JPH08225729A - Flame-retardant polyester-based resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition useful as a material for functional parts, having excellent mechanical strength, fluidity, external appearance of molding and flame-retardance by blending a thermoplastic polyester with a specific epoxy resin, a PS-based resin, an Sb compound and a filler. CONSTITUTION: This composition is obtained by blending (A) 100 pts.wt. of a thermoplastic polyester (e.g. a polyethylene terephthalate-based resin having >=80% ethylene terephthalate repeating unit or a tetramethylene terephthalate having >=80% tetramethylene terephthalate repeating unit) with (B) 0.05-10 pts.wt. of an epoxy compound of formula I ((q) is 1-40), (C) 1-50 pts.wt. of a PS-based resin of formula II (R is H or CH3 ; X is Br or C1; (m) is 1-5; (n) is >=10), (D) 0.1-20 pts.wt. of an antimony oxide compound and (E) 0-150 pts.wt. of a reinforcing filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester resin composition which has excellent mechanical strength and fluidity and has a good molded product surface.

[0002]

2. Description of the Related Art Thermoplastic polyester resins typified by polyethylene terephthalate and polytetramethylene terephthalate have been widely used as fibers, films, molding materials, etc. because of their excellent mechanical properties and electrical properties. There is. Furthermore, since mechanical strength and thermal properties are significantly improved by blending a reinforcing filler such as glass fiber with these thermoplastic polyester resins, the reinforcing composition thus obtained is a so-called functional material. Is suitable as In recent years, especially in the field of electric or electronic parts, the demand for safety against fire has increased, and flame retardation of resins has been performed, and resin compositions containing various flame retardants have been put on the market. The flame-retardant method of the polyester resin composition is disclosed in, for example, JP-A-50-92346, JP-A-4-198357 or JP-A-5-140427, in which a halogenated polystyrene resin is added to a thermoplastic polyester resin. 50-35257 and JP-A-62-15256, a method of adding a halogenated bisphenol A type epoxy resin, JP-A-59-149954.
Has proposed a method of adding a high molecular weight halogenated bisphenol A type phenoxy resin.

[0003]

However, when a halogenated bisphenol A type epoxy resin is used as the flame retardant, the flame retardant has a relatively low molecular weight during injection molding, so that it easily bleeds onto the surface of the molded article. There is a problem that the surface property deteriorates. When a high molecular weight halogenated bisphenol A-type phenoxy resin having an epoxy group at the terminal is used as the flame retardant, the fluidity of the resin is lowered because the flame retardant has a high molecular weight, and a thermoplastic polyester is used. Has poor dispersibility and causes a decrease in mechanical strength. Furthermore, in the method of adding halogenated polystyrene, there is a problem that the fluidity and mechanical strength of the polyester itself is significantly reduced, and in order to improve this point, a method of adding a specific epoxy compound and antimony trioxide (Tokuhei 1-600
56) has been proposed. However, in this method, even if the reduction of the mechanical strength is suppressed, the effect of improving the fluidity is insufficient, and the flow pattern is likely to occur on the surface of the molded product under the present circumstances.

[0004]

The present inventors have diligently studied a flame-retardant polyester resin composition having the above problems, excellent mechanical strength and fluidity, and having a good molded product surface. As a result, by using a specific epoxy compound and a halogenated polystyrene and / or a halogenated poly-α-methylstyrene as a flame retardant, and an antimony oxide compound as a flame retardant aid in combination, it was found that the above problems can be achieved. Invented.

That is, in the present invention, (B) the following general formula (I) is added to 100 parts by weight of (A) thermoplastic polyester.

[0006]

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0.05 to 10 parts by weight of a novolac type epoxy compound represented by the formula (wherein q represents an integer of 1 to 40), (C) the following general formula (II)

[0008]

[Chemical 4]

(In the formula, R is H or CH ₃ group, X is bromine or chlorine atom, m is an integer of 1 to 5, and n is an integer of 10 or more.) Or 1 to 50 parts by weight of halogenated poly-α-methylstyrene, 0.1 to 20 parts by weight of (D) antimony oxide compound,
And (E) a flame-retardant polyester resin composition containing 0 to 150 parts by weight of a reinforcing filler.

As the thermoplastic polyester (A) used in the present invention, terephthalic acid or a derivative thereof having an ester forming ability is used as an acid component, and a glycol having 2 to 10 carbon atoms or a derivative thereof having an ester forming ability is used as a glycol component. It is a polyester resin obtained by using it, and specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate, and polyhexamethylene terephthalate.

