JP2000119491A - Flame-retardant, antistatic polyester-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. excellent in the antistatic property, flame retardancy, heat resistance, mechanical strengths, processability and low mold- staining, by blending each specified amt. of a thermoplastic polyester, a poly(alkylene terephthalate)based block copolymer, an ionic surfactant, a bromine- based flame retardant, and an antimony compd. SOLUTION: A compsn. comprises a blend of 100 pts.wt. of a thermoplastic polyester, 40-30 pts.wt. of a block copolymer consisting of a poly(alkylene terephthalate) unit and a unit expressed by the formula, 3-40 pts.wt. of an ionic surfactant, 5-100 pts.wt. of a bromine-based flame retardant, and 3-30 pts.wt. of an antimony compd. In the formula, R1 is 2-5C alkyl; X is a divalent bonding group or a single bond; m and n are each an integer of 1 or more, and (m+n) is 3 or more. The ionic surfactant is pref. an anionic surfactant. The ionic surfactant has an m.p. pref. higher than a cold crystallizing point of the thermoplastic polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in antistatic properties, flame retardancy, heat resistance, mechanical strength, moldability and low mold contamination, and is suitable for various uses, in particular, electricity, electronics, home appliances, OA. The present invention relates to a thermoplastic polyester resin composition suitable as an equipment part, and a molded product molded using the same.

[0002]

2. Description of the Related Art Thermoplastic polyester resins represented by polyethylene terephthalate and polytetramethylene terephthalate have been widely used as fibers, films, molding materials and the like because of their excellent mechanical and electrical properties. I have. By blending a reinforcing filler such as glass fiber with these thermoplastic polyester-based resins, a mechanically-strengthened, heat-resistant thermoplastic polyester-based resin reinforced composition is obtained, and this reinforced composition is It is suitable as a material for a so-called functional component. Furthermore, by incorporating a flame retardant into these thermoplastic polyester resins, a resin composition having high flame retardancy can be obtained without impairing mechanical strength and heat resistance, and this reinforced flame retardant resin composition is In recent years, as the demand for fire safety has increased, it has been widely used in various fields. On the other hand, it is known that a thermoplastic resin composition containing a polyester-based resin is easily charged, and in recent years, in addition to such functions as mechanical strength or heat resistance,
In particular, in the field of home appliances and OA equipment, a function of preventing resin from being electrostatically charged is required.

[0003] As a method of giving an antistatic property to a resin,
Methods of adding conductive carbon black and metal fibers are well known, and are described in, for example, JP-A-49-99734, JP-A-10-11090, and JP-A-07-53778. However, when the conductive carbon black is added to the flame-retardant polyester-based resin composition to impart antistatic properties, the toughness of the obtained resin composition is reduced because the carbon black is insoluble in the resin component. There was a problem of doing. In the course of recent cost reductions, the use of screws has been promoted in order to reduce the number of assembly steps for products, and the method has been changed from using screws for resin parts to installing nails on the products and mounting them by mounting. I am doing it. In order to cope with such a fitting type, it is necessary to improve the snap fitting property of the resin, that is, the toughness. In addition, when conductive carbon black is used, the resulting resin composition is limited to black, and thus it has not been possible to meet the demand for coloring, particularly in the field of home appliances.

On the other hand, a method of adding a surfactant is generally known as a method for imparting antistatic properties to a resin without using conductive carbon black. However, even if a surfactant is added to the thermoplastic polyester resin, the resulting composition has a resistance value of 1E14Ω.
The antistatic level is on the order of cm and is the antistatic level required in the market (1E10 to 1E12Ω · c
m) was difficult to achieve. To cope with this, if the amount of surfactant in the resin is increased, the decomposition of the resin is promoted and the mechanical strength is reduced, and the bleeding amount of the surfactant on the surface of the molded product is increased. Problem (fogging) occurs. Furthermore, since the processing temperature of the thermoplastic polyester resin is high, if a normal surfactant is added, it will volatilize from inside the resin due to the reduced pressure during extrusion processing, causing clogging of the extruder vent line and volatilization during molding processing. The components adhered to the mold surface and caused mold contamination.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides an antistatic layer having a resistance value of an antistatic level without using conductive carbon black while maintaining high heat resistance, flame retardancy and mechanical strength. An object of the present invention is to provide a flame-retardant antistatic polyester resin composition which has a good appearance, can be colored, has an improved snap fit property, and has good mold contamination during molding.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a thermoplastic polyester has a polyalkylene terephthalate unit together with a brominated flame retardant and an antimony compound. By adding a block copolymer with a polyether unit of a specific structure and an ionic surfactant, the desired low resistance level can be obtained without using conductive carbon black, and at the same time, the snap-fit Is improved, and furthermore, by using a specific antimony compound, the thermal stability of the obtained molded article is greatly improved,
The present inventors have found that the surface appearance is good and that the mold contamination during molding is greatly suppressed, and the present invention has been completed. That is, the present invention includes a flame-retardant antistatic polyester resin composition comprising the following components (A) to (E), and a molded article molded using the same. (A) 100 parts by weight of a thermoplastic polyester (B) Block copolymers 20 to 3 of a polyalkylene terephthalate and a unit represented by the following general formula (1)
00 parts by weight

