JP7091310B2 - Flame-retardant polyester composition - Google Patents

Description

This application claims priority under US Provisional Application No. 62 / 369,938 filed on August 2, 2016, the entire contents of which are incorporated herein.

The present invention relates to a flame-retardant polyester composition, a method for producing the same, and an article containing the same.

Glass-reinforced or non-reinforced thermoplastic polyester is used, among other things, in the manufacture of electronic components such as connectors, frames, moving parts, transformers and micromotors. Flame retardants are required for most of these applications and are usually provided by flame retardant systems based on a combination of brominated flame retardants and antimony trioxide as a synergistic agent.

However, this type of flame retardant is a very efficient synergist, antimony trioxide, which tends to significantly increase smoke production, which impairs visibility and causes evacuation problems for people in the event of a fire. There are restrictions on the system. In addition, antimony trioxide has a very high bulk density, which increases the specific gravity of the molded part. This is not particularly desirable in transportation and aviation. Moreover, in recent years, the price of antimony trioxide has risen significantly. In addition, some recently introduced ecolabels require the removal of antimony trioxide from thermoplastic components.

There is a clear need for flame retardant plastics that do not contain low antimony trioxide or antimony trioxide, but it usually requires a significant increase in the amount of brominated flame retardant.

Several phosphorus-containing materials have been used, such as the aluminum salt of diethylphosphinic acid (DEPAL), but it still has increased viscosity, low fluidity, more difficult moldability, longer injection molding time, and inadequate. It introduces various processing problems such as recyclability, inferior mechanical and thermal properties, and undesired aging resistance.

A combination of bisphosphate, melamine polyphosphate (MPP), brominated flame retardants and drip retardants provides flame retardant additives for thermoplastic polymers, more specifically thermoplastic polyesters, preferably glass-reinforced polybutylene terephthalates. Provided, it has been unexpectedly found herein that it provides suitable flame retardant efficiencies for thermoplastics in electrical and electronic applications without the need for the use of antimony trioxide.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、任意にヘテロ原子で中断された、それぞれ独立して約３０個までの炭素原子を含むアリールまたはアリールアルキルであり、Ｘは約２０個までの炭素原子を含む二価有機基であり、ｎは約１．０～約２．０の平均値を有する。）、
（ｃ）メラミンポリホスフェート、
（ｄ）少なくとも一種の臭素化難燃剤、および
（ｅ）少なくとも一種の防滴剤
を含む難燃性ポリエステル組成物に関する。 The present invention is: (a) at least one type of polyester,
(B) Bisphosphate of the general formula (I)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are aryl or aryl alkyl each independently containing up to about 30 carbon atoms, each independently interrupted by a heteroatom. , X is a divalent organic group containing up to about 20 carbon atoms, and n has an average value of about 1.0 to about 2.0),.
(C) Melamine polyphosphate,
It relates to a flame retardant polyester composition comprising (d) at least one brominated flame retardant and (e) at least one drip retardant.

Further, the present invention comprises the polyester (a), such as PBT, a bisphosphate (b) of the general formula (I), such as a hydroquinone bisdiphenyl phosphate ester, MPP (c), a brominated flame retardant (D), such as poly. The present invention relates to a method for producing the flame retardant polyester composition, which comprises blending a pentabromobenzyl acrylate (PBBPA), a drip retardant (e), and any solid filler.

Furthermore, the present invention relates to articles made by the methods described above, such as polyesters, fiberglass, bisphosphate (b), MPPs, brominated flame retardants, drip retardants, and any fillers, antioxidants. It also relates to molded parts containing processing aids and colorants.

The present invention, in one non-limiting embodiment, comprises, is essentially composed of, or can be composed of any of the components (a)-(e) described herein. In one embodiment, any combination of endpoints in any range or combinations of endpoints in the range described herein are also contemplated.

The use of the present invention herein is that a bisphosphate, such as a hydroquinone bisdiphenyl phosphate ester (b), acts as a processing aid, especially with respect to the use of the bisphosphate (b) of the general formula (I). In that respect, it provided a better plasticizing effect than DEPAL. Moreover, said use of bisphosphate (b) has lower viscosity and better fluidity of the resulting compound compared to DEPAL, and as a result, better moldability, shorter injection cycle time, It provides better recyclability, maintained mechanical and thermal properties, and good aging resistance.

