JPH0320351A - Flame-retarding polyester composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in flame retardancy, impact resistance and blooming resistance and desirable for electronic components, etc., by mixing a thermoplastic polyester with a specified graft polymer, a rubbery polymer and a flame retardant in a specified weight ratio. CONSTITUTION:A flame-retarding polyester composition is produced by mixing 9-99wt.% thermoplastic polyester (A) with 0.5-40wt.% polymer (B) prepared by grafting a vinyl copolymer onto a copolymer based on an unsaturated compound (e.g. acrylic acid) having an olefin unit and a functional group selected from among epoxy, carboxyl and acid anhydride groups, 0.5-90wt.% rubbery polymer (C) (e.g. polybutadiene) and a flame retardant (D) selected from among a halogenated bisphenol epoxy compound, a halogenated polyphenylene ether and a halogenated benzyl acrylate in such amounts that 5-100 pts. wt. component D is present per 100 pts.wt. total of components A, B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Field of Application The present invention relates to a flame-retardant polyester composition capable of providing flame-retardant, impact-resistant and molded articles free of flame retardant blooming.

(b) Conventional technology Thermoplastic polyesters, represented by polybutylene terephthalate and polyethylene terephthalate, are used as molded products in a wide range of fields such as electrical, electronic, and automobile fields due to their excellent properties. It has the disadvantage of low Izod impact strength. As a method to improve this drawback, a method of blending a rubber component into thermoplastic polyester has been proposed.

On the other hand, there is a need to maintain the excellent impact resistance of these thermoplastic polyester/rubber assemblies and impart flame retardancy, but many of the commonly used flame retardants reduce the impact resistance. This will lead to the loss of the effect of using the rubber component. Furthermore, even if good results were obtained regarding flammability, there was a phenomenon in which the flame retardant oozed out on the surface of the molded product (pluming), and a good molded appearance could not be obtained in many cases.

(c) Problems to be Solved by the Invention It is an object of the present inventors to provide a material that has excellent flame retardancy and impact resistance, and is free from blooming of flame retardants.

(d) Means for Solving the Problems The present inventors have developed a thermoplastic polyester using a specific polymer,
We have discovered that by adding a specific flame retardant when melt-kneading a rubbery polymer, a flame-retardant thermoplastic resin composition with unprecedented performance can be obtained, and based on this knowledge, we have arrived at the present invention. Ta.

That is, the present invention provides (1) (a) 9 to 99% by weight of thermoplastic polyester (b
) Vinyl copolymer consisting of a copolymer mainly composed of an olefin unit and an unsaturated compound having at least one functional group selected from an epoxy group, a carboxyl group, and an acid anhydride group, and at least one vinyl monomer. 0.5 to 40% by weight of polymer grafted with coalescence (c) 0.5 to 40% by weight of rubbery polymer. 5 to 90% by weight, and (d) a halogenated bisphenol-type epoxy compound,
At least one selected from halogenated polyphenylene ether and halogenated benzyl acrylate is blended in an amount of 5 to 100 parts by weight based on 100 parts by weight of the total amount of components (a) + (b) + (c). The present invention provides a thermoplastic resin composition characterized by the following.

(e) Detailed description of the present invention The thermoplastic polyester component (a) used in the present invention is a polyester compound consisting of a dicarboxylic acid and a diol compound, and is a relatively high molecular weight, almost linear thermoplastic polymer. . Preferred are polymeric glycol esters of terephthalic acid and isophthalic acid.

Although these polymers are already commercially available, they can be manufactured by known manufacturing techniques (US Pat. No. 2,465,319, US Pat. No. 3,047,539).

That is, it can be produced by alcoholysis of phthalate ester with glycol and subsequent polymerization reaction, and there is also a method for producing it by polymerization reaction by heating free phthalic acid or its halide derivative and glycol. It can also be manufactured by a similar manufacturing method.