[0007]

Embedded image (Wherein, R1 represents an alkyl group having 2 to 5 carbon atoms, X represents a divalent linking group or a direct bond, m and n each represent an integer of 1 or more, and m + n represents an integer of 3 or more; And n
(R1 may be different from each other) (C) 3 to 40 parts by weight of an ionic surfactant (D) 5 to 100 parts by weight of a brominated flame retardant (E) 3 to 30 parts by weight of an antimony compound In a preferred embodiment In the above, the ionic surfactant of the component (C) is an anionic surfactant.

[0008] In a preferred embodiment, the ionic surfactant of the component (C) has a melting point higher than the cold crystallization temperature (Tch) of the thermoplastic polyester of the component (A). In a preferred embodiment, the antimony compound as the component (E) is sodium antimonate and / or a mixture of antimony pentoxide and sodium oxide.

[0009] In a preferred embodiment, the resin composition of the present invention further comprises (F) a reinforcing filler. In a preferred embodiment, (G) a crystallization accelerator is further added to the resin composition of the present invention. In a preferred embodiment, (H) a polyfunctional compound is further added to the resin composition of the present invention.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic polyester (A) used in the present invention is preferably terephthalic acid or an ester-forming derivative thereof as an acid component, and a glycol having 2 to 10 carbon atoms as a glycol component. Or a terephthalic acid-based polyester resin obtained by using a derivative having an ester-forming ability thereof. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, and the like. The thermoplastic polyester (A) can be copolymerized with the flame-retardant antistatic polyester resin composition of the present invention within a range that does not impair the properties such as flame retardancy, electrostatic properties, and surface appearance. Ingredients can be included. Examples of such a component include a divalent or higher valent aromatic carboxylic acid having 8 to 22 carbon atoms, a divalent or higher valent aliphatic carboxylic acid having 4 to 12 carbon atoms,
Further, carboxylic acids such as divalent or higher valent alicyclic carboxylic acids having 8 to 15 carbon atoms and ester-forming derivatives thereof, aliphatic compounds having 3 to 15 carbon atoms, 6 to 20 carbon atoms
And compounds having 6 to 40 carbon atoms and having two or more hydroxyl groups in the molecule, and ester-forming derivatives thereof. Specifically, as carboxylic acids, other than terephthalic acid,
For example, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-
Bis (phenoxy) ethane-4,4′-dicarboxylic acid,
Adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3-cyclohexanedicarboxylic acid,
Examples thereof include carboxylic acids such as 1,4-cyclohexanedicarboxylic acid and decahydronaphthalenedicarboxylic acid, and derivatives thereof having ester-forming ability. Examples of the hydroxyl group-containing compounds include ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2′-bis (4-hydroxyphenyl) propane, Compounds such as 2,2′-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, and derivatives having ester forming ability thereof are exemplified. In addition, oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid, and ester-forming derivatives thereof, and cyclic esters such as ε-caprolactone can also be used. Further, polyalkylene glycol units such as polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymerized polyethylene glycol, and polytetramethylene glycol are partially included in the polymer chain. Those copolymerized can also be used. The content of the copolymerizable component of the above components is generally at most 20% by weight, preferably at most 15% by weight, more preferably at most 10% by weight. If it exceeds 20% by weight, the balance of physical properties such as mechanical strength and heat resistance tends to deteriorate. The thermoplastic polyester used in the present invention is preferably a thermoplastic polyester containing ethylene terephthalate and / or tetramethylene terephthalate as a main component in consideration of the balance between mechanical properties and moldability. The intrinsic viscosity of the thermoplastic polyester used in the present invention is 0.35 or more, preferably 0.4 to 2.0, more preferably 0.1 to 2.0.
45 to 1.5. If the intrinsic viscosity is less than 0.35, the mechanical strength tends to decrease. In the present invention, the thermoplastic polyesters are used alone or in combination of two or more. The intrinsic viscosity of phenol: 1, 1, 2, 2
It is determined by measuring at 25 ° C. using a mixed solvent of tetrachloroethane = 1: 1 (weight ratio). The (B) block copolymer used in the present invention is a polyester / ether block copolymer composed of a polyester unit having an alkylene terephthalate unit as a main component and a polyether unit having a specific structure. The polyester unit in (B) is preferably a terephthalic acid-based one obtained by using terephthalic acid or an ester-forming derivative thereof and a glycol having 2 to 10 carbon atoms or an ester-forming derivative thereof, Among them, those having an ethylene terephthalate unit and a tetramethylene terephthalate unit as main components are preferable. The main part of the polyether unit in (B) is represented by the following general formula (1)