As used herein, the at least one type of polyester (a) is intended to include any polymeric thermoplastic material containing an ester group-OC (O) -in the backbone. More specifically, the polyester (a) is any thermoplastic polyester produced by polycondensation polymerization of a glycol component and an acid component in a preferred embodiment.

The glycol component is a glycol such as ethylene glycol, trimethylene glycol, 2-methyl-1,3-propaneglycol, 1,4-butylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol or neopentylene glycol. Can include one or more of.

The acid components are terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-di. It can contain one or more of acids such as phenoxyetanedicarboxylic acid, p-hydroxybenzoic acid, sebacic acid, adipic acid and their polyester-forming derivatives.

A polyester blend can also be used as the polyester (a) in the flame retardant polyester composition. Preferred polyesters are poly (ethylene terephthalate), poly (1,3-trimethylene terephthalate) and poly (1,4-butylene terephthalate). When a blend of these preferred components is used, the polyester component (a) is about 1 to about 99 parts by weight of one polyester and about 99 to about 1 part by weight based on 100 parts by weight of both components combined. Can contain different polyesters.

In one embodiment, the at least one polyester component (a) is poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene. It is selected from the group consisting of furanoate (PEF) and combinations thereof.

In one embodiment, the bisphosphate (b) of the general formula (I) is such that in the formula, ^R1 , ^{R2 ,} R3 and ^R4 are each independently and optionally interrupted by a heteroatom, respectively. Independently, it is an aryl or arylalkyl containing up to about 30 carbon atoms, preferably up to 12 carbon atoms, X is a divalent organic group containing up to about 20 carbon atoms, and n is about 1. It can have an average value of 0.0 to about 2.0.

In one aspect of the invention, the phosphate represented by the general formula (I), where n has an average value of about 1.0 to about 1.4, preferably 1.0 to about 1.1, and X is hydroquinone. Is in the form of an easily fluid powder. Typically, but not limited to, the "easy fluid powder" applied to the phosphate of formula I has an average particle size of about 10 μm to about 80 μm. These I Ching powders, when compounded with a thermoplastic resin, avoid various handling problems and impart improved thermal properties such as resin fluidity.

Generally, the hydroquinone bisphosphate of the present invention is produced by reacting diarylhalophosphate with hydroquinone in the presence of a catalyst. In a preferred embodiment of the invention, diphenylchlorophosphate (DPCP) is reacted with hydroquinone in the presence of MgCl ₂ to produce hydroquinone bis- (diphenyl phosphate). According to the present invention, the hydroquinone bis (diphenyl phosphate) represented by the general formula (I) produced by this method will have an average n value of about 1.1 or less.

（式中、各Ｒは独立して１～４個の炭素原子のアルキルであり、各Ｙは独立して塩素または臭素であり、ｐは０～３であり、およびｑは０～５であり、ｐとｑの合計は０～５であり）、Ｘが式（ＩＩａ）のヒドロキノン部分：

（式中、破線はＸ部分に結合したＯ原子への結合を示す。）
または式（ＩＩｂ）のレゾルシノール部分：

（式中、破線はＸ部分に結合したＯ原子への結合を示し、およびｎは約１．０～約１．４の平均値を有する。）であるようなものである。 In one embodiment of the present specification, in the bisphosphate of the general formula (I), R ¹ , R ² , R ³ and R ⁴ are independently phenyl groups of the general formula (II).

(In the formula, each R is independently an alkyl of 1 to 4 carbon atoms, each Y is independently chlorine or bromine, p is 0 to 3, and q is 0 to 5. , The sum of p and q is 0-5), where X is the hydroquinone moiety of formula (IIa):

(In the equation, the broken line indicates the bond to the O atom bonded to the X part.)
Or the resorcinol moiety of formula (IIb):

(In the equation, the dashed line indicates the bond to the O atom bonded to the X moiety, and n has an average value of about 1.0 to about 1.4).

In a more specific embodiment, the bisphosphate represented by the above formula (I) is hydroquinone bis (diphenyl phosphate) (HDP), i.e., R ₁ , R ₂ , R ₃ and R ₄ are phenyl, respectively. ..

In other embodiments herein, the bisphosphate (b) of the general formula (I) is hydroquinone bis (diphenylphosphate).

