JPS59122540A - Flame-retardant polyester resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having remarkably improved flame retardance keeping the injection molding temperature tolerance and the surface characteristics of the molded article, by adding a flame retardant and a halogenated phenyl monoglycidyl ether compound to a resin, and introducing a polyvalent epoxy compound of the mixture. CONSTITUTION:The objective composition is prepared by compounding (A) 100pts.wt. of a thermoplastic polyester resin (preferably polyethylene terephthalate resin which may be incorporated with a nucleation agent such as metal oxide), (B) 0.2-6pts.wt., preferably 1-4pts.wt. of a halogenated phenyl monoglycidyl ether compound, preferably tribromophenyl monoglycidyl ether, (C) 0.02-3pts.wt. of a polyvalent epoxy compound, preferably a bisphenol-type diepoxide, and (D) 2-30pts.wt. of a flame-retardant.

Description

[Detailed description of the invention] The present invention relates to a flame-retardant polyester resin composition.

More specifically, by introducing a polyvalent epoxy compound into a thermoplastic polyester resin containing a flame retardant and a saponified phenyl monoglycidyl ether compound, the surface properties of the molded product can be maintained at injection molding temperatures. The present invention relates to a flame-retardant polyester resin composition that has a stable high degree of flame retardancy.

Thermoplastic polyester resin has a high softening point and has excellent electrical and mechanical properties, including heat resistance, chemical resistance, and light resistance, so it is widely used in fibers, films, and molded products. However, it has poor flame retardancy, which poses problems especially when applied to building material parts and electrical parts, and there are cases where there are significant limitations in terms of use.

Conventionally, it has been known that flame retardant methods for thermoplastic polyester resins include the use of halokene compounds, phosphorus compounds, nitrogen compounds, etc. together with flame retardant aids. In some cases, thermal decomposition occurs during actual injection molding, resulting in an extremely low viscosity, which often results in a significant loss of mechanical strength and surface properties of the molded product.

These drawbacks can be overcome by adding a halogenated phenyl monoglycidyl ether compound to the thermoplastic polyester resin together with a flame retardant. However, the flame retardant test piece obtained by this method was rated at UL-9.
When a combustion test is conducted using a test method in accordance with 4, a so-called dripping phenomenon may occur, in which the burned resin particles ignite the cotton placed underneath. There are times when it is not possible to say that.

The inventors of the present invention have conducted intensive studies based on this viewpoint, and have surprisingly found that polyvalent epoxy The present invention has been achieved based on the discovery that by introducing a specific amount of a compound, stable and high flame retardance can be imparted without impairing the injection molding temperature or the surface properties of the molded article.

That is, the present invention includes (a) 100 parts by weight of a thermoplastic polyester resin, (b) 0.2 to 6 parts by weight of a rogogenated phenyl monoglycidyl ether compound, and (C) 0.0 parts by weight of a polyvalent epoxy compound. '02 to 3 parts by weight, and (d) a flame retardant polyester resin composition containing 2 to 30 parts by weight.

In the present invention, the thermoplastic polyester resin (a) includes a dicarboxylic acid component in which at least 90 mol% is terephthalic acid, and at least 90 mol% is ethylene glycol, furopane-1,3-thiol, butane-
Obtained by direct esterification or transesterification and polycondensation with diol components such as 1,4-diol, pentane-1,5-diol, hexane-1,6-diol, and cyclohexane-1,4-dimetatool. It is something.

Dicarboxylic acid component of thermoplastic polyester resin from 0 to
10 mol% is another aromatic dicarboxylic acid having 6 to 14 carbon atoms, an aliphatic dicarboxylic acid having 4 to 8 carbon atoms, or 8 to 1 carbon atoms
It may also be an alicyclic dicarboxylic acid of No. 2. Examples of such dicarboxylic acids include phthalic acid, isophthalic acid,
, 6-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylethane-4,4-dicarboxylic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and the like. Also, 0 to 10 mol% of the diol component
is another aliphatic diol having 3 to 10 carbon atoms, 6 to 1 carbon atoms
Other alicyclic diols having 5 or aromatic diols having 6 to 12 carbon atoms may also be used.

Examples of such diols include 2,2-dimethylpropane-1,3-diol, 2,2-bis-(4-hydroxycyclohexyl)-pronogne, 2,2-bis-
Examples include (4'-hydroxyphenyl)furopane and hydroquinone. Furthermore, an amount of oxycarboxylic acid below (10 mol% or less of the dicarboxylic acid component and diol component),
For example, ε-oxycaproic acid, hydroxybenzoic acid, etc. may be copolymerized. Of course, the thermoplastic polyester resin may be branched with a trivalent or tetravalent alcohol, or a tribasic or tetrabasic acid; examples of suitable branching agents include trimesic acid, trimellitic acid, Examples include trimethylolpropane and pentaerythritol.

From an industrial standpoint, polyethylene terephthalate resins, polypropylene terephthalate resins, polyethylene terephthalate resins, and the like are preferred, and polyethylene terephthalate resins are preferred for the triwa. These thermoplastic polyester resins may be used alone or in a blend of two or more. Furthermore, for the purpose of increasing crystallinity, organic acid salts such as sodium acetate, sodium benzoate, sodium hydrogen phthalate, disodium phthalate, magnesium stearate, sodium stearate, calcium stearate, etc.; By adding nucleating agents such as inorganic salts such as l-IJum, calcium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, etc.; metal oxides such as zinc oxide, magnesium oxide, titanium oxide, etc. Alternatively, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be copolymerized or mixed. It may contain a compound having a structure having an acid metal salt.