[0011]

Embedded image (Wherein, R1 represents an alkyl group having 2 to 5 carbon atoms, X represents a divalent linking group or a direct bond, m and n each represent an integer of 1 or more, and m + n represents an integer of 3 or more; And n
R1 may be different from each other). Specific examples of R1 in the general formula (1) include, for example, ethylene, propylene, isopropylene, butylene and the like, and these are used alone or in combination of two or more. Specific examples of X in the general formula (1), for example _{-C (CH 3) 2 -,} - CH 2 -, - S -, - SO 2 -,
A divalent linking group such as —S (CH ₃ ) ₂ — and —CO— or a direct bond is exemplified. M and n in the general formula (1)
Is an integer of 1 or more, and m + n is an integer of 3 or more. In addition, each is a unit having a molecular weight of 400 or more. The molecular weight of the polyether unit is preferably from 600 to 600.
0, more preferably 800 to 3000. When the molecular weight is less than 400, the melting point of the obtained copolymer decreases,
If the molecular weight exceeds 6000, the compatibility becomes poor and a uniform copolymer cannot be obtained, which is not preferable. (B) The block copolymer can be produced, for example, by the method shown in Japanese Patent Publication No. 5-8941. In addition, these block copolymers are usually 0.35 dl / g to 1.20 d.
It has an intrinsic viscosity of 1 / g, but preferably has an intrinsic viscosity of 0.40 dl / g to 1.00 dl / g from the viewpoint of balance between moldability and mechanical properties and electrical properties. Those having 0.50 dl / g to 0.90 dl / g are more preferable. When the intrinsic viscosity is 0.35 dl / g or less,
The mechanical strength and heat resistance of the composition decrease, and 1.20 dl /
When the amount exceeds g, the fluidity of the composition is reduced, the moldability is deteriorated, and the electric resistance value cannot be sufficiently reduced. (B) In the block copolymer, the ratio of the polyether unit to the polyester unit having an alkylene terephthalate unit as a main component is preferably from 3 to 60% by weight of the polyether unit in 100% by weight of the copolymer. Is 25 to 60% by weight, more preferably 25 to 50% by weight, and 97 to 40% by weight, preferably 75 to 40% by weight, more preferably 75 to 50% by weight of a polyester unit having an alkylene terephthalate unit as a main component. % Is used. If the amount of the polyether unit is less than 3% by weight, the surface properties of the composition obtained are insufficiently improved.
Heat resistance and the like tend to decrease. (B) The addition amount of the block copolymer is preferably 20 to 300 parts by weight, more preferably 40 to 250 parts by weight, based on 100 parts by weight of (A). When the amount of the block copolymer (B) is less than 20 parts by weight, the electric resistance of the molded article is not sufficiently reduced, and when the amount of (B) exceeds 300 parts by weight, the heat resistance of the obtained molded article is poor. It is not preferable because it decreases. As the ionic surfactant (C) used in the present invention, a commercially available ionic surfactant can be used. For example, anionic surfactants include aliphatic alkyl sulfates such as 2-ethylhexyl sulfate, aliphatic alcohol sulfates such as oleyl alcohol sulfate, sodium such as alkylsulfonic acid, alkylbenzenesulfonic acid, and alkylnaphthalenesulfonic acid. Salts, potassium salts and the like, and cationic surfactants include alkylamine salts, quaternary ammonium salts, pyridine derivatives and the like. From the viewpoint of the balance between the mechanical properties and the electrical properties of the composition obtained, an anionic surfactant is preferred. Further, the melting point of the ionic surfactant (C) is preferably higher than the cold crystallization temperature (Tch) of the thermoplastic polyester (A). When the melting point of the ionic surfactant is lower than the cold crystallization temperature of the thermoplastic polyester, bleed out from the composition increases, which causes mold contamination and deterioration of the appearance of the molded product. (C) The compounding amount of the ionic surfactant is 3 to 4 with respect to 100 parts by weight of the thermoplastic polyester.
0 parts by weight, preferably 5 to 40 parts by weight, more preferably 8 to 35 parts by weight. If it is less than 3 parts by weight, the antistatic effect is not sufficient, and if it exceeds 40 parts by weight, mechanical strength and heat resistance are reduced, and mold contamination is also deteriorated. As the brominated flame retardant (D) used in the present invention, commercially available ones can be used. For example, brominated polystyrene, brominated epoxy resin, brominated phenoxy resin, brominated imide, brominated polycarbonate, polybromobenzyl acrylate, brominated diphenylalkane and the like can be mentioned. Among them, brominated polystyrene, brominated diphenylalkane,