Preferred thermoplastic polyesters used in the present invention include high molecular weight polymeric glycol terephthalate or glycol isophthalate having repeating units of the following formula;
and mixtures of these esters.

Here, n is preferably an integer of 2 to 10, and particularly preferably 2 to 4 in view of the physical properties of the composition. Copolymers of terephthalic acid and isophthalic acid containing up to 30% of isophthalic acid units can also be suitably used.

As particularly preferred polyesters, polyethylene terephthalate and poly-1,4-butylene terephthalate can be used.

Also, branched polyethylene terephthalate, branched polyethylene terephthalate,
1,4-butylene terephthalate can also be used. Such a branched polymer may contain a small amount of a branching component having at least three ester-forming groups, for example up to 5 mol % based on the terephthalic acid units.

The branching component may form a branch on the polyol unit in addition to the acid unit of the polyester, or may be a mixture of both. An example of such a component is:
tri- or tetracarboxylic acids, such as trimesic acid,
such as trimellitic acid, pyromellitic acid and lower alkyl esters thereof, or polyols, preferably tetrols, such as pentaerythritol and triols, such as trimethylolpropane, or dihydroxycarboxylic acids and hydroxydicarboxylic acids and their derivatives, such as hydroxy Examples include dimethyl terephthalate.

These branched polyesters are described, for example, in U.S. Pat.
Branched poly(1,
(4-butylene terephthalate) resin can be manufactured by the same manufacturing method as the resin.

Copolyesters are also useful as polyesters for use in the present invention, and are described, for example, in U.S. Pat. No. 3,651.014, U.S. Pat. A large number of repeating ether esters and/or
Alternatively, a segmented copolyester having ester units can be suitably used.

The amount of component (a) used is (a) + (b) + (
c) It is 9 to 99% by weight, preferably 15 to 95% by weight, and more preferably 20 to 95% by weight. If it is less than 9% by weight, it is difficult to achieve flame retardancy, and if it exceeds 99% by weight, impact resistance will be poor.

A copolymer mainly consisting of an olefin unit in the polymer used as component (b) of the present invention and an unsaturated compound having at least one functional group selected from an epoxy group, a carboxyl group, and an acid anhydride group. One is a binary copolymer of an olefin and an unsaturated group-containing monomer, or a ternary copolymer of an olefin, an unsaturated group-containing monomer, and other unsaturated monomers by high-pressure radical polymerization. or a multi-component copolymer, and the olefin in the above copolymer is particularly preferably ethylene, with 60 to 99.5% by weight of ethylene, 0.5 to 40% by weight of unsaturated compound monomer containing a functional group, and other olefins. Unsaturated monomer O~
A copolymer comprising 39.5% by weight is preferred.

Epoxy group-containing unsaturated compounds include glycidyl methacrylate, allyl glycidyl ether, etc., carboxyl group-containing unsaturated compounds include acrylic acid, methacrylic acid, maleic acid, etc., and acid anhydride group-containing unsaturated compounds include mylene anhydride. There are acids, itaconic anhydride, etc.

Specifically, the vinyl copolymer of the polymer (b) used in the present invention includes styrene, nuclear-substituted styrene, such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylene styrene, chlorstyrene, and α-styrene. Substituted styrenes, such as vinyl aromatic monomers such as α-methylstyrene and α-ethylstyrene; C1-7 alkyl esters of acrylic acid or methacrylic acid, such as methyl, ethyl, propyl, isoprobyl, methacrylate; (meth)acrylic acid ester monomers such as butyl esters; (meth)acrylonitrile monomers; vinyl acetate,
Vinyl ester monomers such as vinyl propionate; (
Meth)acrylamide monomer: A (co)polymer obtained by polymerizing one or more vinyl monomers such as maleic anhydride, maleic acid monoester, and diester.

