JPH0689237B2 - Flame-retardant aromatic polyester composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant polyester composition having excellent antistatic properties, heat resistance, flame retardancy and mechanical properties, and mainly as an engineering plastic. It is used.

[Conventional technology]

Since polybutylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, etc., it has been widely used in recent years for applications such as mechanical parts and electric parts. On the other hand, in addition to the balance of general chemical and physical properties, these industrial materials are strongly required to have safety against flames, that is, flame retardancy. At present, it is necessary to impart flame retardancy to polybutylene terephthalate applications. It is no exaggeration to say that it is a prerequisite for expansion. Recently, in addition to such flame retardancy, applications that require antistatic properties are spreading.

It is well known that a combination of an organic bromine compound and an antimony compound is used as a flame retardant-imparting agent for polybutylene terephthalate (see JP-A-55-5958).

In addition, various methods have been proposed as methods for imparting antistatic properties to polybutylene terephthalate. Among them, the methods of adding both polyalkylene glycol or its derivative and metal salt of alkylsulfonic acid, which are shown in JP-A-52-47072 and JP-A-53-149246, are relatively excellent. Therefore, attempts have been made to combine these two technologies.

[Problems to be solved by the invention]

However, when the above method of adding an alkylsulfonate and a polyalkylene glycol or a derivative thereof together to a polybutylene terephthalate resin containing an organic bromine compound and an antimony compound is applied, mechanical properties are significantly lowered, Further, since a large amount of flame retardancy is required, there is a problem that the extrudability and heat resistance are significantly reduced.

Therefore, the present inventors have achieved the present invention as a result of extensive studies to solve such problems.

Therefore, an object of the present invention is to provide an aromatic polyester composition which is excellent not only in flame retardancy but also in antistatic property, and also in heat resistance and mechanical properties, particularly rigidity and impact resistance.

[Means for solving problems]

That is, the flame-retardant aromatic polyester composition of the present invention comprises (B) 0.01 to 10 parts by weight of an alkylsulfonic acid metal salt represented by the following general formula (I) with respect to (A) 100 parts by weight of polybutylene terephthalate resin. Department (In the formula, R is an alkyl group having a carbon number of m, R'is an alkyl group having a carbon number of n (where m and n are integers satisfying m ≧ 2, n ≧ 2,6 ≦ m + n ≦ 30), and M is a metal. Atoms and P indicate the number of charges of the metal M.

(C) 1 to 60 parts by weight of an organic bromine compound and (D) 1 to 40 parts by weight of an antimony compound are blended.

Hereinafter, the constitution of the present invention will be described more specifically.

The (A) polybutylene terephthalate resin used in the present invention is obtained by a condensation reaction using terephthalic acid or its ester-forming derivative as an acid component and 1,4-butanediol or its ester-forming derivative as a diol component. It is a polymer.

If the acid component is 20 mol% or less, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4 Even if a dicarboxylic acid other than terephthalic acid such as ′ -diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid or an ester-forming derivative thereof is used. Well, if the diol component is 20 mol% or less, ethylene glycol, 1,2-propanediol, 1,3-propanediol,
1,5-pentanediol, 1,6-hexanediol, 1,10
-Decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, 2-methyl-1,3-propanediol, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, etc.
A diol other than 4-butanediol may be used.

As a polybutylene terephthalate resin, 0.5%
The relative viscosity of the orthochlorophenol solution of 1. is measured at 25 ° C., the relative viscosity is preferably 1.30 to 2.00, and more preferably 1.35 to 1.70. When the relative viscosity of the polybutylene terephthalate resin is less than 1.30, sufficient mechanical strength cannot be obtained, and when it exceeds 2.00, the fluidity at the time of molding becomes poor, which is not preferable either.

The metal salt of alkyl sulfonic acid (B) used in the present invention has the following general formula: (In the formula, R and R'are alkyl groups having carbon numbers m and n, M is a metal atom, P is the number of charges of the metal M, and m and n are integers satisfying the following conditions. M2, n
2,6m + n30).

The alkyl group of R and R'may be linear or branched, and the sum of carbon numbers of R and R '(m +
n) is 6 to 30, preferably 10 to 20. The compound of formula (I) may be a single compound or a mixture of different compounds.

Preferred examples of M include alkali metals and alkaline earth metals, of which lithium, sodium and potassium are more preferred, and sodium is particularly preferred.

Preferred specific examples of the compound represented by the formula (I) include:
The compound of the following general formula may be mentioned.

Of the compounds represented by the general formulas (II) to (IV), compounds having m + n (the number of carbon atoms of the alkyl group bonded to C adjacent to S) of 12 to 16 are particularly preferable.