Brominated phenoxy resins are preferred. These brominated flame retardants may be used alone or in combination of two or more. The halogen content in the brominated flame retardant used in the present invention is preferably 20% by weight or more, more preferably 25% by weight or more.
% By weight or more. When the halogen content is less than 20% by weight, the flame retardancy is insufficient, which is not preferable. The amount of the brominated flame retardant varies depending on the type of the flame retardant, but is 5 to 100 parts by weight, preferably 10 to 95 parts by weight, more preferably 1 to 100 parts by weight based on 100 parts by weight of the thermoplastic polyester.
5 to 85 parts by weight. If the amount is less than 5 parts by weight, the flame retardancy is not sufficient, and if it exceeds 100 parts by weight, the mechanical strength decreases. The (E) antimony compound used in the present invention is a flame retardant aid, and the flame retardant effect is significantly enhanced by adding it together with the (D) bromine flame retardant. Commercially available antimony compounds can be used, for example, antimony trioxide,
Examples include antimony tetroxide, antimony pentoxide, sodium antimonate, and antimony tartrate, and these may be used alone or in combination of two or more. Above all, from the viewpoint of balance between suppression of thermal decomposition of resin during melt processing and flammability, such as extrusion compounds and injection molding,
A mixture of sodium antimonate and / or antimony pentoxide and sodium oxide is preferably used. The compounding amount of the antimony compound is 3 to 30 parts by weight, preferably 5 to 25 parts by weight based on 100 parts by weight of the thermoplastic polyester. If the amount is less than 3 parts by weight, the flame retardancy is not sufficient. If the amount exceeds 30 parts by weight, the resin deteriorates and the mechanical strength decreases. The composition of the present invention may further contain (F) a reinforcing filler to enhance mechanical strength and heat resistance. Conventionally used reinforcing fillers can be used as they are. For example, glass fiber, carbon fiber, potassium titanate fiber, ceramic beads, glass beads, glass balloon, ceramic balloon, glass flake, calcium silicate, calcium carbonate, calcium sulfate, magnesium silicate, barium sulfate, mica, talc, kaolin, mica , Clay and the like. When a fibrous reinforcing agent such as glass fiber or carbon fiber is used, it is preferable to use a material treated with a sizing agent from the viewpoint of economy and workability. Particularly, when glass fiber is used as the reinforcing filler, the diameter is 1 to 20 μm and the length is 0.01.
About 50 mm is preferable. If the fiber length is too short, the effect of reinforcement is not sufficient, and if it is too long, the surface properties and molding processability of the molded product are unfavorably deteriorated. In order to enhance the adhesion between the resin and the fibrous reinforcing agent, those obtained by treating the surface of the fibrous reinforcing agent with a coupling agent or those using a binder are preferably used. As the coupling agent on the surface of the fibrous reinforcing agent, for example, alkoxysilane compounds such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane are preferably used. As the binder, for example, an epoxy resin, a urethane resin or the like is preferably used, and these are used alone or in combination of two or more, but are not limited thereto. The reinforcing filler used in the present invention can be used alone or in combination of two or more. The amount of reinforcing filler used is thermoplastic polyester 10
The amount is 0 to 200 parts by weight, preferably 5 to 180 parts by weight, based on 0 parts by weight. 200 reinforced fillers used
If the amount is more than 10 parts by weight, the fluidity of the composition is greatly reduced, the moldability is deteriorated, and the surface appearance is also reduced. The composition of the present invention may further contain (G) a crystallization accelerator to improve heat resistance and moldability. For example, organic acid salts such as sodium pt-butyl benzoate, sodium montanate, calcium montanate, sodium palmitate, calcium stearate; and inorganic salts such as calcium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, and talc Salts: metal oxides such as zinc oxide, magnesium oxide, and titanium oxide. These crystallization accelerators are used alone or in combination of two or more. Of the above-mentioned crystallization accelerators, sodium pt-butyl benzoate and sodium montanate are particularly preferred from the viewpoint of improving heat resistance and molding workability.
The compounding amount of these crystallization accelerators is used within a range that does not impair the properties of the present composition. In the case of organic acid salts, the amount is 0.01 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin. In the case of inorganic salts, 0.1 to 10 parts by weight is preferable, and in the case of metal oxide, 0.1 to 10 parts by weight is preferable. The composition of the present invention may further comprise (H) a polyfunctional compound to increase the mechanical strength. A polyfunctional compound is a compound having two or more functional groups, such as -OH group or-