The polymer (b) referred to in the present invention is usually a polymer having a multiphase structure, and is an olefin copolymer or An olefin copolymer having at least one functional group selected from a vinyl (co)polymer or an epoxy group, a carboxyl group, and an acid anhydride group, which is a different component from the vinyl (co)polymer matrix. are uniformly dispersed in a spherical shape. The particle diameter of the dispersed polymer is 0.001 to 10 μm, preferably 0.01 to 5 μm. Dispersed resin particle size is 0.001
If it is less than μm or more than 10 μm, the dispersibility will be poor when blended with aromatic polyester resin.
For example, it is undesirable because the appearance deteriorates or the effect of improving impact resistance is insufficient.

The number average degree of polymerization of the vinyl (co)polymer of the multiphase structural polymer (b) of the present invention is 5 to 10,000, preferably 10 to 5.
,000 range. If the number average degree of polymerization is 5 or less, the heat resistance of the thermoplastic resin composition of the present invention decreases, which is not preferable. On the other hand, if the number average degree of polymerization exceeds 10,000, the melt viscosity will be high, the moldability will be lowered, and the surface gloss will be lowered, which is not preferable.

The multiphase thermoplastic resin (b) of the present invention has an epoxy group,
At least one selected from carboxyl group and acid anhydride group
The olefin copolymer having various functional groups comprises 5 to 95% by weight, preferably 20 to 90% by weight,
This is preferable in achieving the object of the present invention.

The grafting method for producing the component (b) of the present invention may be any of the generally well-known methods such as chain transfer method and ionizing radiation irradiation, but the most preferred method is This is the method described in No. 48856.

In the step (b) of the present invention, the amount of the vinyl (co)polymer grafted to the functional group-containing olefin copolymer, that is, the grafting ratio, is preferably at least 1% by weight or more. The amount of component (b) used is (a) + (b) of the present invention.
) + 0.5 to 40% by weight in component (c), preferably 1
~35% by weight, more preferably 2~35% by weight. (b) The amount of the ingredient used is less than 0.5% by weight, or 4
If it exceeds 0% by weight, impact resistance will be poor.

Examples of the rubbery polymer as component (e) of the present invention include polybutadiene, styrene-butadiene copolymer, hydrogenated styrene-butadiene random copolymer, acrylonitrile-butadiene copolymer, and hydrogenated acrylonitrile-butadiene copolymer. Polymers, polyisoprene (meth)acrylic acid alkyl ester-conjugated diene copolymers and hydrogenated diene rubbers, ethylene-α-olefin copolymers, ethylene-α-olefin-polyene copolymers,
Non-diene rubber such as polyacrylic acid ester, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer, ethylene ionomer resin, hydrogen Examples include styrene-isoprene block copolymers.

The α-olefin used in the ethylene-α-olefin-(polyene) copolymer is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, such as propylene, pentene-1, pentene-1, hexene-1 , heptene-1, 4-methylbutene-1, 4-methylpentene-1
Among them, propylene is particularly preferred. The weight ratio of ethylene and α-olefin is 95:5 to 5:
95, preferably <95:5 to 20:80. Also, preferred Mooney viscosity (ML, 100°C) 1+
4 is 5 to 200, preferably 5 to 100 in terms of impact resistance.
It is.

As a block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound, the general formula (A-B), (A-B}-A,n
n (A-B}-X n (wherein, A is an aromatic vinyl compound polymer block, B is a conjugated diene compound polymer block, X is a coupling agent residue, and n is an integer of 1 or more.) It is expressed as

Here, the polymer block mainly composed of an aromatic vinyl compound refers to a conjugated diene compound block in which the conjugated diene compound block contains a conjugated diene compound alone or a conjugated diene compound containing a conjugated diene compound in an amount of 60% by weight or more, preferably 80% by weight or more. It may be a copolymer block with an aromatic vinyl compound, and may have one or more so-called tapered blocks in which vinyl aromatic compounds are randomly bonded or gradually increased.

Furthermore, polymer blocks mainly composed of conjugated diene compounds include those having blocks in which conjugated diene compounds are bonded in a low cis type and blocks in a high cis type.