Known components that can be copolymerized can be used in the thermoplastic polyester as long as the flame retardancy and moldability of the flame retardant polyester resin composition are not impaired. As the component, a divalent or more aromatic carboxylic acid having 8 to 22 carbon atoms, a divalent or more aliphatic carboxylic acid having 4 to 12 carbon atoms, and further a divalent or more alicyclic carboxylic acid having 8 to 15 carbon atoms. Carboxylic acids such as acids and ester-forming derivatives thereof, aliphatic compounds having 3 to 15 carbon atoms, 6 to 2 carbon atoms
Examples thereof include alicyclic compounds having 0, aromatic compounds having 6 to 40 carbon atoms and compounds having 2 or more hydroxyl groups in the molecule, and ester-forming derivatives thereof.

Specifically, as carboxylic acids, other than terephthalic acid, for example, isophthalic acid, naphthalene dicarboxylic acid, bis (p-carboxyphenyl) methaneanthracene dicarboxylic 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, 1,4-cyclohexanedicarboxylic acid, decahydronaphthalenedicarboxylic acid Carboxylic acids such as acids or derivatives thereof having the ability to form an ester,
As the hydroxyl group-containing compounds, in addition to ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol,
Cyclohexanedimethanol, cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl)
Examples thereof include compounds such as propane, hydroquinone, glycerin, and pentaerythritol, or derivatives thereof having ester-forming ability. In addition, p-oxybenzoic acid, p-
Oxyacids such as hydroxyethoxybenzoic acid and their ester-forming derivatives, cyclic esters such as ε-caprolactone and the like can also be used. Further, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, ethylene oxide addition polymer of bisphenol A, propylene oxide addition polymer, tetrahydrofuran addition polymer, polytetramethylene glycol It is also possible to use those obtained by partially copolymerizing a polyalkylene glycol unit such as

The copolymerization amount of the above components is generally 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less. Furthermore, from the balance of mechanical strength and moldability, ethylene terephthalate and / or
Alternatively, a thermoplastic polyester containing a tetramethylene terephthalate unit as a main component is preferable.

Intrinsic viscosity of the thermoplastic polyester [phenol: 1,1,2,2-tetrachloroethane = 1: 1
(Weight ratio) Measured at 25 ° C. using mixed solvent] is 0.
It is 35 or more, preferably 0.4 to 2.0, and more preferably 0.45 to 1.5. If it is less than 0.35, the mechanical strength of the flame-retardant resin composition is insufficient and 2.0
If it exceeds the range, the molded article is deteriorated, which is not preferable.
The thermoplastic polyesters may be used alone or in combination of two or more.

The novolak type epoxy compound (B) used in the present invention is represented by the above general formula (I), and is, for example,
It is a compound synthesized by the reaction of novolak resin obtained from phenol and formaldehyde with epichlorohydrin and the like. In the general formula (I), the degree of polymerization q is in the range of 1-40. When q is 0, the surface of the molded product is deteriorated, and when q is 41 or more, fluidity and mechanical strength are poor.

The amount of the novolac type epoxy compound (B) used is 0.05 to 10 parts by weight, preferably 0.1 to 7 parts by weight, more preferably 0, based on 100 parts by weight of the thermoplastic polyester (A). 0.1 to 5 parts by weight.
When the amount of the epoxy compound (B) is less than 0.05 parts by weight, the effect of improving the mechanical strength and fluidity of the obtained molded article is small, and when it exceeds 20 parts by weight, the fluidity of the resulting composition is low. Significantly reduced, mechanical strength is inferior.

The (C) halogenated polystyrene and halogenated poly-α-methylstyrene used in the present invention are represented by the above general formula (II), and specific examples thereof include polydibromostyrene, polytribromostyrene and polypenta. Bromostyrene, polydichlorostyrene, polytrichlorostyrene, polypentachlorostyrene, polytribromo α-
Methyl styrene and the like can be mentioned, and these can be used alone or in combination of two or more kinds. Halogenated polystyrene or halogenated poly-α-methylstyrene is produced by polymerizing halogenated styrene or halogenated-α-methylstyrene, or halogenating polystyrene or poly-α-methylstyrene. The halogen content is preferably 20% by weight or more, more preferably 2
It is 5% by weight or more. When the halogenation rate is less than 20% by weight, the flame retardance is insufficient, which is not preferable. Also,
In the general formula (II), X is preferably a bromine atom from the viewpoint of flame retardancy. Further, when n is 9 or less, the mechanical strength and the surface property of the molded product are poor.