A compound having a functional component that can easily react with any of the COOH groups, or a compound that is thermally or otherwise decomposed to produce such a functional component.
Examples of the functional group reactive with the polyester include an epoxy group, a carbodiimide group, an oxazoline group, an isocyanate group, a carboxylic acid group, a carboxylic anhydride group, and an acid halide compound. A functional group selected from the group consisting of an epoxy group and an oxazoline group is preferred from the viewpoint of reactivity and by-products generated after the reaction. As the compound having an epoxy group, bisphenol type epoxy resin,
Epoxidation of brominated bisphenol type epoxy resin, novolak type epoxy resin, polyvalent aliphatic, alicyclic, aromatic glycidyl ester compound, aliphatic or alicyclic compound having plural unsaturated groups with acetic acid and peracetic acid Epoxy compounds, polyvalent aliphatic, alicyclic, aromatic glycidylamine compounds, and copolymers of olefins and glycidyl (meth) acrylate. Among them, (brominated) bisphenol A type epoxy resin and / or novolak type epoxy resin and ethylene-glycidyl methacrylate-vinyl acetate copolymer are preferable in view of the balance of physical properties of the obtained resin composition. The compound having an oxazoline group is a compound having at least two or more oxazoline groups in a molecule. Among them, bifunctional oxazoline compounds are preferable from the viewpoint of physical property balance and the like,
2,2 ′-(1,3-phenylene) bis (2-oxazoline) and the like are commercially available. These polyfunctional compounds are used alone or in combination of two or more. The compounding amount of this polyfunctional compound is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.15 parts by weight, based on 100 parts by weight of the thermoplastic polyester (A).
~ 2 parts by weight. (H) When the amount of the polyfunctional compound is less than 0.05 part by weight, the effect of improving the mechanical strength of the obtained composition is small, and when it exceeds 5 parts by weight, the fluidity of the obtained composition decreases. In addition, the moldability is significantly inferior, and the mechanical strength is also deteriorated. The flame stability can be further improved by adding an antioxidant to the flame-retardant antistatic polyethylene terephthalate resin composition of the present invention, if necessary. Examples of such antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate, 1,3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, n-octadecyl-3- (3 ',
5'-di-t-butyl-4'-hydroxyphenyl) propionate, N, N'-bis-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionylhexamethylenediamine, tris -(3,5-di-t-
Phenolic antioxidants such as butyl-4-hydroxybenzyl) isocyanurate, and tris (2,4-di-t-
Butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,6-di-t-
Butyl-4-methylphenyl) pentaerythritol-
Phosphorus antioxidants such as di-phosphite; thioether antioxidants such as distearyl-3,3'-thiodipropionate and pentaerythritol-tetrakis- (β-lauryl-thiopropionate). Can be These antioxidants are used alone or in combination of two or more. The flame-retardant antistatic polyethylene terephthalate-based resin composition of the present invention may further contain known and commonly used ultraviolet absorbers, light stabilizers, lubricants, release agents, plasticizers, pigments, dyes, dispersants, and compatibilizers. , An antimicrobial agent, an ionomer resin and the like can be used alone or in combination of two or more. In the composition of the present invention, any other thermoplastic or thermosetting resin within a range that does not impair the effects of the present invention, for example, an unsaturated polyester resin, a liquid crystal polyester resin, a polyester ester elastomer resin, Polyester ether elastomer resin,
Polyolefin resin, polystyrene resin, polyamide resin, polycarbonate resin, rubbery polymer reinforced styrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin,
Polysulfone resins, polyarylate resins, and the like may be added alone or in combination of two or more. The method for producing the polyester resin of the present invention is not particularly limited. For example, after drying the components (A) to (E), or one or more of the components (F), (G), and (H), and other additives, resins, etc. It can be produced by a melt kneading method using a melt kneader such as a twin screw extruder. The molding method of the thermoplastic resin composition produced in the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, for example, injection molding, hollow molding, extrusion molding, Forming methods such as sheet forming, roll forming, press forming, laminating forming, film forming by melt casting, and spinning can be applied.

