preferable.

  The flame retardant comprising at least one or more selected from (B) phosphinic acid salts, diphosphinic acid salts and polymers thereof in the present invention includes phosphinic acid salts of the following formula (1), diphosphinic acid salts of the following formula (2) and It is a flame retardant composed of one or more of these polymers.

R1 and R2 in the formula are the same or different and are a C1 to C6 alkyl group or aryl group, which may be linear or branched, such as methyl, ethyl, propyl, isopropyl Group, n-butyl group, tert-butyl group, pentyl group, phenyl group and the like. R3 is a linear or branched C1-C10 alkylene group or a C6-C10 arylene group, an alkylarylene group, or an arylalkylene group, such as a methylene group, an ethylene group, a propylene group, an isopropylene group, n-butylene group, tert-butylene group, pentylene group, octylene group, dodecylene group, phenyl group, naphthylene group, methylphenylene group, ethylphenylene group, methylnaphthylene group, ethylnaphthylene group, tert-butylphenylene group, and tert-butyl group And a butylnaphthylene group.
M is calcium, aluminum or zinc. As M, aluminum is preferable. M is 1-4, n is 1-4, and x is 1-4.

  Examples of commercially available products include “Exolit” (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan. In addition, from the same company, a mixture containing the component (B), a nitrogen-containing compound and / or a boron-containing compound is also commercially available. Examples of commercially available products include OP1312, and OP1240 can be preferably used.

  In this invention, the compounding quantity of the flame retardant which consists of at least 1 or more types chosen from (B) phosphinate, diphosphinate, and these polymers is 1 to 30 weight%, 2 to 25 weight% is preferable, 3 to More preferred is 20% by weight. When the amount is 1% by weight or more, a sufficient flame retardant effect is obtained, and when the amount is 30% by weight or less, good mechanical properties are obtained.

  In the present invention, by adding (C) an acid component neutralizing agent, thermal decomposition and hydrolysis characteristics can be remarkably improved. (C) A flame retardant thermoplastic polyester resin composition that neutralizes the acid generated from the component (B), prevents hydrolysis of the component (A), and has excellent mechanical properties by blending an acid component neutralizer. The thing is presumed to have been obtained.

  (C) Preferred examples of the acid component neutralizing agent include compounds of alkaline earth metals such as magnesium, calcium and barium. Examples of the alkaline earth metal compounds include inorganic acid salts such as hydroxides, oxides, carbonates, sulfates, acetates, phosphates, acetates, lactates, oleic acids of alkaline earth metals. And organic acid salts such as palmitic acid, stearic acid, and montanic acid. Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate, Barium sulfate, magnesium phosphate, calcium phosphate, barium phosphate, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and magnesium of organic acids such as oleic acid, palmitic acid, stearic acid, montanic acid Salt, calcium salt, barium salt and the like can be mentioned. Among these, hydroxides and carbonates of alkaline earth metals are preferably used, particularly magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably used. Such alkaline earth metals can be used alone or in combination of two or more. In addition, calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk), etc. are known depending on the production method. Can be used for invention. These alkaline earth metal compounds may be treated with one or more surface treatment agents selected from silane coupling agents, organic substances, inorganic substances, etc., and the shape may be powder, plate or fiber Although it does not matter, it is preferable from the viewpoint of dispersibility to use it in a powder form of 10 μm or less. Further, if the particle size is fine, the effect of improving hydrolyzability is large and preferable.

  Moreover, the compounding quantity of the (C) acid component neutralizing agent in this invention is 0.01-3 weight%, 0.02-2.5 weight% is preferable and 0.03-2 weight% is more preferable. . The effect of neutralizing the acid component is sufficiently obtained at 0.01% by weight or more, and good mechanical properties are obtained at 5% by weight or less.

  In the present invention, the component (B) used as a flame retardant does not melt sufficiently even when heated to around 300 ° C., which is the processing temperature of the flame retardant thermoplastic polyester resin composition of the present invention. Reduces fluidity during processing. Therefore, in the present invention, for the purpose of improving fluidity during molding such as injection molding, (D) a polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units is blended. It is necessary.

  The (D) polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units may be a low molecular compound, a polymer, a trifunctional compound, Any polyhydric alcohol compound having one or more alkylene oxide units having three or more functional groups such as a tetrafunctional compound and a pentafunctional compound is preferably used. The functional groups of three or more functional groups are a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, It is preferably at least one selected from a silanol group and a silyl ether group, more preferably three or more functional groups that are the same or different from these groups, particularly fluidity, mechanical properties, More preferably, they are the same functional group in terms of durability, heat resistance, and productivity. (D) An alkylene of a polyhydric alcohol compound having one or more alkylene oxide units having three or more functional groups. As a preferred example of the oxide unit, an aliphatic alkylene oxide unit having 1 to 4 carbon atoms is effective. And methylene oxide units, ethylene oxide units, trimethylene oxide units, propylene oxide units, tetramethylene oxide units, 1,2-butylene oxide units, 2,3-butylene oxide units or isobutylene oxide units. In the invention, it is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit, particularly in terms of excellent fluidity, recyclability, durability, heat resistance and mechanical properties. It is particularly preferable to use a compound containing a propylene oxide unit from the viewpoint of excellent properties and toughness (tensile elongation at break), and the number of alkylene oxide units is monofunctional in terms of excellent fluidity and mechanical properties. Base Preferably the alkylene oxide units is 0.1 to 20, more preferably from 0.5 to 10, more preferably from 1 to 5.

  In addition, as a preferred example of a polyhydric alcohol compound having (D) three or more functional groups and containing one or more alkylene oxide units, when the functional group is a hydroxyl group, (poly) oxymethylene glycerin, (poly) oxy Ethylene glycerol, (poly) oxytrimethylene glycerol, (poly) oxypropylene glycerol, (poly) oxyethylene- (poly) oxypropylene glycerol, (poly) oxytetramethylene glycerol, (poly) oxymethylene diglycerol, (poly) Oxyethylene diglycerin, (poly) oxytrimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylenetrimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpro , (Poly) oxypropylene trimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethylene Ditrimethylolpropane, (poly) oxytrimethyleneditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly ) Oxypropylene pentaerythritol, (poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol Ritol, (Poly) oxymethylene dipentaerythritol, (Poly) oxyethylene dipentaerythritol, (Poly) oxytrimethylene dipentaerythritol, (Poly) oxypropylene dipentaerythritol, (Poly) oxymethylene glucose, (Poly) oxy Examples thereof include ethylene glucose, (poly) oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, and (poly) oxytetramethylene glucose.