7. It may also contain aliphatic polyester oligomers of dibasic acids, such as adipic acid, and diols, such as butanediol, and may contain so-called ionomers such as sodium salts of ethylene/acrylic acid copolymers. may have been done. Furthermore, with the aim of improving the mechanical and electrical properties of thermoplastic polyester resin,
It may contain polyamide polymers, polycarbonate polymers, etc., diene rubbers, acrylic rubber polymers, butyl rubber polymers, ethylene-propylene rubber copolymers, ethylene-vinyl acetate copolymers. , urethane rubber,
It may also contain thermoplastic rubber such as epichlorohydrin rubber or silicone rubber.

In the present invention, the halogenated phenyl monoglycidyl ether compound (b) is a compound represented by the following formula (1), and has a structure in which one epoxy group is bonded to a halogenated benzene nucleus. .

(Here, X represents Br or Cβ, and n represents an integer from 1 to 5.) Specific examples include dibromophenyl monoglycidyl ether, dichlorophenyl monoglycidyl ether, tribromophenyl monoglycidyl ether, and trichlorophenyl monoglycidyl ether. Examples include ethers, but tribromophenyl monoglycidyl ether is particularly preferred. In order to exhibit a sufficient effect when added to the composition, 0.2 to 6 parts by weight, preferably 1 to 4 parts by weight, of the halogenated phenyl monoglycidyl ether is required. If the amount is less than 0.2 parts by weight, it is impossible to improve the molding temperature, and if it exceeds 6 parts by weight, the mechanical strength will be reduced and it will not be able to withstand use as a resin. .

In the present invention, the polyvalent epoxy compound (C) refers to a compound having two or more oxirane rings in the molecule, and various commercially available epoxy compounds can be used. Specifically, bisphenol type epoxide, novolanc type epoxide, resol type epoxide, aliphatic type epoxide,
Examples include alicyclic epoxides, polyhydric alcohol epoxides, and epoxides having an aromatic ring, with bisphenol diepoxides, terephthalic acid diglycidyl ester, and phthalic acid diglycidyl ester being particularly preferred. The amount added varies depending on the epoxy equivalent, but generally speaking it is 0.02 to 3 parts by weight.If the amount added is less than 0.02 parts by weight, there is no effect, and if it exceeds 3 parts by weight, injection molding is prohibited. often inhibits.

In the present invention, the flame retardant (d) refers to all flame retardants commonly used to impart flame retardancy.

Specifically, halogenated diphenyl ether compounds, halogenated polycarbonate compounds, halogenated polyphenylene oxide compounds, halogen-containing S-triazine compounds, halogenated bisphenol epoxy resins, halogenated polystyrene resins, phosphorus compounds, and red phosphorus. , nitrogen-based compounds, and the like. Although the amount added varies, it is generally 2 to 30 parts by weight, and the amount necessary for flame retardation is added. In addition, these flame retardants can have a synergistic effect if necessary in combination with a flame retardant auxiliary agent. Specific examples of flame retardant aids include antimony compounds,
Examples include boron compounds, zirconium compounds, molyfden compounds, and antimony trioxide is preferred.

Furthermore, reinforcing fillers such as glass fibers, mineral fibers, talc, and mica may be added to the composition of the present invention, and additives such as ultraviolet stabilizers, oxidative deterioration inhibitors, heat stabilizers, plasticizers, lubricants, and colorants. In order to produce the composition of the present invention, a thermoplastic polyester resin (a), a norogenated phenyl monoglycyl ether compound (b),
The polyvalent epoxy compound (C) and the flame retardant (d) can be blended using a known method) 0 Method of adding and blending during production of thermoplastic polyester resin, method of mixing and extruding using an extruder, etc. can be mentioned. A highly flame-retardant composition is thus obtained which is stable at injection molding temperatures and without impairing the surface properties of the molded body.

The composition of the present invention can be widely used for molding various molded parts, containers, containers, etc., and is particularly suitable for electrical parts, building material parts, automobile parts, etc., and can also be used for fibers, films, and sheets. It is.

The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. In addition, in the examples, the tensile strength of the molded product is ASTM-D 688, the heat distortion temperature (18.6 kii'/cm2) is A, and the STM-
D648 and flame retardancy were measured according to the UL-94 vertical test method. The injection molding temperature was evaluated by changing the barrel temperature of the injection molding machine and evaluating the surface appearance and tensile strength retention. The amounts added in each example are parts by weight.

Examples 1-2, Comparative Example 1 Polyethylene terephthalate resin, decafromodiphenyl ether, tribromophenyl monoglycidyl ether (Br content 61.8% by weight, melting point 116-118.
5°C), terephthalic acid diglycidyl ester, antimony trioxide, and glass fiber with a fiber length of 3 mm were extruded and mixed at various ratios shown in Table 1, followed by various molding temperatures, holding pressure for 10 seconds, and cooling for 30 seconds. A test piece was obtained by injection molding. As shown in Table 1, it had a high degree of flame retardancy while maintaining retention and surface properties.

As Comparative Example 1, an example that does not contain terephthalic acid diglycidyl ester is also shown, but the flame retardance is shown in Table 1. Examples 3 to 4

Claims (2)

[Claims] (1) (a) Thermoplastic polyester resin 100 weight @
Melon (b) 0.2 to 6 parts by weight of a halokenated phenylmonocrinone ether compound, (c) 002 to 3 parts by weight of a polyvalent epoxy compound, and (d) a flame retardant.
A flame-retardant polyester resin composition containing 2 to 30 parts by weight. (2) The composition according to claim 1, wherein the thermoplastic polyester resin is a polyethylene terephthalate resin.