[0012]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the following, “parts” means parts by weight and “%” means% by weight, unless otherwise specified.

Reference Example 1 3500 g of polyethylene terephthalate (intrinsic viscosity = 0.6 dl / g) synthesized using antimony trioxide as a catalyst, having an average molecular weight of about 1
2,000 bisphenol A ethylene oxide addition polymer and ADK STAB AO-60 2
5 g was charged into a 10-liter autoclave (made of Japan pressure-resistant glass), and the mixture was stirred for 290 under a nitrogen stream.
After the temperature was raised to 1 ° C., the pressure was reduced to 1 Torr or less. 1T
After stirring for 3 hours after reaching orr or below, the polymerization was terminated by returning to normal pressure with nitrogen, and the block copolymer (B-1)
I got The intrinsic viscosity of the obtained copolymer is 0.8 dl / g
Met. (Reference Example 2) A block copolymer (B-B) was prepared in the same manner as in Reference Example 1 except that polytetramethylene terephthalate (intrinsic viscosity = 0.8 dl / g) was used instead of polyethylene terephthalate of Reference Example 1. 2) was obtained. The intrinsic viscosity of the obtained copolymer was 1.0 dl / g.

(Example 1) (A-1) Polyethylene terephthalate (intrinsic viscosity =
0.6 dl / g, Tch = 120 ° C.), 100 parts (B
-1) obtained in Reference Example 1 as a block copolymer,
67 parts of an ethylene terephthalate copolymer, (C-
2) 8.3 parts of an anionic surfactant (trade name: Electrostripper PC-03: manufactured by Kao Corporation: Tm = 150 ° C) as an ionic surfactant, and (D-2) bromine as a brominated flame retardant 35 parts of fluorinated polystyrene (trade name: Pyrocheck 68PB: Nissan Ferro-Organic Chemical Co., Ltd .: bromine content: 68%), and (E-2) sodium antimonate (trade name: San-Epoc NA10) as an antimony compound
70 L: 9 parts of Nissan Chemical Industry Co., Ltd.) and (G-1) 0.3 parts of sodium pt-butyl benzoate (trade name: Nonsal TBAN, manufactured by NOF Corporation) as a crystallization accelerator. , Irganox 1010 as an antioxidant
(Ciba Geigy Special Co., Ltd.) (0.5 parts) was added and mixed, and the barrel temperature was set to 280 ° C. with a twin screw extruder equipped with a TEX44 vent manufactured by Japan Steel Works, Ltd.
I put it in from the hopper. Further, 55 parts of glass fiber (T-195H, manufactured by NEC Corporation) was added as a fibrous reinforcing agent (F-1) from the side feeder of the extruder and melt-extruded to obtain a resin composition. Was. Evaluation Method After the obtained resin composition and comparative resin composition were dried at 140 ° C. for 4 hours, injection molding was performed at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using a 35-t injection molding machine to obtain a thickness of 0 mm. 2.8mm, 1.6mm (each 12.7m wide
m, length 127 mm) bar and 80 mm x 40 m
5. A mx3 mm flat plate is processed at a cylinder temperature of 280 ° C and a mold temperature of 90 ° C using an 80t injection molding machine.
4mm (width 12.7mm, length 127mm) bar, AS
TM1 dumbbell (3.2mm thickness), 120 × 120 ×
A 3 mm flat plate test piece was obtained, and the following evaluation was performed.

<Flame Retardancy> Flame retardancy was evaluated using a 0.8 mm thick and 1.6 mm thick bar according to the vertical burning test method described in UL94.

<Volume resistivity, surface resistivity> 12
ASTM D-25 using a 0 × 120 × 3 mm flat plate
The resistivity was measured according to No. 7, and the volume resistivity was determined.

<Tensile Strength> A 3.2 mm thick dumbbell was used to perform a tensile test in accordance with ASTM D-638 to determine the maximum strength.