As the vinyl aromatic compound used here, those mentioned above are used, but styrene is preferred.

Conjugated diene compounds include 1,3-butadiene, 2-
Methyl-1,3-butadiene, 2,3-dimethyl-1.
3-ptadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano 1
, 3-butadiene, substituted linear conjugated pentagenes, linear and side chain conjugated hexadiene, and the like. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferably used, and 1,3-butadiene is particularly preferably used.

The weight average molecular weight of the entire block copolymer is preferably 10,000 to 500,000, more preferably 20
,000-300.000.

There is no problem in using not only one type of block copolymer, but also a combination of block copolymers having different structures and different vinyl aromatic compound contents. Further, as a block copolymer, a hydrogenated version of the above block copolymer can also be used.

Furthermore, a hydrogenated product of a random polymer of a vinyl aromatic vinyl compound and a conjugated diene compound can also be used. Preferred are hydrides of styrene-butadiene random copolymers, hydrides of acrylonitrile-butadiene copolymers, (meth)acrylic acid alkyl ester-conjugated diene copolymers and their hydrides, and ethylene-propylene-(polyene). Copolymers, styrene-butadiene block copolymers, hydrogenated styrene. -butadiene block copolymer. More preferably, hydrides of styrene-butadiene random copolymers, hydrides of (meth)acrylic acid alkyl ester-butadiene copolymers, ethylene-bupyrene-(boriene) copolymers, and styrene-butadiene block copolymers It is a hydride.

The amount used in (c) above is (a) + (b) of the present invention.
It is 0.5 to 90% by weight, preferably 2 to 85% by weight, and more preferably 2 to 80% by weight in the +(c) component. If the amount used is less than 0.5% by weight, impact resistance will be poor, and if it exceeds 90% by weight, it will be difficult to achieve flame retardancy.

Various types of halogenated bisphenol type epoxy can be used as the component (d). Particularly preferred compounds are those represented by the following general formula (I).

R (X is bromine or chlorine atom, Y is hydrogen, glycidyl group,
A group selected from alkyl groups, phenol groups, benzyl groups and their derivatives, R is a direct bond, a group selected from alkylene groups, carbonyl groups, ether groups, thioether groups, and sulfone groups, n is an epoxy equivalent of 2,500 or more. The integer required to do this, P is an integer from 1 to 4. ) In the general formula (I), X is a bromine atom or a chlorine atom, but a bromine atom is more preferable than a chlorine atom from the viewpoint of imparting flame retardance.

In general formula (I), if the epoxy equivalent is less than 2,500, that is, if the amount of epoxy groups in the molecule increases, gel etc. may occur during the production of the resin composition of the present invention, making it difficult to operate. Therefore, the epoxy equivalent is 1
A value of 0,000 or more is desirable. From the viewpoint of heat resistance of the final composition, gels may be preferable as long as they do not cause any problems in production. Also, if the epoxy equivalent becomes too large, n becomes too large and the compatibility with the resin to be blended decreases, so the epoxy equivalent is usually 2,500 to 40,
000 is preferred. Furthermore, 3,500 to 30.
000 is preferred.

The halogenated polyphenylene ether according to the present invention has the general formula (II) (X is a bromine or chlorine atom, m is an integer of 5 to 200, n
is an integer from 1 to 5, and the rest are hydrogen atoms. ), and preferred ones are those in which X is bromine and n is 2.

The halogenated polybenzyl acrylate has the general formula (II
I) (X is a bromine or chlorine atom, m is an integer of 10 to 200,
n is an integer from 1 to 5, and the rest are hydrogen atoms. ), and preferred ones are those in which X is a bromine atom and n is 5.

These components (d) and a may be used alone or in combination of two or more. The most preferred one in terms of the balance between heat resistance and impact resistance is chlorogenated polyphenylene ether.