In yet another embodiment of the specification, the bisphosphate (b) of the general formula (I) is hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), tetrakis (2). , 6-Dimethylphenyl) 1,3-phenylene bisphosphate, biphenylbis (diphenylphosphate) and combinations thereof are selected from the group.

In one embodiment of the specification, the MPP component (c) is available from BASF.

The at least one brominated flame retardant (d) used in the present invention can be any known brominated flame retardant, for example, brominated polystyrene, polydibromostyrene, polytribromostyrene, polypentabromostyrene. , Decabromodiphenyl ethane, tetrabromodecabromodiphenoxybenzene, ethylenebistetrabromophthalimide, 2-ethylhexyltetrabromophthalic acid ester, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A Bis (2,3-dibromopropyl ether), Tris (tribromophenoxy) triazine, Tris (tribromoneopentyl) phosphate, tetrabromodiphenyl sulfide, tetrabromobisphenol S bis (2,3-dibromopropyl ether), brominated Polyacrylates such as poly (pentabromobenzyl acrylate), brominated phenoxy resin, bis (tribromophenoxy) ethane, polydibromophenylene oxide, epoxy-terminated brominated phenoxy resin, terminally blocked bromine sold as F-3000 series. Examples thereof include brominated epoxy polymers, brominated polycarbonates, phenoxy-terminated carbonate oligomers of tetrabromobisphenol A, and combinations thereof. The brominated polystyrene, such as polydibromostyrene, is prepared by brominating polystyrene or poly (α-methylstyrene) or by polymerizing brominated styrene or brominated α-methylstyrene.

In one embodiment of the specification, the at least one brominated flame retardant is a polymer flame retardant, preferably a polymer brominated epoxy polymer. In another embodiment, the at least one brominated flame retardant is decabromodiphenylethane.

Specifically, some suitable brominated flame retardants (d) of the present invention include flame retardant compounds of the following formula.

Decabromodiphenyl ether sold under the trade name of FR-1210

Tetrabromobisphenol A sold under the trade name FR-1524

Tetrabromobisphenol A-bis (2,3-dibromopropyl ether) sold under the trade name of FR-720.

Tris (tribromophenoxy) triazine sold under the trade name FR-245

Tris (tribromoneopentyl) phosphate sold under the trade name FR-370

Poly (pentabromobenzyl acrylate) sold under the trade name of FR-1025.

Brominated polystyrene sold under the trade name of FR-803P

Epoxy-terminated brominated phenoxy resin sold under the trade name of F-2000 series

End-blocking brominated epoxy polymer sold under the trade name of F-3000 series

Phenoxy-terminated carbonate oligomer of tetrabromobisphenol A

Decabromodiphenylethane

Tetrabromodecabromodiphenoxybenzene

Ethylene bistetrabromophthalimide

Tetrabromobisphenol S-bis (2,3-dibromopropyl ether)

Polydibromophenylene oxide

2-Ethylhexyltetrabromophthalate ester

Bis (tribromophenoxy) ethane

のポリペンタブロモベンジルアクリレートであり、ＩＣＬ－ＩＰ Ａｍｅｒｉｃａ社から入手可能で商品名ＦＲ－１０２５で販売されている。 In one particular embodiment herein, the at least one brominated flame retardant component (d) is of formula:

Polypentabromobenzyl acrylate, available from ICL-IP America, and sold under the trade name FR-1025.

The flame-retardant polyester composition may further comprise one or more drip-proofing agents (e) that prevent or delay the dripping of the polyester resin while the resin is exposed to combustion conditions. Specific examples of such agents include silicone oil, silica (which also functions as a reinforcing filler), asbestos and fibrillated fluoropolymers. Some non-limiting examples of fluorinated polymers include fluorinated polyolefins such as poly (tetrafluoroethylene), tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, poly (vinylidene fluoride). , Poly (chlorotrifluoroethylene) and the like, and mixtures containing at least one of the above drip-proof agents.

A preferred drip-proof agent is poly (tetrafluoroethylene) encapsulated with a styrene-acrylonitrile (SAN) copolymer. When used, the drip-proof agent is present in an amount of 0.02 to 2% by weight, more specifically 0.05 to 1% by weight, based on the total polymerization of the composition.

In one embodiment, the drip-proof agent (e) can be polytetrafluoroethylene (PTFE). It is commercially available in a variety of product qualities. These include additives, such as Hostaflon® TF2021 or PTFE blends, eg, Chematura® A-3800 (about 40% PTFE CAS 9002-84-0 and about 60% methacrylic). Methyl acid / butyl acrylate copolymer CAS 25852-37-3: Mitsubishi Rayon) or Chemtura's Blendex® B449 (about 50% PTFE and about 50% SAN [80% styrene and 20% acrylonitrile]). Is. Blendex® B449 is preferably used.

The inorganic filler of the present invention can be added to the flame-retardant polyester composition for the purpose of lowering the molding shrinkage rate and the coefficient of linear expansion of the obtained molded product and improving the high and low thermal shock resistance, which is desired. Depending on the article, various fillers in a fibrous or non-fibrous (eg, powder, plate) state can be used. Some examples of fibrous fillers, which are a type of inorganic filler, include glass fibers having a non-circular cross section such as glass fibers and flat fibers, carbon fibers, silica fibers, silica-alumina fibers, zirconia fibers, and boron nitride fibers. Examples include silicon nitride fibers, boron fibers, potassium titanate fibers, as well as metal fibrous materials such as stainless steel, aluminum, titanium, copper and brass.

In particular, the typical fibrous filler is glass fiber or carbon fiber. On the other hand, the inorganic filler is a powdery filler, for example, silicates such as carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicate stone. , Metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, as well as silicon carbide, silicon nitride, boron nitride, And various metal powders.

Other examples of inorganic fillers can be plate-like fillers such as mica, glass flakes and various metal foils. These inorganic fillers can be used alone or in combination of two or more. When using these inorganic fillers, it is desirable to treat them with a sizing agent or a surface treatment agent in advance as necessary.

The amount of the inorganic filler in the polyester flame retardant composition may be 1 to 50% by weight, preferably 10 to 45% by weight, and most preferably 20 to 40% by weight. If the amount is too small, the effect of improving the thermal impact resistance is small, and if it is too large, the molding process becomes difficult.

The polyester flame retardant composition may also further comprise an impact modifier such as an elastomer and a core-shell polymer. These elastomers are solids having rubber-like elasticity at room temperature, but their viscosities decrease when heated, so they can be thermoplastic elastomers that can be melt-mixed with the thermoplastic polyester resin (a). The specific thermoplastic elastomer used is not particularly limited, and elastomers based on olefin-, styrene-, polyester- (excluding component (a)), polyamide-, and urethane-are used as non-limiting examples. Can be done.

The core-shell polymer is a core-shell type graft copolymer having a multi-layer structure, preferably a rubber layer having an average particle size of 1.0 μm or less and being wrapped with a vitreous resin. The rubber layer of the core-shell type copolymer has an average particle size of 1.0 μm or less, preferably 0.2 to 0.6 μm. If the average particle size of the rubber layer exceeds 1.0 μm, the effect of improving impact resistance may be insufficient. As the rubber layer of this core-shell type copolymer, one obtained by copolymerizing / graft-copolymerizing at least one of a silicon-based, diene-based or acrylic-based elastomer can be used.

Other components typically used in an amount of less than 10% by weight, preferably less than 5% by weight, of the flame-retardant thermoplastic composition free of antimony trioxide include lubricants, heat stabilizers, and said. Other non-limiting examples include other additives used to enhance the properties of the resin.

Typically, transesterification inhibitors are used in amounts of 0.01% to 0.5% by weight, including monozinc phosphate, zinc phosphate, or other types of inhibitors. Conventional stabilizer additives are preferably available in an amount of 0.01-5% by weight of the total polyester flame retardant composition and include examples such as hindered phenols and antioxidants.

In one embodiment of the specification, the polyester flame retardant composition is an amount of about 40 to about 90 weight percent of polyester (a), about 5 to about 5 to about, based on the total weight of the polyester flame retardant composition. 30% by weight of the hydroquinone bisdiphenyl phosphate (b) of the general formula (I), about 1 to about 10% by weight of the MPP component (c), about 10 to about 30% by weight of the brominated. It contains the flame retardant component (d) and the drip retardant (e) in an amount of about 0.02 to 2% by weight.