The amount of the halogenated polystyrene and / or the halogenated poly-α-methylstyrene used is 1 to 50 parts by weight, preferably 10 to 30 parts by weight, and 1 part by weight based on 100 parts by weight of the thermoplastic polyester. If the amount is less than 50% by weight, the flame retardance is insufficient, and if it exceeds 50 parts by weight, the mechanical strength is lowered.

The composition of the present invention contains (D) as a flame retardant aid.
The flame retardant effect is remarkably enhanced by adding the antimony oxide compound together. Examples of the antimony compound include antimony trioxide, antimony tetroxide, antimony pentoxide, and the like. These may be used alone or in combination of two or more, and antimony trioxide is particularly preferable.

The amount of the antimony compound used varies depending on the novolac type epoxy resin used in combination, but is 0.1 to 2 per 100 parts by weight of the thermoplastic polyester resin.
It is 0 part by weight, preferably 1 to 15 parts by weight. If it is less than 0.1 part by weight, the flame retardancy is insufficient, and if it exceeds 20 parts by weight, the mechanical strength of the thermoplastic polyester resin is lowered.

The flame-retardant polyester resin composition of the present invention includes, in addition to the above components, a composition containing (E) a reinforcing filler, that is, a reinforced flame-retardant polyester composition. Therefore, known and conventional ones can be used as they are. Examples of the reinforcing filler include glass fiber, carbon fiber, potassium titanate fiber, glass beads, glass flakes, calcium carbonate, calcium sulfate, barium sulfate and the like. As the reinforcing filler, fibrous reinforcing agents such as glass fibers and carbon fibers are preferable, and from the viewpoint of workability, it is preferable to use chopped strand glass fibers treated with a sizing agent. Further, in order to enhance the adhesiveness between the resin and the fibrous reinforcing agent, it is preferable that the surface of the fibrous reinforcing agent is treated with a coupling agent, and a binder may be used.

Examples of the coupling agent include γ-
Alkoxysilane compounds such as aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, and binders such as epoxy resin and urethane resin are preferably used, but not limited thereto. . These are used alone or in combination of two or more.

When glass fiber is used as the reinforcing filler,
A diameter of 1 to 20 μm and a length of 0.01 to 50 mm are preferable. If the fiber length is too short, the reinforcing effect is insufficient, and conversely, if the fiber length is too long, the surface properties and molding processability of the molded product deteriorate, which is not preferable.

The reinforcing filler may be used alone or in combination of two or more. The amount of the reinforcing filler used is 1 with respect to 100 parts by weight of the (A) polyester-based thermoplastic polyester.
It is 50 parts by weight or less, preferably 120 parts by weight or less, and more preferably 2 to 100 parts by weight. If the amount of the reinforcing filler used exceeds 150 parts by weight, the moldability will deteriorate.

In the composition of the present invention, any other thermoplastic or thermosetting resin within the range not impairing the present invention, for example, saturated or unsaturated polyester resin other than polyethylene terephthalate resin, liquid crystal polyester -Based resin, polyester ester elastomer-based resin, polyester ether elastomer-based resin, polyolefin-based resin, polyamide-based resin, polycarbonate-based resin, rubbery polymer reinforced styrene-based resin, polyphenylene sulfide-based resin, polyphenylene ether-based resin, polyacetal-based resin, You may add polysulfone type resin, polyarylate type resin, etc. individually or in combination of 2 or more types.

If necessary, the well-known crystal nucleating agents, crystallization accelerators, antioxidants, heat stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retarding aids, and UV absorption are also used. Additives such as agents, light stabilizers, pigments, dyes, antistatic agents, dispersants, compatibilizers, antibacterial agents can be used 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, from (A) above
After drying component (E), other additives, resins, etc.,
It can be produced by a method of melt-kneading with a melt-kneader such as a twin-screw extruder.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, sheet molding, and rolls are used. Molding methods such as molding, press molding, laminated molding, film molding by a melt casting method, and spinning can be applied.

[0029]

EXAMPLES The present invention will now 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.