The amount of component (d) used in the resin knit sole of the present invention is (
The amount is 5 to 100 parts by weight, preferably 6 to 80 parts by weight, more preferably 6 to 70 parts by weight, based on 100 parts by weight of the total amount of a) + (b) + (c) bokmin. If the amount of component (d) used is less than 5 parts by weight, the flame retardant effect will be small;
If more than 0.00 parts by weight is added, the impact resistance will be poor.

The antimony compound used as a flame retardant aid is one that significantly enhances the flame retardant effect when added in combination with the above flame retardant (component (d)). Specific examples include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, and antimony phosphate, among which antimony dioxide and sodium antimonate can be particularly preferably used.

The amount of flame retardant aid used is not particularly limited, but is usually 10 to 50% by weight of (d). Further, it is preferable to use Teflon particles because flammability is improved. The amount thereof is determined to be 0.000 parts by weight based on 100 parts by weight of the composition of the present invention from the viewpoint of economy. 1~
Approximately 5 parts by weight is preferable.

The composition of the present invention may further contain an inorganic filler to improve stiffness and heat distortion temperature.

Specific examples of inorganic fillers include glass fiber, asbestos, potassium titanate, ceramic fiber, metal fiber, carbon fiber, wollastenite, mica, clay, glass flakes, glass beads, talc, calcium carbonate, titanium oxide, and barium sulfate. , aluminum oxide, calcium sulfate, etc., and chopped strand type glass fiber is particularly preferably used. These inorganic fillers may be treated with a coupling agent such as epoxy cyan.

The inorganic filler can be used in an amount of 5 to 150 parts by weight based on 100% by weight of the thermoplastic resin composition.

Furthermore, the composition of the present invention may contain an antioxidant (preferably a phenolic antioxidant), an ultraviolet absorber, a lubricant, a mold release agent, a coloring agent, a nucleating agent, as long as the object of the present invention is not impaired.
An antistatic agent or the like may be added.

Depending on the required performance, other polymers, such as AB
S resin, HIPS, polystyrene, polyamide, polyethylene, polypropylene, polycarbonate, polysulfone, polyethersulfone, polyimide, pps, polyetheretherketone, vinylidene fluoride polymer,
Polyphenylene ether and the like can be appropriately blended.

Furthermore, component (c) can be crosslinked to impart excellent elastomer properties.

As the crosslinking method used here, peroxide crosslinking, resin crosslinking, sulfur crosslinking, etc., which are used for ordinary rubber, are used.

As for specific crosslinking agents, for example, the crosslinking agents, crosslinking aids, crosslinking accelerators, etc. described in "Crosslinking Agent Book" (written by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha) are used.

The crosslinking method includes a static crosslinking method in which (a), (b), (c) and the flame retardant component are melt-mixed, the crosslinking agent is added, and the crosslinking is further kneaded, followed by crosslinking using a hot press or the like. Although there is a dynamic crosslinking method in which a crosslinking agent is added and crosslinking is performed while continuing the melt-mixing state, the dynamic crosslinking method is preferred because of its excellent performance.

In the dynamic crosslinking method, the crosslinking agents are (a), (b), (c)
It may be added simultaneously with all components of (a), (b), (
c) Any component or part of the bosan may be mixed with the crosslinking agent and the remaining bosan may be added later;
After melt-mixing all or part of (b) and (c) and adding the remaining components, a crosslinking agent may be added to perform crosslinking. Further, the flame retardant (component (d)) can be added at any point.

A composition suitable for crosslinking by adding the above-mentioned crosslinking agent is a composition in which the amount of component (a) in components (a) + (b) + (c) is 50% by weight or more, more preferably 55% by weight. That's all.

The composition of the present invention can be applied to various extruders, Hanbury mixers,
It can be obtained by kneading the above components using a kneader, rolls, etc. The order of addition of each component during melt-kneading is not particularly limited, but methods include a method in which all the components are mixed and kneaded, and a method in which any component is kneaded and then the remaining components are added and kneaded.