In the present invention, when R or R ′ has 1 or less carbon atoms, that is, when the metal sulfonate group is present at the terminal of the alkyl group or at the β-position, the antistatic property is not exhibited when added to the polybutylene terephthalate resin. Further, when the sum (m + n) of the carbon numbers of both is less than 6, the mechanical properties of the polybutylene terephthalate resin tend to be deteriorated, while when it exceeds 30, the antistatic effect tends to be deteriorated. Not preferable.

The amount of the alkyl sulfonic acid metal salt added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin.
Parts by weight. If the addition amount is less than 0.01 parts by weight, the effect of improving the antistatic property is not recognized, and if it exceeds 10 parts by weight, the mechanical properties of the polybutylene terephthalate resin tend to deteriorate, which is not preferable.

Other antistatic agents (such as sodium dodecylbenzene sulfonate, sodium linear alkyl sulfonate, aryl metal hypophosphite, etc., provided that 50% by weight or more of the total amount of the antistatic agent is the alkyl sulfonate metal salt of the present invention. Salt, etc.) may be used together.

The organic bromine compound used as the component (C) in the present invention has a bromine atom in the molecule, and a known organic bromine compound which is usually used as a flame retardant can be used. % Or more is preferable. Specifically, hexabromobenzene, pentabromotodiene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene bis- ( Tetrabromophthalimide), a low molecular weight organic bromine compound such as tetrabromobisphenol A, a brominated polycarbonate (for example, a polycarbonate oligomer produced from brominated bisphenol A as a raw material), a brominated epoxy compound (for example, brominated bisphenol A and epichlorohydrin) Reaction-produced diepoxy compounds or monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin), poly ( Fluorinated benzyl acrylate),
Brominated polyphenylene ether, brominated bisphenol
Examples include condensates of A / cyanuric chloride / brominated phenol, brominated polymers such as brominated polystyrene and oligomers, or mixtures thereof. Particularly preferred are brominated epolycarbonate oligomers and brominated epoxy compounds, including bromine, alkyl or A brominated polycarbonate oligomer end-capped with an aryl-substituted phenol is most preferably used.

The amount of the organic bromine compound (C) added is 1 to 60 parts by weight, based on 100 parts by weight of the folybutylene terephthalate resin,
It is preferably 5 to 30 parts by weight. If the amount added is less than 1 part by weight, the flame retardancy is not sufficient, and if it exceeds 60 parts by weight, the physical properties of the composition deteriorate, which is not preferable.

The antimony compound used as the component (D) in the present invention is not particularly limited as long as it is usually used as a flame retardant aid for polyester. Specific examples of antimony compounds include antimony trioxide, antimony pentoxide, antimony hexaoxide, antimony trioxide, and other antimony oxides, sodium antimonate, potassium antimonate, antimony sulfide, antimony potassium tartrate, antimony caproate. , Triethoxy antimony, triphenyl antimony and the like, and antimony oxide, particularly antimony trioxide can be preferably used. Further, zirconium oxide, zinc sulfide, barium sulfate or the like may be used together with the antimony compound.

The addition amount of the antimony compound in the present invention is 1 to 40 parts by weight based on 100 parts by weight of polybutylene terephthalate resin,
The amount is preferably 3 to 20 parts by weight, and particularly preferably 1 antimony atom per 2 to 5 bromine atoms in the composition.

Although not essential to the resin composition of the present invention, an inorganic filler can be added to improve rigidity, dimensional accuracy and the like.
The specific inorganic filler may be in any form such as fibrous or granular, and specifically, glass fiber, carbon fiber, metal fiber, asbestos, wollastonite, potassium whisker titanate, clay, mica, bentonite, glass beads. , Titanium oxide, calcium carbon, barium sulfate, gypsum, aluminum oxide, titanium oxide, talc and the like, and chopped strand type glass fiber can be preferably used. When the inorganic filler is added, the addition amount thereof is 150 parts by weight or less, preferably 100 parts by weight or less based on 100 parts by weight of the polybutylene terephthalate resin. If the addition amount exceeds 150 parts by weight, the mechanical properties of the polybutylene terephthalate resin tend to be impaired, which is not preferable.

It is generally said that such an inorganic filler has a small effect of improving rigidity when an antistatic agent is present in the composition, but in the case of the present invention, such a tendency is not observed.

Incidentally, the composition of the present invention is a weather resistance and an ultraviolet absorber (for example, various resorcinol, salicylate, benzotriazole, benzophenone, etc.), a lubricant and a mold release agent (for example, stearic acid and the like thereof) within a range that does not impair the object of the present invention. One or more usual additives such as salts, esters, half esters, stearyl alcohol, stearamide), dyes, colorants including pigments, and crystallization accelerators can be added. A small amount of another thermoplastic resin (for example, polyethylene, polypropylene, polyamide, polyacetal, polycarbonate, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / vinyl acetate copolymer, Ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / butene-1 copolymer, acrylic rubber, polyether ester elastomer, etc., ethylene / glycidyl methacrylate copolymer and ethylene / methacryl Glycidyl acid / vinyl acetate copolymer is preferable), and a thermosetting resin may be added.
You may use together 1 or more types.