In a more specific embodiment, the polyester flame retardant composition is an amount of polyester (a) of about 40 to about 90% by weight, about 5 to about 30 based on the total weight of the polyester flame retardant composition. Hydroquinone bisdiphenyl phosphate (b) of the general formula (I) in an amount of about 1% to about 10% by weight of the MPP component (c) in an amount of about 1 to about 10% by weight, said bromination resistance in an amount of about 10 to about 30% by weight. Approximately 10 to about 35% by weight based on the total weight of the polyester flame retardant composition containing the flame retardant component (d) and the drip retardant (e) in an amount of about 0.05 to 1% by weight. Contains an amount of inorganic filler.

These amounts of the flame-retardant additive (b), (c), (d), (e) and the inorganic filler in the polyester flame-retardant thermoplastic composition are the flame-retardant effective amounts thereof. ..

The polyester flame-retardant thermoplastic compositions herein have one or more flame-retardant classifications of HB, V-2, V-1, V-0 and 5VA according to the UL-94 protocol. Can be done. In one embodiment, the polyester flame retardant composition can have at least V1 or V-0 flame retardancy.

The method of blending the compositions of the present invention is not important and can be practiced by conventional techniques. One convenient method is to blend the polyester (a) and other components (b)-(e) in optional powder or granular form, extrude the blend, and pellet or other the blend. Includes grinding into suitable shapes.

Although not essential, best results can be obtained by premixing the ingredients, pelletizing and then molding. Pre-formulation can be performed with conventional equipment. For example, after careful pre-drying of the polyester resin (a), other components, and optionally other additives and / or fortifiers, the uniaxial screw extruder is fed with a dry blend of the composition for use. The screw has a long transition to ensure proper melting. On the other hand, a resin or an additive can be supplied to the supply port of a twin-screw extruder, for example, a ZE25 (L / D = 32, manufactured by Berstrff) extruder to have downstream reinforcement. In either case, a generally suitable mechanical temperature is about 220-320 ° C.

The premixed composition can be extruded and cut or chopped into conventional granules, pellets and other molding compounds by standard techniques.

The polyester flame retardant composition can be molded by any device conventionally used for thermoplastic compositions. For example, in an injection molding machine, such as the Arburg 320S Allrounder 500-150 type, good results are obtained at conventional temperatures, such as 230-270 ° C. If necessary, depending on the molding properties of the PBT (a), the amount of the additive and / or the reinforcing filler and the crystallization rate of the polyester component (a), those skilled in the art will use a molding cycle containing the composition. Customary adjustments could be made in.

In another embodiment of the present specification, a molded product containing the polyester flame-retardant composition, preferably a molded product manufactured by injection molding, is provided.

In one embodiment, the molded article has a thickness of 0.8 mm or 0.4 mm and a V-0 flame retardancy.

In another embodiment, the article is measured at ASTMD1238 270 ° C./1.2 kg and has a melt flow index of 10-50, preferably 15-50, more preferably 15-40, most preferably 20-40. Has (MFI).

The polyester flame retardant composition of the present invention is useful for manufacturing electronic components such as connectors, frames, moving components, transformers and micromotors.

In certain embodiments herein, polyester polymer (a), hydroquinone bisdiphenyl phosphate (b), MPP (c), brominated flame retardant (d), drip retardant (e), and any glass fiber are used. Injection molded parts including, eg electronic parts, are provided.

In another embodiment, the flame retardant articles described herein, such as electronic components, preferably injection molded electronic components, manufactured by the methods described above are provided.

The present invention will be described with reference to the following examples.
(Example)
This example evaluated flammability at thicknesses of 1.6, 0.8 and 0.4 mm, as well as mechanical properties. The amount of flame retardant (FR) system was divided into three main levels (L-1, L-2 and L-3).

Level 1 (L-1): Due to the presence of FR-1025, it contains 8% by weight bromine and is assessed with 5% synergistic agent, ie HDP.

Level 2 (L-2): Due to the presence of FR-1025, it contains 8% by weight bromine and is assessed with 7.5% synergist, ie HDP.

Level 3 (L-3): In the presence of FR-1025, it contains 10% by weight bromine and is evaluated with 7.5% synergistic agent.

Level 4 (L-4) is a comparative evaluation of 7.1 wt% bromine in the presence of FR-1025, using a 10% aluminum salt (DEPAL) of diethylphosphinic acid, a synergist available from Clariant. Evaluated.

(material)
The materials used in this study are shown in Table 1.

(Mixing)
The polymer and additives were premixed and fed via feeder # 1 and FR was fed directly to the extruder port via feeder # 2. Glass fiber (GF) was supplied to the fifth portion of the extruder via the side feeder via feeder # 3.

The compounding was carried out in a twin-screw co-directional rotary extruder ZE25 (L / D = 32, manufactured by Bertorff). The extruded strands were pelleted with a pelletizer 750/3 manufactured by Accrapak Systems Limited.

The resulting pellets were dried at 120 ° C. for 4 hours in a circulating air oven manufactured by Heraeus Instruments.

(conditioning)
Prior to testing, the specimens were conditioned at 23 ° C. for 1 week.

(injection molding)
Specimens were prepared by injection molding in Allrounder 500-150 (manufactured by Arburg).

(Test method)
The test method is shown in Table 2.

(Main results):
(ATO):
ATO Criteria (L-1): For 8% Br (FR-1025) and 5% ATO, all thicknesses were rated as V-0.

(ATO synergistic agent):
Level 1 (L-1): None of the synergists tested were able to achieve V-0 at 0.8 mm or 0.4 mm.

Level 2 (L-2): Only the pharmaceutical product containing MPP + HDP was evaluated as V-0 at 0.8 mm. None of the synergists tested above was able to achieve V-0 at 0.4 mm.

Level 3 (L-3): The pharmaceutical product containing MPP + HDP was rated V-0 at all thicknesses.

The formulations containing only HDP and the formulations containing only MPP were rated as V-0 at 0.8 mm, but could not achieve V-0 at 0.4 mm.

Level 4 (L-4): Those containing 10% Exolit 1240 and 7.1% Br (FR-1025) were rated V-0 at all thicknesses.

Mechanical properties: The ATO standard was best for Izod impact. All synergists tested showed acceptable mechanical properties.

MFI: HDP alone and HDP containing MPP had improved flow performance as measured by the Melt Flow Index (MFI). MFI is a measure of the ease of flow during the machining phase. This feature is very important in the manufacture of thin electronic components. The MFI performance of HDP alone and HDP containing MPP was much better than that of pharmaceutical product L-4 containing DEPAL. The MFI was also better than the ATO standard.

GWIT: High GWIT values were observed with all the synergists tested.

Although the present invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various modifications may be made without departing from the scope of the invention and that elements and equivalents may be substituted. Will be understood. Moreover, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope of the invention. Accordingly, the invention is not limited to the particular embodiments disclosed as the best embodiments intended for carrying out the invention, but is intended to include all embodiments within the scope of the appended claims. Will be done.

Claims (25)

(A) At least one kind of polyester,
(B) Bisphosphate of the general formula (I)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are aryls or arylalkyls each independently containing up to 30 carbon atoms, each independently interrupted by a heteroatom. X is a divalent organic group containing up to 20 carbon atoms, and n has an average value of 1.0 to 2.0).
(C) Melamine polyphosphate,
(D) At least one brominated flame retardant, and (e) at least one drip retardant, and
Free of phosphate-based glass , antimony compounds, borate metal salts, and organic phosphinates ,
Flame-retardant polyester composition. The bisphosphate of the general formula (I) is a phenyl group of the general formula (II) in which R ¹ , R ² , R ³ and R ⁴ are independent of each other.

(In the formula, each R is independently an alkyl of 1 to 4 carbon atoms, each Y is independently chlorine or bromine, p is 0 to 3, and q is 0 to 5. , The sum of p and q is 0-5), where X is the hydroquinone moiety of formula (IIa):

(In the equation, the broken line indicates the bond to the O atom bonded to the X part.)
Or the resorcinol moiety of formula (IIb):