The flame-retardant thermoplastic polyester composition of the present invention can be obtained by kneading each component at a temperature of 200 to 350°C using various extruders, Banbury mixers, kneaders, rolls, etc.

The flame-retardant thermoplastic polyester composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.

The various molded products obtained by the above molding method can be used for automobile interior parts, various electric/electronic parts, housings, etc. by taking advantage of their excellent performance.

[Examples] The present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the content of the present invention. In addition, in each of the following examples, parts and % indicate parts by weight and % by weight, respectively.

(a) and (b) of the present invention used in Examples and Comparative Examples of the present invention
), (c), and (d) components are shown below.

1, (a) Bokubun The following polybutylene terephthalate obtained from terephthalic acid dimethyl ester and butanediol and the following polyethylene terephthalate obtained from terephthalic acid dimethyl ester and ethylene glycol were used. [η] was measured in 0-chlorophenol at 25°C.

A-1: Polybutylene terephthalate [η] = 1.2 A-2: Polybutylene terephthalate [η] = 1.0 A-3 = Polybutylene terephthalate [η] = 0.8 A-4: Polybutylene terephthalate [ η]=0.8 2. Component (b) Add 250 parts of distilled water and 0.25 parts of polyvinyl alcohol to a stainless steel autoclave, and add the ethylene-maleic anhydride copolymer (maleic anhydride content: 1
0%) was added and dispersed. 0.15 parts of penzoyl peroxide as a radical polymerization initiator and 0.6 parts of t-butylperoxymethacryloyloxyethyl carbonate as a radical (co)polymerizable organic peroxide were dissolved in 21 parts of styrene and 9 parts of acrylonitrile and added. did.

By raising the temperature to 60 to 65°C and carrying out a polymerization reaction for 2 hours, the vinyl monomer containing a radical polymerization initiator and a radical (co)polymerizable organic peroxide was impregnated. Next, the temperature was raised to 80-85°C, and a polymerization reaction was carried out for 7 hours. A grafted precursor was obtained by washing with water and drying. This grafting precursor was extruded using an extruder (200° C.) to carry out a grafting reaction, thereby obtaining a multiphase thermoplastic resin B-1. The dispersed particle size of B-1 was 0.3 to 0.4 μm when observed with a scanning electron microscope, and the grafting ratio of the styrene polymer to the ethylene-maleic anhydride copolymer was 32%.

B-2 to B-4 B-2 to B-5 were produced by changing the functional group-containing olefin polymer or vinyl monomer type under the production conditions of B-1.

Margin below 3. (c) Component 1) Ethylene-propylene copolymer C-1 = EP911PML manufactured by Nippon Synthetic Rubber ■
, 100℃ 15 1+4 C-2 Made by Nippon Synthetic Rubber ■ EPOIPML ,
100℃ 19 1+4 C-3 Nippon Goso Rubber side EPO2PML,
100℃ 24 1+4 2) Hydrogenated product of styrene-butadiene-styrene block copolymer C-4: Kraton ■ G1650 manufactured by Shell Co. 3) Polymer C-5 ■ Cyclohexane 50 degassed and dehydrated in an autoclave
After charging 70 parts of 1,3-butadiene, 0.0 parts of n-butyllithium was added. 1 part was added to carry out polymerization. Isothermal polymerization was carried out at a polymerization temperature of 50°C. After the conversion rate reached 31%, 2.5 parts of tetrahydrofuran was added and the temperature was increased from 50°C to 8°C.
Polymerization was carried out at a temperature of 0°C. After the conversion rate reached approximately 100%, 30 parts of styrene was added and polymerization was carried out for 15 minutes. The obtained polymer has a styrene block, a low cis butadiene block and a high cis butadiene block (A-B-
C block copolymer), and its molecular characteristics were as follows.