The method for producing the composition of the present invention is not particularly limited, but a preferable method is a method in which a polybutylene terephthalate resin, an alkyl sulfonate, an organic bromine compound and an antimony compound are melt-kneaded using an extruder.

〔Example〕

 The effects of the present invention will be described in more detail below with reference to examples.

Examples 1 to 4, Comparative Examples 1 to 4 100 parts by weight of polybutylene terephthalate having a relative viscosity of 1.45 was added to brominated polycarbonate (manufactured by Teijin Chemicals Ltd.).
FG-7500) 20 parts by weight, 7 parts by weight of antimony trioxide and the type and amount of the antistatic agent shown in Table 1 are added, kneaded with a ribbon blender, and then melt mixed by a screw extruder set at 250 ° C. Pelletized. Next, using the 5 ounce screw in-line type injection molding machine which set the pellets obtained at 250 ° C, 3mm x 60mm x 60mm square plate, ASTM1
No. 1 dumbbell, 1/4 "wide Izod impact test pieces and 1/32" thick combustion test pieces were prepared. Among these test pieces, with respect to the tensile test and the Izod impact test with V notch, the performance was compared with and without aging treatment at 130 ° C. for 3 hours. Furthermore, using a super-insulation resistor, the resistivity of the rectangular plate molded product and the half-life of charge decay (the time required for this charge to decay to half the initial value after applying 8000V charge for 120 seconds (half-life )) Measurement and UL-94 combustion test. The results are shown in Table-1.

When the alkyl sulfonate of the present invention is added to the polybutylene terephthalate resin in combination with the organic bromine compound and the antimony compound, the antistatic effect is large as can be seen from the comparison between Examples 1 and 2 and Comparative Example 3, It is also clear that polybutylene terephthalate having high heat resistance, high rigidity and good flame retardancy can be obtained as compared with Comparative Example 4.

Examples 5-7 Instead of the brominated polycarbonate of Example 2, (E) brominated epoxy compound (FR-500 manufactured by Dainippon Ink and Chemicals, Inc.),
(F) Brominated polystyrene (manufactured by Nissan Fuero Co., Ltd. 68P
B), (G) Brominated polyphenylene oxide (PO-64P manufactured by Great Lakes) was used, and extrusion, molding and evaluation were carried out in the same manner as in Example 2. The results are shown in Table-2.

From the results shown in Table 2, it can be seen that excellent antistatic property and heat resistance are provided even when an organic bromine compound such as brominated epoxy, brominated polystyrene, brominated polyphenylene oxide is used as the flame retardant.

Example 8 and Comparative Examples 5 to 6 Processing and physical properties were evaluated in the same manner as in Example 1 except that 30% by weight of chopped strand glass fiber having a fiber length of 3 mm was added to Example 1 (Example 8). .

For comparison, a composition obtained by adding 30% by weight of the same glass fiber as in Example 8 to the composition excluding the antistatic agent (Comparative Example 5) and the composition having a different antistatic agent (Comparative Example 4) (Comparison) Example 6) was also evaluated, and the results are shown in Table 3.

From the results shown in Table 3, when glass fibers are blended with polybutylene terephthalate, a specific metal salt of an alkyl sulfonic acid and an organic bromine compound, not only the antistatic property and heat resistance are improved, but also the molding having excellent mechanical properties is achieved. You can see that the product is obtained.

〔The invention's effect〕

As described above, the composition of the present invention is obtained by blending polybutylene terephthalate with a specific metal salt of an alkyl sulfonic acid, an organic bromine compound and an antimony compound in a specific amount, and thus flame retardancy as well as antistatic property and A molded article having excellent heat resistance and mechanical properties, particularly rigidity and impact resistance, can be provided, and its use as various engineering plastics is expected by injection molding or extrusion molding.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-52-47072 (JP, A) JP-A-53-149246 (JP, A) JP-A-54-65757 (JP, A)

Claims (1)

[Claims] 1. A polybutylene terephthalate resin (A) 10
0.01 to 10 parts by weight of (B) an alkyl sulfonic acid metal salt represented by the following general formula (I), relative to 0 parts by weight. (In the formula, R is an alkyl group having a carbon number of m, R'is an alkyl group having a carbon number of n (where m and n are integers satisfying m ≧ 2, n ≧ 2,6 ≦ m + n ≦ 30), and M is a metal. Atoms and P indicate the number of charges of the metal M. (C) 1 to 60 parts by weight of an organic bromine compound and (D) 1 to 40 parts by weight of an antimony compound are blended, which is a flame-retardant aromatic polyester composition. object.