(In the equation, the broken line indicates the bond to the O atom bonded to the X portion, and n has an average value of 1.0 to 1.4.))
The flame-retardant polyester composition according to claim 1. The flame-retardant polyester composition according to claim 1, wherein the bisphosphate (b) of the general formula (I) is hydroquinone bis (diphenyl phosphate). The bisphosphate (b) of the general formula (I) is hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), tetrakis (2,6-dimethylphenyl) 1,3-phenylene. The flame-retardant polyester composition according to claim 1, which is selected from the group consisting of bisphosphate, biphenylbis (diphenylphosphate) and combinations thereof. The first aspect of the present invention, wherein the at least one type of polyester (a) is selected from the group consisting of poly (ethylene terephthalate), poly (butylene terephthalate), polytrimethylene terephthalate, polyethylene naphthalate, polyethylene furanoate and combinations thereof. The flame-retardant polyester composition described. The flame-retardant polyester composition according to claim 1, wherein the polyester is poly (1,4-butylene terephthalate). The flame-retardant polyester composition according to claim 1, wherein the at least one brominated flame retardant is a polymer flame retardant. The flame-retardant polyester composition according to claim 1, wherein the at least one brominated flame retardant is a polymer brominated epoxy polymer. The flame-retardant polyester composition according to claim 1, wherein the at least one brominated flame retardant is decabromodiphenylethane. The at least one brominated flame retardant is brominated polystyrene, polydibromostyrene, polytribromostyrene, polypentabromostyrene, decabromodiphenylethane, tetrabromodecabromodiphenoxybenzene, ethylenebistetrabromophthalimide, 2-ethylhexyl. Tetrabromophthalic acid ester, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A bis (2,3-dibromopropyl ether), tris (tribromophenoxy) triazine, tris (tribromo) Neopentyl) phosphate, tetrabromodiphenyl sulfide, tetrabromobisphenol S bis (2,3-dibromopropyl ether), brominated polyacrylate, brominated phenoxy resin, bis (tribulmophenoxy) ethane, polydibromophenylene oxide, epoxy terminal The flame-retardant polyester composition according to claim 1, which is selected from the group consisting of a brominated phenoxy resin, a terminal-sealed brominated epoxy polymer, a brominated polycarbonate, a phenoxy-terminal carbonate oligomer of tetrabromobisphenol A, and a combination thereof. .. The flame-retardant polyester composition according to claim 1, wherein the at least one bromide flame retardant is polypentabromobenzyl acrylate. The flame-retardant polyester composition according to claim 1, wherein the at least one drip-proof agent is selected from the group consisting of silicone oil, silica, asbestos, and a fibrillated fluorine-containing polymer. The fibrillated fluorine-containing polymer is poly (tetrafluoroethylene), tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, poly (vinylidene fluoride), poly (chlorotrifluoroethylene), and their respective. The flame-retardant polyester composition according to claim 12, which is selected from the group consisting of mixtures. As the abundance of the components (b)-(e), (b) is 5 to 30% by weight, (c) is 1 to 10% by weight, (d) is 10 to 30% by weight, and (e) is 0. The flame-retardant polyester composition according to claim 1, which is 02 to 2% by weight. The flame-retardant polyester composition according to claim 1, further comprising a filler. The flame-retardant polyester composition according to claim 15, wherein the filler is glass fiber. The flame-retardant polyester composition according to claim 1, further comprising an impact modifier. The flame-retardant polyester composition according to claim 1, further comprising a heat stabilizer and / or an antioxidant. A molded product containing the flame-retardant polyester composition according to claim 1. The molded product according to claim 19, wherein the molded product has a thickness of 0.8 mm and a flame retardancy of V-0. The molded product according to claim 19, wherein the molded product has a thickness of 0.4 mm and a flame retardancy of V-0. The molded product according to claim 19, wherein the molded product has a melt flow index of 10 to 50. (A) At least one kind of polyester,
(B) Bisphosphate of the general formula (I)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are aryls or arylalkyls each independently containing up to 30 carbon atoms, each independently interrupted by a heteroatom. X is a divalent organic group containing up to 20 carbon atoms, and n has an average value of 1.0 to 2.0).
(C) Melamine polyphosphate,
(D) At least one kind of brominated flame retardant,
(E) Containing at least one drip-proof agent and optionally at least one inorganic filler, impact modifier, antioxidant and heat stabilizer .
A method for producing a flame-retardant article, which comprises blending a raw material group containing no phosphate-based glass, an antimony compound, a boric acid metal salt, and an organic phosphinate . A flame-retardant article manufactured by the method according to claim 23. The flame-retardant article according to claim 24, wherein the article is an injection molded electronic component.