  (D) As a preferred example of a polyhydric alcohol compound having three or more functional groups and containing at least one alkylene oxide unit, when the functional group is a carboxylic acid, propane-containing a (poly) methylene oxide unit 1,2,3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) trimethylene oxide units, (poly) Propane-1,2,3-tricarboxylic acid containing propylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) tetramethylene oxide units, 2-methylpropane-1 containing (poly) methylene oxide units , 2,3-Triscarboxylic acid, 2-methylpropane-1,2,3-toe containing (poly) ethylene oxide units Sucarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) trimethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) propylene oxide units, Contains 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) tetramethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) methylene oxide units, and (poly) ethylene oxide units Butane-1,2,4-tricarboxylic acid, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, Butane-1,2,4-tricarboxylic acid containing (poly) tetramethylene oxide units, (poly) methylene oxide -Containing butane-1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) ethylene oxide units, butane-1 containing (poly) trimethylene oxide units , 2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, butane-1,2,3 containing (poly) tetramethylene oxide units 4-tetracarboxylic acid, trimellitic acid containing (poly) methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) trimethylene oxide units, including (poly) propylene oxide units Trimellitic acid, trimellitic acid containing (poly) tetramethylene oxide units, trimellitic acid containing (poly) methylene oxide units Mesic acid, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) trimethylene oxide units, trimesic acid containing (poly) propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, (poly ) Hemimellitic acid containing methylene oxide units, Hemimellitic acid containing (poly) ethylene oxide units, Hemimellitic acid containing (poly) trimethylene oxide units, Hemimellitic acid containing (poly) propylene oxide units, (Poly) tetra Hemimellitic acid containing methylene oxide units, pyromellitic acid containing (poly) methylene oxide units, pyromellitic acid containing (poly) ethylene oxide units, pyromellitic acid containing (poly) trimethylene oxide units, (poly) propylene oxide Including units Romellitic acid, pyromellitic acid containing (poly) tetramethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) methylene oxide units, cyclohexane-1,3,5-containing (poly) ethylene oxide units Tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid containing (poly) trimethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide units, (poly) tetramethylene oxide units Examples thereof include cyclohexane-1,3,5-tricarboxylic acid.

  In addition, as a preferred example of the polyhydric alcohol compound (D) having three or more functional groups and containing one or more alkylene oxide units, when the functional group is an amino group, 1,2 containing (poly) methylene oxide units , 3-triaminopropane, 1,2,3-triaminopropane containing (poly) ethylene oxide units, 1,2,3-triaminopropane containing (poly) trimethylene oxide units, (poly) propylene oxide units 1,2,3-triaminopropane containing, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) methylene oxide units , 1,2,3-triamino-2-methylpropane containing (poly) ethylene oxide units, (poly) trimethylene oxide alone 1,2,3-triamino-2-methylpropane containing, 1,2,3-triamino-2-methylpropane containing (poly) propylene oxide units, 1,2,3 containing (poly) tetramethylene oxide units -Triamino-2-methylpropane, 1,2,4-triaminobutane containing (poly) methylene oxide units, 1,2,4-triaminobutane containing (poly) ethylene oxide units, (poly) trimethylene oxide units 1,2,4-triaminobutane containing 1,2,4-triaminobutane containing (poly) propylene oxide units, 1,2,4-triaminobutane containing (poly) tetramethylene oxide units, 1,2,3,4-tetraminobutane containing poly) methylene oxide units, 1,2,3,4-containing (poly) ethylene oxide units Tolaminobutane, 1,2,3,4-tetraminobutane containing (poly) trimethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) propylene oxide units, including (poly) tetramethylene oxide units 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane containing (poly) methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, (poly) tri 1,3,5-triaminocyclohexane containing methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triamino containing (poly) tetramethylene oxide units Cyclohexane, 1,2,4-triaminocyclo containing (poly) methylene oxide units Hexane, 1,2,4-triaminocyclohexane containing (poly) ethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) trimethylene oxide units, 1,2,4 containing (poly) propylene oxide units 4-triaminocyclohexane, 1,2,4-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) methylene oxide units, (poly) ethylene oxide units 1,2,4,5-tetraminocyclohexane containing, 1,2,4,5-tetraminocyclohexane containing (poly) trimethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) propylene oxide units , 1,2 containing (poly) tetramethylene oxide units 4,5-tetraminocyclohexane, 1,3,5-triaminobenzene containing (poly) methylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, (poly) trimethylene oxide units 1,3,5-triaminobenzene containing, 1,3,5-triaminobenzene containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, (poly ) 1,2,4-triaminobenzene containing methylene oxide units, 1,2,4-triaminobenzene containing (poly) ethylene oxide units, 1,2,4-triamino containing (poly) trimethylene oxide units Benzene, 1,2,4-triaminobenzene containing (poly) propylene oxide units, (poly) tetramethyl Including N'okishido units 1,2,4-aminobenzene, and the like.

  Further, (D) as a preferred example of a polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units, when the functional group is an ester group, an aliphatic acid ester or an aromatic acid ester, Examples include ester derivatives.

  Moreover, (D) As a preferable example of the polyhydric alcohol compound which has one or more alkylene oxide units which has a 3 or more functional group, when a functional group is an amide group, an amide derivative etc. are mentioned.

  In addition, from the viewpoint of the fluidity of the flame-retardant polyester resin composition, (D) as a particularly preferable example of a polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units, the functional group is a hydroxyl group. In the case of (poly) oxyethylene glycerol, (poly) oxypropylene glycerol, (poly) oxyethylene diglycerol, (poly) oxypropylene diglycerol, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylol Propane, (poly) oxyethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, (poly Oxypropylene dipentaerythritol, and when the functional group is a carboxylic acid, propane-1,2,3-tricarboxylic acid containing a (poly) ethylene oxide unit, propane-1,2, containing a (poly) propylene oxide unit 3-tricarboxylic acid, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) propylene oxide units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, ( Examples thereof include cyclohexane-1,3,5-tricarboxylic acid containing a poly) ethylene oxide unit and cyclohexane-1,3,5-tricarboxylic acid containing a (poly) propylene oxide unit. When the functional group is an amino group, (poly) 1,2,3-toe containing ethylene oxide units Aminopropane, 1,2,3-triaminopropane containing (poly) propylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3 containing (poly) propylene oxide units Examples include 5-triaminocyclohexane, 1,3,5-triaminobenzene containing a (poly) ethylene oxide unit, and 1,3,5-triaminobenzene containing a (poly) propylene oxide unit.

  The polyhydric alcohol compound having one or more alkylene oxide units (D) having three or more functional groups used in the present invention reacts with (A) the thermoplastic polyester resin, and the main chain and side of the component (A) You may introduce | transduce into the chain | strand and may keep the structure at the time of mixing | blending, without reacting with (A) component.

  The viscosity of the polyhydric alcohol compound (D) having three or more functional groups and containing one or more alkylene oxide units used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and has fluidity and mechanical properties. From this point, it is more preferably 5000 m · Pa or less, and particularly preferably 2000 m · Pa or less. Although there is no particular lower limit, it is preferably 100 m · Pa or more from the viewpoint of bleeding property during molding. When the viscosity at 25 ° C. is larger than 15000 m · Pa, the fluidity improving effect is insufficient, which is not preferable.

  (D) The molecular weight or weight average molecular weight (Mw) of the polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units used in the present invention is gel permeation using hexafluoroisopropanol as a solvent. The value measured by chromatography (GPC) and quantified in terms of polymethyl methacrylate (PMMA) is preferably in the range of 50 to 10,000, and in the range of 150 to 8,000 in terms of fluidity. Is more preferable, and the range of 200 to 6000 is even more preferable.

  The moisture content of the polyhydric alcohol compound having at least one alkylene oxide unit (D) having three or more functional groups used in the present invention is preferably 1% or less. More preferably, the moisture content is 0.5% or less, even more preferably 0.1% or less, and there is no particular lower limit of moisture content. A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.

  In the present invention, (D) the blending amount of the polyhydric alcohol compound having one or more alkylene oxide units having three or more functional groups is 0.01 to 4% by weight, and 0.05 to 3% by weight. Preferably, 0.1 to 2% by weight is more preferable. When the amount is 0.01% by weight or more, the effect of improving fluidity is sufficiently obtained, and when the amount is 4% by weight or less, good mechanical properties are obtained.

  The (E) vinyl-based resin in the present invention is blended in the resin composition of the present invention for the purpose of improving electrical characteristics such as tracking resistance, arc resistance and voltage resistance characteristics. In addition, the vinyl resin containing a rubber component in the vinyl resin of the present invention (E) is preferably used as a material having an effect of improving toughness such as the above-described electrical characteristics and impact strength.

  In the present invention, the relative tracking index of a molded article made of the flame-retardant thermoplastic polyester resin composition containing the (E) vinyl-based resin is preferably 600 V or more from the viewpoint of electrical characteristics.

  As the (E) vinyl resin in the present invention, one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, and maleimide monomers are used. Polymerized resins, or those obtained by graft polymerization of these monomers to rubber components such as polybutadiene rubber, or those obtained by copolymerization, can be mentioned. Aromatic vinyl compounds, vinyl cyanide compounds, (meth ) A graft polymer containing 50% by weight or more of one or more monomer components selected from the group consisting of alkyl acrylates and maleimide monomers, or a copolymerized vinyl resin These may be collectively referred to as “(co) polymer”).

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and divinylbenzene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the (meth) acrylic acid alkyl ester, Examples include (meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate. Examples of the body include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. In addition, vinyl resins with the following components that can be copolymerized with the above vinyl resins can also be used in the present invention. Specific examples of components capable of such copolymerization include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers.

  (E) Examples of preferred (co) polymers of vinyl resins include polymethyl methacrylate, methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, styrene / N- Vinyl (co) polymers such as phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high Impact-Styrenic resin modified with a rubbery polymer such as polystyrene resin, and styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene as block copolymer / Styrene resin, etc. are mentioned, in particular, polystyrene resin and acrylonitrile / styrene resin are preferable, and acrylonitrile / styrene copolymer, which is a copolymer obtained by copolymerizing acrylonitrile and styrene, is more preferable. Indicates polymerization).

  The acrylonitrile / styrene resin is particularly preferably an acrylonitrile / styrene resin containing acrylonitrile in an amount of 10 wt% to less than 50 wt%.

  Further, (E) a vinyl resin obtained by graft polymerization or copolymerization of an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride, or an epoxy group-containing vinyl monomer with a vinyl resin may be used. . Of these, vinyl resins obtained by graft polymerization or copolymerization of unsaturated acid anhydrides or epoxy group-containing vinyl monomers are preferable.

  The unsaturated acid anhydrides are compounds that share both a vinyl group capable of radical polymerization and an acid anhydride in one molecule, and preferred examples include maleic anhydride.

  In addition, the epoxy group-containing vinyl monomer is a compound that shares both radically polymerizable vinyl group and epoxy group in one molecule, and specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, Examples include glycidyl esters of unsaturated organic acids such as glycidyl itaconate, glycidyl ethers such as allyl glycidyl ether, and the above derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. it can. Moreover, these can be used individually or in combination of 2 or more types.

  The amount of unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride or epoxy group-containing vinyl monomer used for graft polymerization or copolymerization is 0.05 to (E) vinyl resin. It is preferable that it is weight% or more. Copolymerization in a large amount tends to decrease fluidity and gelation, and is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.

  Further, (E) a vinyl resin that is epoxy-modified with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid may be used. In this case, it is preferable that a diene monomer is randomly copolymerized or block copolymerized with the vinyl resin in order to effectively perform the epoxy modification. As examples of diene monomers, butadiene, isoprene and the like are preferably used. Examples of suitable methods for producing these epoxy-modified vinyl resins are disclosed in JP-A-6-256417, JP-A-6-220124 and the like.

  Moreover, (E) vinyl-type resin which consists of a multilayer structure is also used preferably. The multilayer structure is formed of an innermost layer (core layer) and one or more outer layers (shell layer) covering the innermost layer (core layer), and (E) a vinyl-based resin is configured as one type of outer layer (shell layer). A polymer having a so-called core-shell type structure in which adjacent layers are composed of different polymers is preferable.

  The number of layers constituting the multilayer structure is not particularly limited, and may be two or more.

  The multilayer structure is preferably a multilayer structure having at least one rubber layer inside.

  In the multilayer structure, the type of the rubber layer is not particularly limited as long as it is composed of a polymer component having rubber elasticity. For example, rubber composed of a polymer obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, or the like can be given. Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, acrylonitrile units, It is a rubber constituted by polymerizing a nitrile component such as a methacrylonitrile unit and a conjugated diene component such as a butanediene unit or an isoprene unit. A rubber composed of a combination of two or more of these components and copolymerized is also preferably used.

  In the multilayer structure, the outer layer (shell layer) is composed of (E) vinyl resin, and includes polymethyl methacrylate, methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / Vinyl-based (co) polymers such as butadiene resin, styrene / N-phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene Resin (MABS resin), high impact-styrene resin modified with rubber polymer such as polystyrene resin, and block copolymer as styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, For example, polystyrene resin and acrylonitrile / styrene resin are preferably used. (E) Unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides for vinyl resins Alternatively, a vinyl resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer, or (E) a vinyl resin with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid. Epoxy-modified vinyl resin may be used.

  Preferred examples of the multilayer structure include those in which the core layer is a dimethylsiloxane / butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer, and the core layer is a butanediene / styrene polymer. In which the outermost layer is a methyl methacrylate polymer or acrylonitrile / styrene copolymer, and the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer. Can be mentioned. Furthermore, it is more preferable that either one or both of the rubber layer and the outermost layer is a polymer containing glycidyl methacrylate units.

  In the multilayer structure, the weight ratio of the core to the shell is not particularly limited, but the core layer is preferably 10 parts by weight or more and 90 parts by weight or less with respect to the entire multilayer structure polymer. Furthermore, it is more preferably 30 parts by weight or more and 80 parts by weight or less.

  Moreover, as a multilayer structure, the commercial item which satisfy | fills above-described conditions may be used, and it can also produce and use by a well-known method.

  Commercially available multilayer structures include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kane Ace” manufactured by Kaneka Chemical Industry Co., “Paraloid” manufactured by Kureha Chemical Industry Co., Ltd., “Acryloid” manufactured by Rohm and Haas Co., Ltd., Takeda Examples thereof include “STAPHYLOID” manufactured by Yakuhin Kogyo Co., Ltd. and “Parapet SA” manufactured by Kuraray Co., Ltd. These may be used alone or in combination of two or more.

  Moreover, 0.1-10 weight% is preferable, as for the compounding quantity of (E) vinyl-type resin of this invention, 0.5-9 weight% is more preferable, and 1-8 weight% is especially preferable. When the content is 0.1% by weight or more, electrical characteristics and toughness are improved, and when the content is 10% by weight or less, good flame retardancy is obtained.

  In addition, the flame retardant aid (F) of the present invention is combined with a flame retardant consisting of at least one or more selected from (B) phosphinic acid salts, diphosphinic acid salts and polymers thereof, thereby providing flame retardancy. For the purpose of improving, a flame retardant aid can be blended.

  In the present invention, the relative tracking index of the molded article made of the flame retardant thermoplastic polyester resin composition containing the (F) flame retardant aid is preferably 600 V or more from the viewpoint of electrical characteristics.

  The flame retardant aid (F) of the present invention is selected from a nitrogen compound flame retardant, an inorganic flame retardant, a silicone flame retardant, a phenol resin, and a phosphorus flame retardant other than the component (B) or a fluorine resin described later. One or more flame retardant aids. The nitrogen-based flame retardant, the inorganic flame retardant, and the phosphorus-based flame retardant other than the component (B) form an effect of absorbing heat generated during combustion and a carbonized layer to prevent combustion. In addition, the silicone flame retardant and the phenol resin exhibit the effect of a flame retardant aid in a small amount because the silicone flame retardant and the phenol resin move to the surface of the molded product due to the heat of combustion and prevent combustion from the molded product surface. However, blending in a large amount is not preferred because the mechanical properties are significantly reduced.

  The compounding amount of the nitrogen-based flame retardant, the inorganic flame retardant, and the phosphorus flame retardant other than the component (B) of the flame retardant auxiliary (F) of the present invention is preferably 1 to 50% by weight, and 2 to 45% by weight. % Is more preferable, and 3 to 40% by weight is particularly preferable. When the content is 1% by weight or more, good flame retardancy is obtained, and when it is 50% by weight or less, good mechanical properties are obtained.

  The blending amount of the silicone-based flame retardant (F) flame retardant aid of the present invention and the phenol resin is preferably 0.1 to 5% by weight, more preferably 0.2 to 4% by weight, and 0.3 to 3% by weight. % Is particularly preferred. When the amount is 1% by weight or more, good flame retardancy is obtained, and when it is 3% by weight or less, good mechanical properties are obtained.

  Examples of the nitrogen compound flame retardant include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides and aromatic amides, urea and thiourea.

  Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like.

Examples of the aromatic amine include aniline and phenylenediamine.
Examples of the nitrogen-containing heterocyclic compound include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and a triazine compound.

Examples of the cyan compound include dicyandiamide. Examples of the aliphatic amide and aromatic amide include N, N-dimethylacetamide and N, N-diphenylacetamide.

  The triazine compound exemplified in the nitrogen-containing heterocyclic compound is a nitrogen-containing heterocyclic compound having a triazine skeleton, and includes triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, and triazine. Examples thereof include phenyltriazine, amelin, amellide, thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine, and melamine cyanurate and melamine isocyanurate are preferably used. As the melamine cyanurate or melamine isocyanurate, an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and usually has a composition of 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio). The adduct which has can be mentioned. Although it is produced by a known method, for example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form. The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. When the dispersibility is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as a metal oxide such as polyvinyl alcohol and silica may be used in combination. The average particle size before blending with the resin is preferably 100 to 0.1 μm, preferably 50 to 0.5 μm, more preferably from the viewpoint of flame retardancy, mechanical strength, and surface properties of the molded product. Is 10 to 1 μm, and the average particle size is an average particle size measured with a 50% cumulative particle size by the laser micron sizer method. MC-4000, MC-6000 manufactured by Nissan Chemical Co., Ltd. is preferably used. .

  Examples of the inorganic flame retardant include magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, Tin oxide salt, zinc sulfate, zinc oxide, calcium borate hydrate, zinc borate, zinc borate hydrate, zinc hydroxide ferrous oxide, ferric oxide, stannous oxide, stannic oxide, boric acid Ammonium, ammonium octamolybdate, metal salt of tungstic acid, complex oxide acid of tungsten and metalloid, ammonium sulfamate, zirconium compound, guanidine compound, hydrotalcite, graphite, swellable graphite, etc. , Surface treatment with a fatty acid or a silane coupling agent, etc. , Swellable graphite are preferred.

Examples of the silicone flame retardant include silicone resin and silicone oil. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.

  The above-mentioned phenol resin is effective as a flame retardant aid that moves to the surface during combustion and assists the formation of a carbonized layer. The above phosphorus flame retardant, nitrogen compound flame retardant, silicone flame retardant and other inorganic flame retardants It is preferably used in combination with at least one selected from flame retardants. Further, the phenol resin is arbitrary as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak-type, resol-type and thermal reaction-type resins, and resins obtained by modifying these. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Among these, novolak-type phenol resins or melamine-modified novolak-type phenol resins which are non-thermally reactive with no addition of a curing agent are preferred in terms of flame retardancy, mechanical properties and economy.

  Further, the shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, liquids, and the like can be used, and one or more can be used as necessary. The phenolic resin is not particularly limited, and commercially available ones are used. For example, in the case of a novolak type phenol resin, the reaction vessel is charged with a molar ratio of phenols to aldehydes of 1: 0.7 to 1: 0.9, and further oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfone. After adding a catalyst such as an acid, the mixture is heated and refluxed for a predetermined time. In order to remove the produced water, it can be obtained by a method of vacuum dehydration or standing dehydration and further removing remaining water and unreacted phenols. These resins or co-condensed phenol resins obtained by using a plurality of raw material components can be used alone or in combination of two or more.

  In the case of a resol type phenol resin, the molar ratio of phenols to aldehydes is charged into the reaction vessel at a ratio of 1: 1 to 1: 2, and sodium hydroxide, aqueous ammonia, other basic substances, etc. After adding the catalyst, it can be obtained by the same reaction and treatment as the novolak type phenol resin.

  Here, as phenols, phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy Examples include phenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol. These phenols can be used singly or in combination. On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can be used alone or in combination of two or more as required.

  The molecular weight of the phenol resin is not particularly limited, but is preferably 200 to 2,000 in terms of number average molecular weight, and particularly preferably in the range of 400 to 1,500 because of excellent mechanical properties, fluidity, and economy. The molecular weight of the phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a polystyrene standard sample.

  The phosphorus-based flame retardant other than the component (B) is a phosphorus-based flame retardant containing a phosphorus component, and includes an aromatic phosphate compound, a phosphazene compound, a phosphaphenanthrene compound, red phosphorus, a phosphate ester amide, and Examples thereof include ammonium polyphosphate, and one or more phosphorus flame retardants selected from aromatic phosphate ester compounds, phosphazene compounds, and phosphaphenanthrene compounds are particularly preferably used.

  Examples of the aromatic phosphate compound include triphenyl phosphate, tris (dimethylphenyl) phosphate, trixylenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl dixylenyl phosphate, trimethyl phosphate, triethyl phosphate and Condensed phosphoric acid esters and the like can be mentioned, and the condensed phosphoric acid ester is preferably used because it is hydrolyzable and generates less gas at high temperature, and its commercial products include PX-202, CR- manufactured by Daihachi Chemical Industry Co., Ltd. 741, PX-200, PX-201, Adeka Co., Ltd. FP-500, FP-600, FP-700, PFR, etc. can be used.

  The phosphazene compound is a phosphonitrile linear polymer and / or a cyclic polymer, and in particular, those mainly composed of a linear phenoxyphosphazene are preferably used, and the phosphonitrile linear polymer and / or the cyclic polymer are used. Can be synthesized by known methods described in the author Sugawara “Synthesis and Application of Phosphazene Compounds”, for example, phosphorus pentachloride or phosphorus trichloride as a phosphorus source, ammonium chloride or ammonia gas as a nitrogen source. It can be synthesized by reacting by a known method (the cyclic product may be purified) and substituting the obtained substance with alcohol, phenol and amines. “Ravitor” manufactured by Fushimi Pharmaceutical Co., Ltd. FP-110 or the like is preferably used.

  The phosphaphenanthrene compound is a phosphorus-based flame retardant having at least one phosphophenanthrene skeleton in the molecule, and commercially available products include HCA, HCA-HQ, BCA, SANKO- manufactured by Sanko Co., Ltd. 220, M-Ester, etc. are mentioned. In particular, M-Ester can be expected to undergo reaction between the terminal hydroxyl group and the end of (A) thermoplastic polyester resin at the time of melt kneading, and is effective in suppressing bleed out under high temperature and high humidity. Preferably used.

  The above-mentioned phosphoric ester amide is an aromatic amide flame retardant containing phosphorus atom and nitrogen atom, and is a powdery substance at room temperature having a high melting point, excellent handling property at the time of blending, and having a heat distortion temperature. A high flame-retardant polyester resin is obtained, and as a commercial product, SP-703 manufactured by Shikoku Kasei Co., Ltd. is preferably used.

Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and carbamyl polyphosphate ammonium, and the like, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, and urea resin exhibiting thermosetting properties. It may be covered with a thermosetting resin such as, and may be used alone or in combination of two or more.

Examples of the melamine polyphosphate include melamine phosphate, melamine pyrophosphate, and melamine polyphosphate such as melamine, melam, and phosphate with melem, which may be used alone or in combination of two or more. “MPP-A manufactured by Sanwa Chemical Co., Ltd., PMP-100 and PMP-200 manufactured by Nissan Chemical Co., Ltd. are preferably used. The red phosphorus is not only untreated red phosphorus but also thermosetting. Red phosphorus treated with at least one compound film selected from the group consisting of a resin film, a metal hydroxide film, and a metal plating film can be preferably used as the thermosetting resin of the thermosetting resin film. Any resin capable of coating red phosphorus can be used without limitation, for example, phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin. The metal hydroxide coating is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide, and the like. The metal of the metal plating film is not particularly limited as long as it is a resin capable of coating red phosphorus, such as Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, or alloys thereof. Furthermore, these coating films may be used in combination of two or more kinds, or may be laminated in two or more kinds.

  Further, in the present invention, a fluorine-based resin can be blended for the purpose of suppressing melting and dropping of the flame-retardant resin composition at the time of combustion and further improving flame retardancy. Treated as one of the fuel aids.

  The fluorine-based resin is a resin containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetra (Fluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer , Polyvinylidene fluoride are preferable, polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

  Moreover, the compounding quantity of a fluororesin is 0.05 to 5 weight% from a flame-resistant viewpoint, Preferably it is 0.1 to 3 weight%, More preferably, it is 0.15 to 2 weight%.

  In the present invention, another resin can be used in combination with the mixture of the thermoplastic polyester resin (A) and the vinyl resin (E). The other resin is a resin that can improve any of flame retardancy, molding processability, heat resistance, or bleed-out characteristics even in a high-temperature and high-humidity atmosphere, or a resin that can improve toughness such as impact strength. Although either a thermoplastic resin or a thermosetting resin can be used, a thermoplastic resin other than the thermoplastic polyester resin is preferable from the viewpoint of moldability. Specific examples of resins other than thermoplastic polyester resins include low-density polyethylene resins, high-density polyethylene resins, polyolefin resins such as polypropylene resins, liquid crystal polyester resins, polyamide resins, polyacetal resins, polyurethane resins, aromatic and aliphatic polyketones. Resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, thermoplastic starch resin, polyurethane resin, aromatic polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene ether resin, poly-4 -Methylpentene-1, polyetherimide resin, cellulose acetate resin, unsaturated polyester resin, melamine resin, urea resin, etc. can be mentioned.

  In addition to the above, the other resin includes ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, natural rubber, thiocol rubber, polysulfide rubber, polyether. Examples include rubber, epichlorohydrin rubber, ethylene-modified acid anhydrides such as maleic anhydride, glycidyl methacrylate, and modified olefin resins epoxy-modified with an epoxidizing agent. And those having a microstructure such as a cis structure or a trans structure. Examples of the modified olefin resin epoxy-modified with ethylene, such as acid anhydride such as maleic anhydride, glycidyl methacrylate and epoxidizing agent, include ethylene / glycidyl methacrylate, ethylene / butene-1 / maleic anhydride, ethylene / propylene / Specific examples include maleic anhydride, ethylene / maleic anhydride, and epoxidized olefin resin obtained by epoxidizing ethylene with a peroxide. Examples of commercially available products include “bond first” manufactured by Sumitomo Chemical Co., Ltd. “E” and the like. Here, the various copolymers, polymers and rubbers mentioned in the above specific examples may be any of random copolymers, block copolymers, graft copolymers and the like. It may be used or two or more types may be used in combination.

  Among the other resins, since the improvement effect is high in any of mechanical properties, flame retardancy, and impact strength, aromatic polycarbonate resin, glycidyl methacrylate, and modified olefin resin modified with an epoxidizing agent are particularly used. Preferably, it is used by 1 or more types.