Example 1 (A-1) Intrinsic viscosity of 0.6 as a thermoplastic polyester
100 parts of polyethylene terephthalate, (B-1)
1 part of novolak type polyepoxide (Epicoat 157S70: Yuka Shell Epoxy Co., Ltd., trade name: Epoxy equivalent 210) as an epoxy compound, (C-1) Brominated polystyrene as a halogenated polystyrene (Pyrocheck 68PB: Nissan Ferro Organic Chemical Co., Ltd.) Company name: bromine content 68%) 15 parts, (D-1) antimony trioxide (antimony oxide C: Sumitomo Metal Mining Co., Ltd. product name) 4 parts mixed, further thioether stabilizer (Adecastap AO-412S: trade name manufactured by Asahi Denka Co., Ltd.) was added to 0.3 part, and after stirring with a super mixer, a barrel temperature was measured using a twin-screw extruder with a vent (TEX44: trade name manufactured by Japan Steel Works Ltd.). Set it to 260 ° C,
Input from hopper. Further, from the side feeder of the extruder, (E-1) glass fiber (T
A resin composition was obtained by introducing 52 parts of -195H / PS: trade name of Nippon Electric Glass Co., Ltd. and performing melt extrusion.

Examples 2 to 8 In addition to the components used in Example 1, (A-2) polytetramethylene terephthalate having an intrinsic viscosity of 0.9 as a thermoplastic polyester, (D-2) antimony pentoxide (sana flame) AM: trade name manufactured by Sanuki Chemical Co., Ltd.) was used, and a resin composition was obtained in the same manner as in Example 1 except that the mixing ratios shown in Table 1 were used.

Comparative Example 1 The same method as in Example 1 except that bisphenol A diepoxide (B-2) (Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd., trade name: epoxy equivalent 189) was used as the epoxy compound. To obtain a resin composition.

Comparative Examples 2 to 8 In the same manner as in Example 1 except that (A), (B), (C), (D), and (E) shown in Table 2 were used and mixed in the proportions shown in Table 2. A resin composition was obtained.

The resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 8 were dried at 140 ° C. for 4 hours by using a hot air dryer, and then a cylinder temperature of 270 was obtained by using a 50t injection molding machine.
℃, mold temperature 120 ℃, molded to obtain a test piece,
It was subjected to physical property measurement and evaluation by the following methods. The results are shown in Tables 1 and 2. <Tensile Test> A dumbbell tensile test was performed in accordance with ASTM D-638 to determine the maximum strength. <Flame retardancy> Using a 1/16 inch bar, flame retardancy was evaluated according to the vertical combustion test method described in UL94. <Flowability> Using pelletized resin composition, JIS K
According to -7210, the cavity setting temperature is 280 ° C. when polyethylene terephthalate is used as the thermoplastic polyester, 230 ° C. or 270 ° C. when polytetramethylene terephthalate is used, and the method B flow is performed at a preheating time of 10 minutes. It was measured. <Evaluation of Surface Appearance of Molded Body> The surfaces of the bar and the dumbbell were visually observed and evaluated according to the following criteria. ◯: Good, Δ: Slightly bad gloss or sticky, X: Poor gloss or sticky.

[0035]

[Table 1]

[0036]

[Table 2]

As is clear from a comparison between Table 1 which is an example and Table 2 which is a comparative example, all of the compositions of the present invention are excellent in flame retardancy, fluidity and mechanical strength. It can be seen that the surface properties of the molded product are good.

[0038]

EFFECTS OF THE INVENTION According to the present invention, a flame-retardant polyester resin composition having excellent mechanical strength and fluidity and a good appearance of a molded article can be provided, and its industrial utility is great.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08L 63/00 NJX C08L 63/00 NJX

Claims (2)

[Claims] 1. To 100 parts by weight of (A) thermoplastic polyester, (B) the following general formula (I): (In the formula, q represents an integer of 1 to 40) 0.05 to 10 parts by weight of a novolac type epoxy compound, (C)
The following general formula (II): (In the formula, R is a H or CH ₃ group, X is a bromine or chlorine atom,
m represents an integer of 1 to 5 and n represents an integer of 10 or more. 1 to 50 parts by weight of halogenated polystyrene and / or halogenated poly-α-methylstyrene, (D) 0.1 to 20 parts by weight of antimony oxide compound, and (E) reinforcing filler of 0 to 150 A flame-retardant polyester resin composition containing 1 part by weight. 2. The flame-retardant according to claim 1, wherein the thermoplastic polyester is a polyethylene terephthalate resin having at least 80% ethylene terephthalate repeating units and / or a polytetramethylene terephthalate resin having at least 80% tetramethylene terephthalate repeating units. Polyester resin composition.