<Bending strength> Using a 6.4 mm thick bar,
A bending test was performed according to ASTM D-790, and a maximum strength and a maximum deflection (bending elongation) were obtained. <Residence Heat Stability> When molding a 6.4 mm thick bar, the cooling time is usually 20 seconds (30 seconds as a molding cycle).
ec) to 170 sec (180 s as molding cycle)
The molding was performed by elongating to ec). Using the obtained test piece, a bending test was performed in accordance with ASTM D-790 to determine a maximum bending strength, and a strength retention ratio to a normal molded product was calculated.

<Heat resistance> Using a 6.4 mm thick bar, A
According to STM D-648, the deflection temperature under load (HDT) at a load of 1.82 MPa was evaluated.

<Surface Appearance> As the surface appearance of the composition,
An 80 mm × 40 mm × 3 mm flat plate was observed, and the appearance was determined based on the following criteria. A: A very good glossy surface is obtained. ：: A good glossy surface is obtained. Δ: Some fogging occurs at the end of the plate. X: Clouding occurs on more than half of the plate. (Examples 2 to 7) (A-2) Polytetramethylene terephthalate (intrinsic viscosity = 0.9, Tch = 50) as thermoplastic polyester
° C) (B-2) Tetramethylene-based copolymer obtained in Reference Example 2 as a block copolymer (C-1) Anionic surfactant (trade name: Electrostripper PC, Tm = 1
(10 ° C .: manufactured by Kao Corporation) (D-1) Brominated diphenylethane (trade name: Saytex8010: Albemarle Co., Ltd.) as a brominated flame retardant
(D-3) Brominated phenoxy resin as brominated flame retardant (trade name: Phenotote YPB-43MK: manufactured by Toto Kasei Co., Ltd .: bromine content: 58%) (E-1) Antimony Antimony trioxide as a compound (trade name: Antimony C: manufactured by Sumitomo Metal Mining Co., Ltd.) (E-3) As an antimony compound, a mixture of antimony pentoxide and sodium oxide (trade name: San-Epoque NA1)
030: manufactured by Nissan Chemical Industries, Ltd.) (F-2) As a reinforcing filler, mica (trade name: mica powder A-41S: manufactured by Mika Yamaguchi Co., Ltd.) (G-2) As a crystallization accelerator, Montanic acid sodium salt (trade name Hostamont NaV101: manufactured by Hoechst Japan K.K.) (H-1) As a polyfunctional compound, Epicoat 828 is used.
(Yukahashi Shell Epoxy Co., Ltd., epoxy equivalent 1
85), and a resin composition was obtained and evaluated in the same manner as in Example 1 except that the components were mixed at the ratios shown in Table 1.

Comparative Example 1 (A-1) As a thermoplastic polyester, polyethylene terephthalate (intrinsic viscosity = 0.6 dl / g, Tch = 1)
20 ° C.), 100 parts of (B-1) an ethylene terephthalate copolymer obtained in Reference Example 1 as a block copolymer, 67 parts of (D-2) a brominated polystyrene as a brominated flame retardant ( 35 parts of trade name Pyrocheck 68PB: Nissan Ferro-Organic Chemical Co., Ltd .: 68% bromine content)
(E-2) 9 parts of sodium antimonate (trade name: San-Epoque NA1070L: manufactured by Nissan Chemical Industries, Ltd.) as an antimony compound, and (G-1) p- as a crystallization accelerator
Sodium t-butyl benzoate (trade name: Nonsal TB)
AN, manufactured by Nippon Yushi Co., Ltd.) and Irganox 1010 (trade name, manufactured by Ciba Geigy Special Co., Ltd.) as an antioxidant were added and mixed by 0.5 part. A resin composition was obtained.

(Comparative Examples 2 to 6) (A-2) Polytetramethylene terephthalate (intrinsic viscosity = 0.9, Tch = 50) as a thermoplastic polyester
° C) (B-2) Tetramethylene-based copolymer obtained in Reference Example 2 as a block copolymer (C-1) Anionic surfactant (trade name: Electrostripper PC, Tm = 1
10 ° C .: manufactured by Kao Corporation) (C-3) As a nonionic surfactant, an ether-modified end-capped polyester oligomer (intrinsic viscosity = 0.5)
(3, Tm = 168 ° C.) (D-1) Brominated diphenylethane (trade name: Saytex 8010: Albemarle Co., Ltd.) as a brominated flame retardant
(D-3) Brominated phenoxy resin as brominated flame retardant (trade name: Phenotote YPB-43MK: manufactured by Toto Kasei Co., Ltd .: bromine content: 58%) (E-1) Antimony Antimony trioxide as a compound (trade name: Antimony C: manufactured by Sumitomo Metal Mining Co., Ltd.) (E-3) As an antimony compound, a mixture of antimony pentoxide and sodium oxide (trade name: San-Epoque NA1)
030: manufactured by Nissan Chemical Industries, Ltd.) (F-2) As a reinforcing filler, mica (trade name: mica powder A-41S: manufactured by Mika Yamaguchi Co., Ltd.) (G-2) As a crystallization accelerator, Montanic acid sodium salt (trade name Hostamont NaV101: manufactured by Hoechst Japan K.K.) (H-1) As a polyfunctional compound, Epicoat 828 is used.
(Yukahashi Shell Epoxy Co., Ltd., epoxy equivalent 1
85), and a resin composition was obtained and evaluated in the same manner as in Example 1 except that the components were mixed at the ratios shown in Table 1. Table 1 shows the results of Examples 1 to 7 and Comparative Examples 1 to 6.