  The blending amount of the other resin used in the present invention is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and further 3 to 40% by weight from the viewpoints of mechanical properties, flame retardancy and impact strength. preferable.

  In the present invention, a release agent can be blended. The mold release agent of the present invention is a component that improves mold release during injection molding.

  Moreover, 0.01-3 weight% is preferable, when adding a mold release agent, 0.02-2 weight% is more preferable, 0.03-1 weight% is further more preferable. When the amount is 0.02% by weight or more, a sufficient releasability effect is obtained, and when the amount is 2% by weight or less, good mechanical properties are obtained.

  In the present invention, a fiber reinforcing material can be blended for the purpose of improving the mechanical strength. Specific examples of the fiber reinforcing material include glass fiber, aramid fiber, and carbon fiber. The above glass fiber is a chopped strand type or roving type glass fiber, such as a silane coupling agent such as an aminosilane compound or an epoxysilane compound, and / or urethane, vinyl acetate, bisphenol A diglycidyl ether, a novolac epoxy compound, or the like. Glass fibers treated with a sizing agent containing one or more epoxy compounds and the like are preferably used, and the silane coupling agent and / or sizing agent may be used in an emulsion liquid. The fiber diameter is 1 to 30 μm, preferably 5 to 15 μm. In addition, although the fiber cross section is circular, a fiber reinforcing material having an arbitrary cross section such as an elliptical glass fiber, a flat glass fiber and an eyebrow-shaped glass fiber having an arbitrary aspect ratio can be used. It is characterized by improved fluidity at the time and a molded product with less warping.

The blending amount of the fiber reinforcement is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, from the viewpoint of fluidity during injection molding and durability of the injection molding machine or mold, and 3 to 40%. Weight percent is particularly preferred. ,
Further, in the present invention, an inorganic filler other than the fiber reinforcing material can be further blended, and the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy, or thermal deformation of the molded product of the present invention. This is to improve a part of the temperature and the like, and in particular, since it is effective in anisotropy, a molded product with less warping can be obtained. Examples of inorganic fillers other than the fiber reinforcement include, but are not limited to, needle-like, granular, powdery and layered inorganic fillers. Specific examples include glass beads, milled fibers, glass flakes, Potassium titanate whisker, calcium sulfate whisker, wollastonite, silica, kaolin, talc, smectite clay mineral (montmorillonite, hectorite), vermiculite, mica, fluorine teniolite, zirconium phosphate, titanium phosphate, dolomite, etc. Used above. In particular, when gas beads, glass flakes, kaolin, talc, and mica are used, a molded product with less warpage can be obtained because of the effect of anisotropy.

  Moreover, surface treatments such as a coupling agent treatment, an epoxy compound, or an ionization treatment may be performed on the inorganic filler other than the fiber reinforcement. The average particle size of the granular, powdery and layered inorganic fillers is preferably 0.1 to 20 μm, particularly preferably 0.2 to 10 μm from the viewpoint of impact strength. In addition, the amount of inorganic filler other than fiber reinforcement is not more than 50% by weight in combination with the amount of fiber reinforcement in terms of fluidity during molding and durability of the molding machine and mold. From the viewpoint of fluidity of time, it is preferable.

  In the present invention, an epoxy compound can be blended for the purpose of improving hydrolyzability, and examples thereof include glycidyl ester compounds, glycidyl ether compounds, and glycidyl ester ether compounds, which can be used singly or in combination. .

  Moreover, the compounding quantity of an epoxy compound is 0.01 to 3 weight% from a viewpoint of a hydrolyzable improvement, 0.02 to 2 weight% is more preferable, and 0.03 to 1 weight% is especially preferable.

  In the present invention, for the purpose of further improving hydrolysis resistance, an oxazoline compound, a carbodiimide-modified isocyanate compound, a carbodiimide compound, and the like can be blended, and may be used alone, but in a blending amount not exceeding the above epoxy compound. It is preferable to use in combination with an epoxy compound.

  In the present invention, a hindered phenolic antioxidant and / or a phosphite antioxidant can be added as a stabilizer that gives extremely good heat aging resistance even when the composition of the present invention is exposed to a high temperature for a long period of time. The blending amount is preferably 0.01 to 3% by weight, more preferably 0.02 to 2% by weight, and particularly preferably 0.03 to 1% by weight, from the viewpoint of improving heat aging resistance.

  In the present invention, the resin is mixed in various colors, weather resistance (light), and electrical conductivity are improved by blending at least one kind of carbon black, titanium oxide, and various color pigments and dyes. The blending amount of the pigment or dye is preferably 0.01 to 3% by weight, more preferably 0.02 to 2% by weight, and particularly preferably 0.03 to 1% by weight. If it is less than 0.01% by weight, there is no effect on the toning, weather resistance (light), and conductivity, and if it exceeds 3% by weight, the mechanical properties deteriorate, such being undesirable.

Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and dibutyl phthalate. carbon black oil absorption 50~400cm 3 ^/ 100g is preferably used, aluminum oxide treatment agent, silicon oxide, zinc oxide, zirconium oxide, polyol, may be treated with a silane coupling agent.

  Further, as the above titanium oxide, a titanium oxide having a rutile form or an anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various thermoplastic resins in order to improve dispersibility with the flame-retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, as the thermoplastic resin, (A) a thermoplastic polyester resin, (E) a vinyl resin and a mixture thereof are preferably used.

  Furthermore, sulfur-based antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, and the like are known as long as the object of the present invention is not impaired with respect to the flame-retardant thermoplastic polyester resin composition and molded article of the present invention. It is also possible to use a material in which one or more of these additives and one or more other thermoplastic resins are blended.

  The molded article comprising the flame-retardant thermoplastic polyester resin composition of the present invention can be used as a mechanical mechanism part, an electric / electronic part, or an automobile part. Specifically, circuit breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, general home appliances, OA equipment housings, variable capacitor case parts, various terminal boards, transformers , Printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases, resistors, metal terminals and conductors Built-in electrical / electronic parts, computer-related parts, audio parts such as acoustic parts, lighting parts, telegraph / telephone equipment-related parts, air conditioner parts, home appliance parts such as VTRs and TVs, copier parts, facsimile parts, optical equipment Parts, automotive ignition device parts, automotive connectors And molded articles such as various types of electrical components for automobiles and the like.

  The flame-retardant thermoplastic polyester resin composition of the present invention can be produced by a known method. For example, (A) a thermoplastic polyester resin, (B) a flame retardant comprising at least one selected from phosphinates, diphosphinates and polymers thereof, (C) an acid component neutralizer, and (D) 3 A polyhydric alcohol compound having one or more alkylene oxide units having one or more functional groups, (E) a vinyl-based resin, (F) a flame retardant aid, and further, (A) if necessary Resins other than the component (E), mold release agent, fiber reinforcement, inorganic fillers other than fiber reinforcement, epoxy compounds, antioxidants, pigments and dyes, and other necessary antistatic agents and plasticizers A method of premixing additives such as additives and supplying them to an extruder, etc., or sufficiently melting and kneading, or a method using a quantitative feeder such as a weight feeder to supply each component to an extruder, etc. Flame retardant thermoplastic polyester resin composition of the present invention is produced by such.

  As an example of the above-mentioned premixing, it is possible to perform dry blending alone, but mixing can be performed using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer. Further, the inorganic filler other than the fiber reinforcing material and the fiber reinforcing material may be added by adding a side feeder in the middle of the original loading part and the vent part of a multi-screw extruder such as a twin screw extruder. . In addition, in the case of liquid additives, a method of adding using a plunger pump by installing a liquid addition nozzle in the middle of the main loading part and the vent part of a multi-screw extruder such as a twin screw extruder and the original loading part For example, a method of supplying with a metering pump may be used.

  Further, in producing a flame retardant thermoplastic polyester resin composition, for example, but not limited to, for example, a single screw extruder, a twin screw extruder, a three screw screw equipped with a “unimelt” or “dalmage” type screw. An extruder, a conical extruder, a kneader type kneader, or the like can be used.

  The flame retardant thermoplastic polyester resin composition thus obtained can be obtained by injection molding by a known method. As the injection molding method, a gas assist method, a two-color molding method, a sandwich molding method, an in-mold molding method, an insert molding method and an injection press molding method are known in addition to the normal injection molding method. it can.

  Hereinafter, the effects of the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Here, “%” and “part” represent “% by weight” and “part by weight”, and “/” in the resin name in the following Reference Examples means copolymerization. Moreover, the measuring method of each characteristic is as follows.

[Reference example]
(A) Thermoplastic polyester resin <A-1> Polyethylene terephthalate resin, Mitsui PET “J005” manufactured by Mitsui Pett Co., Ltd. PET having an intrinsic viscosity of 0.63 was used (hereinafter abbreviated as PET).
<A-2> Polybutylene terephthalate resin, “Toraycon” 1401-X31 PBT having an intrinsic viscosity of 0.80 manufactured by Toray Industries, Inc. was used (hereinafter abbreviated as PBT).

(B) Flame retardant <B-1> phosphinic acid metal salt composed of at least one selected from phosphinates, diphosphinates and polymers thereof, “Exolit” (registered trademark) OP1240 manufactured by Clariant Japan was used.

(C) Acid component neutralizer <C-1> Calcium carbonate, “KSS1000” manufactured by Dowa Calfine Co., Ltd. was used.

(D) Polyhydric alcohol compound <D-1> having three or more functional groups and one or more alkylene oxide units <D-1> Polyoxyethylene pentaerythritol, Nippon Emulsifier Co., Ltd. PNT-60U (molecular weight 400, 1 An alkylene oxide (ethylene oxide) unit number of 1.5 per functional group was used (hereinafter abbreviated as polyhydric alcohol).

(E) Vinyl resin <E-1> Styrene / acrylonitrile / glycidyl methacrylate = 70 / 29.5 / 0.5 wt% epoxy-modified AS resin (hereinafter abbreviated as epoxidized AS).

(F) Flame retardant aid <F-1> Aromatic phosphate ester compound, “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. was used.
<F-2> Phosphazene compound, “Ravitor” (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. was used.
<F-3> Triazine compound, salt of triazine compound and cyanuric acid or isocyanuric acid (melamine cyanurate), MC-4000 manufactured by Nissan Chemical Industries, Ltd. (hereinafter abbreviated as MC salt) .
<F-4> A fluorine resin, polytetrafluoroethylene, “Teflon” (registered trademark) 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., which acts as a melting and dropping (drip) inhibitor during combustion, was used.

(G) Component <G-1> mold release agent to be blended as required, partially calcium saponified montanic acid, “Hoechst Wax-OP” manufactured by Hoechst Japan Ltd. were used.
<G-2> Resins other than components (A) and (E), modified olefin resins epoxy-modified with glycidyl methacrylate, ethylene (88 wt%) / glycidyl methacrylate (12 wt%) copolymer, Sumitomo Chemical Co., Ltd. “BF-E” manufactured by the company was used.
<G-3> (A) Resins other than components (E), aromatic polycarbonate resins, and “A-1900” manufactured by Idemitsu Petrochemical Co., Ltd. were used (hereinafter abbreviated as PC).
<G-4> Transesterification inhibitor, long-chain alkyl acid phosphate compound, “Adeka Stub” AX-71 manufactured by Asahi Denka Co., Ltd. was used.
<G-5> Fiber reinforcing material, chopped strand glass fiber having a fiber diameter of 10 μm, and “CS3J948” manufactured by Nitto Boseki Co., Ltd. (hereinafter abbreviated as GF) were used.
<G-6> Inorganic fillers other than fiber reinforcement, talc, “LMS-100” manufactured by Fuji Talc Kogyo Co., Ltd. were used.
<G-7> Mixture of epoxy compound, versatic acid glycidyl ester, 30% by weight of Japan Epoxy Resin "Cardura E10" and bisphenol A diglycidyl ether, 70% by weight of "Epicoat 828" manufactured by Japan Epoxy Resin.

(H) Acid component neutralizing agent outside the present invention <H-1> Sodium carbonate, reagent primary (I) Polyhydric alcohol outside the present invention <I-1> An alkylene oxide unit having three or more functional groups No polyhydric alcohol compound, pentaerythritol (molecular weight 136, alkylene oxide unit number 0 per functional group, Tokyo Kasei Co., Ltd. reagent was used (hereinafter abbreviated as polyhydric alcohol outside the present invention)
[Measurement method for each characteristic]
In Examples and Comparative Examples, the characteristics were evaluated by the measurement methods described below.

1. Fluidity at the time of injection molding Using a Toshiba Machine IS55EPN injection molding machine, the molding temperature is 250 ° C (the composition containing PET is 270 ° C), the mold temperature is 80 ° C, and the injection time and pressure holding time are the same. Injection molding of a test specimen for mechanical strength evaluation of ASTM No. 1 dumbbell having a thickness of 3.2 mm under a molding cycle condition of 10 seconds and a cooling time of 10 seconds. Abbreviated molding lower limit pressure). In addition, it is excellent in fluidity | liquidity, so that the value of a shaping | molding minimum pressure is low.

2. Mechanical Strength Using the three test pieces for evaluating mechanical strength, the tensile strength was measured according to ASTM D638 (2005), and the value was an average value of the three measured values.

3. Flame retardancy Using a Toshiba Machine IS55EPN injection molding machine, a combustion test with a molding temperature of 250 ° C (a composition containing PET is 270 ° C) and a mold temperature of 80 ° C, a thickness of 1.59 mm and a thickness of 0.79 mm I got a piece. The 1/16 "-thickness combustion test piece was used for the evaluation of flame retardancy of a composition containing no fiber reinforcement. The 0.79 mm-thickness test piece was made of a composition containing a fiber reinforcement. Used for flame retardancy evaluation.

  Using the above-mentioned combustion test piece, flame retardancy was evaluated according to the evaluation criteria defined in the UL94 vertical test. Flame retardancy falls and ranks in the order of V-0> V-1> V-2. Moreover, the material which was inferior in combustibility, did not reach said V-2, and did not correspond to said flame retardance rank was made into the outside of specification.

  Also, during the combustion test, observe whether the test specimens after the first flame contact and the second flame contact are melted by heat and a part of the test piece falls or does not fall. It was evaluated.

4). Gas generation amount at high temperature Three combustion test pieces with a thickness of 0.79 mm were put into Tabai Espec Co., Ltd. gear oven GPHH-200 temperature-controlled at 190 ° C. for 100 hours. The weight loss was determined, and the average value of the three measurements was taken as the amount of gas generated at high temperatures.

5). Tracking resistance According to the test method shown in the IEC (International Electrotechnical Commission) Publication 112 standard, an applied voltage (V: volt) at which tracking occurs on a test piece using a 0.1% ammonium chloride aqueous solution and a platinum electrode, This value was taken as the relative tracking index (V). The higher the applied voltage, the better the tracking resistance.

6). Release force 3. The mold used for flame resistance consists of two plates on the fixed side and the working side that opens and closes the mold. The working side plate is filled with the molded product, and the molded product is ejected by the ejector pin. Is released from the mold. In addition, a load cell for detecting a load is inserted into the protruding pin portion so that the releasing force at the time of releasing can be measured. The mold release force of 5 molded products was measured, and the average value of 5 mold release force values was used. In addition, it is excellent in the mold release property, so that the value of mold release force is small.

7). Impact strength Using an IS55EPN injection molding machine manufactured by Toshiba Machine, injection molding of an Izod impact test piece having a thickness of 3.2 mm under conditions of a molding temperature of 250 ° C. (a composition containing PET is 270 ° C.) and a mold temperature of 80 ° C. In accordance with ASTM D256 (2005), the Izod impact strength without notch was measured, and the value was an average value of seven measured values.

8). Hydrolyzable The three ASTM No. 1 dumbbells obtained in 1) were put into a constant temperature and high humidity tester (Espec Co., Ltd. “Humiday Cabinet” LHL-113) set at a temperature and humidity of 80 ° C. and 95% RH for 400 hours. Next, mechanical strength (tensile strength) was measured according to ASTM D638 (2005), and the value was an average of three measured values. Furthermore, 2. The retention rate (%) relative to the mechanical strength (tensile strength) obtained in the above was obtained and used as a hydrolyzable index.

[Examples 1 to 24], [Comparative Examples 1 to 13]
Using a twin-screw extruder with a screw diameter of 30 mm and L / D35 with the same direction rotating vent (manufactured by Nippon Steel Works, TEX-30α), (A) thermoplastic polyester resin, (B) phosphinate, diphosphinate And a flame retardant comprising at least one or more selected from these polymers, (C) an acid component neutralizing agent, and (D) a polyhydric alcohol compound having one or more alkylene oxide units having three or more functional groups, (E) Vinyl-based resin, (F) Flame retardant aid, if necessary, (A) Resins other than (E) component, release agent, fiber reinforcement, fiber reinforcement Inorganic fillers, epoxy compounds, and the like were mixed in the blending compositions shown in Tables 1 to 6 and added from the original filling portion. In addition, the glass fiber of <G-5> of the fiber reinforcing material was added by installing a side feeder in the middle of the original loading portion and the vent portion.

  Further, the mixture was melt-mixed under the extrusion conditions of a kneading temperature of 270 ° C. and a screw rotation of 150 rpm, discharged into a strand shape, passed through a cooling bath, and pelletized by a strand cutter.

  The obtained pellets were dried with a hot air dryer at 110 ° C. for 6 hours, and various molded products were obtained using an IS55EPN injection molding machine manufactured by Toshiba Machine.

  Furthermore, various values were measured by the above measuring method, and the results are shown in Tables 1 to 6 in the same manner.

  From the comparison between Examples 1 to 13 and Comparative Examples 1 to 9, the flame-retardant thermoplastic polyester resin composition of the present invention is excellent in mechanical properties and fluidity during injection molding, and molding with less gas generation during high-temperature heating. It can be said that it is a product. Moreover, it can be said that the composition which mix | blended (E) vinyl-type resin is a molded article which shows the tracking resistance of 600V or more, maintaining said performance. Moreover, it can be said from Examples 9-13 that the composition which distribute | arranged the fluororesin showed the flame retardance of V-1 by the drip suppression effect at the time of combustion, and can be said to be a molded article which the combustibility improved.

  Moreover, it can be said that the composition which mix | blended the acid component neutralizing agent outside this invention of the comparative examples 10-11 or the polyhydric alcohol outside this invention is inferior to the several performance of this invention effect.

  From the comparison of Examples 14 to 24 and Comparative Examples 10 to 11, the reinforced flame-retardant thermoplastic polyester resin composition of the present invention containing a fiber reinforcement is excellent in mechanical properties and fluidity during injection molding, and is heated at high temperature. It can be said that it is a molded product with little gas generation. Moreover, it turns out that the composition which mix | blended (E) vinyl-type resin shows the tracking resistance of 600V or more, maintaining said performance.

  Moreover, it turns out that the composition of Example 18 which mix | blended the specific mold release agent has fallen greatly and the mold release property improved, maintaining the outstanding performance. It can also be seen that the compositions of Examples 20 and 21 containing resins other than the components (A) and (E) have improved impact strength while maintaining excellent performance. Moreover, it turns out that the composition of Example 23 and 24 which mix | blended the specific epoxy compound has improved hydrolyzability, maintaining the outstanding performance.

Claims (5)

(A) 20 to 95% by weight of a thermoplastic polyester resin, (B) 1 to 30% by weight of a flame retardant composed of at least one selected from phosphinates, diphosphinates and polymers thereof, (C) neutralization of acid components Flame retardant heat comprising 0.01 to 3% by weight of an agent, and (D) 0.01 to 4% by weight of a polyhydric alcohol compound having one or more alkylene oxide units and having three or more functional groups A plastic polyester resin composition. The flame retardant thermoplastic polyester resin composition according to claim 1, wherein (E) 0.1 to 10% by weight of a vinyl resin is blended. (F) The flame-retardant thermoplastic polyester resin composition according to claim 1 or 2, comprising 1 to 50% by weight of a flame-retardant aid. The molded article which consists of a flame-retardant thermoplastic polyester resin composition in any one of Claims 1-3. A molded article having a relative tracking index of 600 V or more, comprising the flame-retardant thermoplastic polyester resin composition according to claim 2 or 3.