The following margin■ Next, in another container, titanocene dichloride 0.39
part was dispersed in cyclohexane and reacted with 0.536 part of triethylaluminum at room temperature. The obtained dark blue, apparently homogeneous solution was added to the polymer solution obtained in step ①, and the mixture was heated at 50°C for 5. A hydrogenation reaction was carried out for 2 hours under a hydrogen pressure of 0 kgf/ct1. Thereafter, the solvent was removed with methanol and hydrochloric acid, 2,6-di-tert-butylcatechol was added, and the mixture was dried under reduced pressure.

The hydrogenation rate of the butadiene unit of the obtained hydrogenated polymer was 90%, and the hydrogenation rate of the styrene unit was 1% or less.

4. (d) Boken (flame retardant) D-1: Brominated bisphenol type epoxy compound (Pratherm EP500 manufactured by Dainippon Ink Chemical Company) D-2 = Brominated polyphenylene ether (PO-64P manufactured by Great Lakes Co., Ltd.) D- 3: Polypentapromobenzyl acrylate (DS
PBA-PA manufactured by Company B) D-4: Brominated polycarbonate (BC-58 manufactured by Great Lakes) D-5 = Brominated polystyrene (Pyrocheck ■ 68PB manufactured by Ferro) D-6 Nidecabromodiphenyl oxide 5 ．． Flame retardant auxiliary antimony trioxide Examples 1 to 12, Comparative Examples 1 to 6 The various polymers, flame retardants, and flame retardant auxiliaries were mixed in the composition ratios shown in Table 1, and mixed using a twin screw extruder. It was kneaded into pellets. After thoroughly drying the obtained pellets using a dehumidifying dryer, test pieces were prepared using an injection molding machine and evaluated according to the following evaluation criteria.

Moreover, the evaluation results are shown in Table-1.

Evaluation method Izod impact strength: Measured at 23° C. with a thickness of 1/8° notched according to ASTM D256.

Falling weight impact strength: Fracture energy was measured using a 1/8" thick flat plate.

Flammability: Flammability was evaluated according to UL94 standard.

Blooming property: After the flat plate was left in a gear oven at 120° C. for 7 days, the appearance (bleeding of flame retardant onto the surface of the molded product) was visually evaluated using the following evaluation criteria.

○: Good appearance (no flame retardant oozing out) ×: Poor appearance (flame retardant oozing out) In Comparative Example 1, the amount of component (b) used was small outside the scope of the present invention, and the impact resistance was poor. inferior in sex.

In Comparative Examples 2 and 3, the flame retardant species of component (d) was outside the range of the present invention, and the impact resistance and combustibility were poor.

In Comparative Example 4, the flame retardant species of component (d) was outside the range of the present invention, and the impact resistance was poor and there was blooming.

In Comparative Example 5, the amount of component (d) used was small and outside the scope of the present invention, and the combustibility was poor.

In Comparative Example 6, the amount of component (d) used was larger than the range of the present invention, and the impact resistance and appearance of the molded product were poor.

Margin below (f) Effects of the Invention The composition of the present invention has excellent flame retardancy, impact resistance, and blooming resistance, and is useful as molded products such as electrical and electronic bolt parts and housings. Therefore, the industrial value is extremely large.

Claims (1)

[Claims] (1) (a) Thermoplastic polyester 9-99% by weight (b
) Vinyl copolymer consisting of a copolymer mainly consisting of an olefin unit and an unsaturated compound having at least one functional group selected from epoxy groups, carboxyl groups, and acid anhydride groups, and at least one vinyl monomer. 0.5 to 40% by weight of a polymer grafted with a polymer (c) 0.5 to 90% by weight of a rubbery polymer, and (d) a halogenated bisphenol type epoxy compound,
At least one selected from halogenated polyphenylene ether and halogenated benzyl acrylate (a
1. A thermoplastic resin composition comprising 5 to 100 parts by weight based on 100 parts by weight of the total amount of components )+(b)+(c).