As is clear from the comparison between the examples in Table 1 and the comparative examples, all of the compositions of the present invention are difficult to reach with non-carbon materials while maintaining high flame retardancy, mechanical strength and heat resistance. The antistatic level of 1E10Ω · cm to 1E
It has excellent electrostatic properties of 11 Ω · cm, furthermore, the retention heat stability is improved, and the appearance of the molded product is also good. further,
As is clear from the comparison between Example 1, Example 6 and Example 7, the addition of (G) a crystallization accelerator and (H) a polyfunctional compound makes it possible to improve the flame retardancy and electrostatic properties. The mechanical strength and heat resistance can be improved without any loss. Furthermore, as is clear from Examples 1 to 4, Examples 6 and 7, and Example 5, by selecting a (C) ionic surfactant whose melting point satisfies specific conditions, the flame retardancy and
The surface appearance of the resin composition can be further improved without impairing mechanical properties and electrostatic properties.

[0024]

Industrial Applicability The flame-retardant antistatic polyester resin composition of the present invention has excellent flame retardancy, mechanical properties and heat resistance, and is difficult to achieve with a surfactant system. It has a level of resistance. Furthermore, since the toughness is improved, it is possible to assemble the parts by the inset type, and since the thermal stability at the time of molding is also good, it is possible to obtain a molded article having a good surface appearance of the molded article, Also very useful.

[0025]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/1515 C08K 5/15 B 5/42 5/42 13/02 13/02 F-term (Reference) 4J002 BC113 BG083 CF031 CF041 CF051 CF061 CF071 CF101 CF102 CF142 CG033 CH083 CM043 DA019 DE058 DE100 DE128 DE130 DE149 DE188 DE189 DE230 DE239 DG040 DG049 DG050 DG059 DJ000 DJ009 DJ039 DJ040 DJ049 DJ059 DL009 EB137 EG037 EB137 EB037 FD137 FD138 FD200 FD316

Claims (8)

[Claims] 1. A flame-retardant antistatic polyester resin composition comprising the following components (A) to (E). (A) 100 parts by weight of a thermoplastic polyester (B) Block copolymers 40 to 3 of a polyalkylene terephthalate and a unit represented by the following general formula (1)
00 parts by weight (Wherein, R1 represents an alkyl group having 2 to 5 carbon atoms, X represents a divalent linking group or a direct bond, m and n each represent an integer of 1 or more, and m + n represents an integer of 3 or more; And n
(C) 3 to 40 parts by weight of an ionic surfactant (D) 5 to 100 parts by weight of a brominated flame retardant (E) 3 to 30 parts by weight of an antimony compound 2. The flame-retardant antistatic polyester resin composition according to claim 1, wherein the ionic surfactant of the component (C) is an anionic surfactant. 3. The ionic surfactant of the component (C) has a melting point higher than the cold crystallization temperature (Tch) of the thermoplastic polyester of the component (A). And a flame-retardant antistatic polyester resin composition. 4. The antimony compound as the component (E),
It is sodium antimonate and / or a mixture of antimony pentoxide and sodium oxide.
4. The flame-retardant antistatic polyester resin composition according to any one of the above items 3. 5. The flame-retardant antistatic polyester resin composition according to claim 1, further comprising (F) a reinforcing filler. 6. The flame-retardant antistatic polyester resin composition according to claim 1, further comprising (G) a crystallization accelerator. 7. The flame-retardant antistatic polyester resin composition according to any one of claims 1 to 6, further comprising (H) a polyfunctional compound. 8. A molded article molded using the flame-retardant antistatic polyester resin composition according to claim 1. Description: