JPH01118567A - Flame-retarding polyester composition - Google Patents

Abstract

PURPOSE:To obtain a polyester composition excellent in flame retardancy and mechanical properties, by adding a polymeric flame retardant to a melt- anisotropic polyester. CONSTITUTION:A polyester composition is prepared by adding 5-60pts.wt. polymeric flame retardant to 100pts.wt. melt-anisotropic polyester. As said polyester, a polyester having an aromatic ring in the main chain and melt anisotropy can be used. Namely, a melt-anisotropic polyester prepared by copolymerizing a p-hydroxyaromatic carboxylic acid and its derivative with other various copolymerizable monomers or polymers can be suitably used. As said polymeric flame retardants, oligomeric or polymeric compounds having halogen atoms. and/or phosphorus atoms., etc. can be used, and examples thereof include a brominated epoxy resin, a brominated polycarbonate resin and a brominated polystyrene resin.

Description

[Detailed description of the invention] [Industrial application field] FIELD OF THE INVENTION This invention relates to flame retardant polyester compositions.

More specifically, the present invention relates to a flame-retardant polyester composition that contains a melt-anisotropic polyester and can be suitably used, for example, in electrical parts and automobile parts.

[Prior art and its problems 1 Melting anisotropic polyester (for example, Japanese Patent Publication No. 56-18
016) is polyalkylene terephthalate (P
Superior tensile modulus, tensile strength,
It has dimensional stability and fluidity, but like PET and PBT, it cannot be said to have sufficient flame retardancy.

Therefore, melt anisotropic polyesters cannot be used as they are in electrical parts, automobile parts, etc. that require flame retardancy, and their uses are limited.

On the other hand, flame retardation using flame retardants has been studied for PET and PBT, but no such studies have been conducted for melt anisotropic polyester.

An object of the present invention is to provide a novel flame-retardant polyester composition with excellent flame retardancy, which does not impair the properties of melt-anisotropic polyester and does not cause deterioration in mechanical properties.

[Means for solving the above problems] In order to solve the above problems, as a result of intensive studies, we found that a predetermined proportion of polymer y! was added to the melting anisotropic polyester. l
This invention was achieved by discovering that by adding a flame retardant, it is possible to obtain a flame-retardant polyester composition with excellent flame retardancy, without impairing the properties of the melt-anisotropic polyester or deteriorating its mechanical properties. .

That is, the structure of the present invention is characterized in that a polymer flame retardant [15 to 60 parts by weight of component (B) is added to 1100 parts by weight of component (A) of melt anisotropic polyester [component (A)] It is a flammable polyester composition.

As the melt anisotropic polyester which is the component (A), a polyester having an aromatic ring in the main chain and having melt anisotropy can be used.

Specifically, a melt anisotropic polyester obtained by copolymerizing p-hydroxy aromatic carboxylic acid and its derivatives with various other copolymerizable monomers or polymers can be suitably used.

For example, a polyester such as polyethylene terephthalate or polybutylene terephthalate can be acid-decomposed with a 7-syloxy aromatic carboxylic acid to generate a polyester fragment, and then this polyester can be copolymerized.

In particular, as the melt anisotropic aromatic polyester used in this invention, [wherein R1 is a cycloalkylene group having 4 to 20 carbon atoms, an alkylene group having 1 to 40 carbon atoms, or an alkylene group having 6 to 16 carbon atoms] R2 represents an alkylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a poly(alkylene oxide) divalent residue having a molecular weight of 200 to 8,000. 10 to 70 mol% of polyester consisting of repeating units represented by (
(repeating unit) and (essence, below margin) Formula: Or formula: ■ [311 in formula (2) 1 formula (3) 1 formula (4), formula (5)
3 represents hydrogen, chlorine, bromine, an alkyl group having 1 to 4 carbon atoms, or a flukoxy group having 1 to 4 carbon atoms, and R
4 represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and in formula (3), X is a direct bond, -CH2-1-(CH
2) z-1CH(CH3)-1-CH(C2H5)-1
-C(CH3), -o-, -5- or -3O2-] and 30 to 90 mol% of one or more 7-syloxy aromatic carbon #30 to 90 mol%, each of the formulas ( 2), has the same meaning as formula (3), formula (4), formula (5), or has the same meaning as that expressed in formula (3)], or diacetoxyphenol Diol derivative selected from the group of phthalenes, polyester and acyloxy aromatic carboxylic acid in a total of 100 mol%
A polyester obtained by adding 20 moles of θ to 20 can be suitably used.

Among these melt anisotropic polyesters, those of the formula (1
), R1 is a phenylene group, and R2 has 2 to 5 carbon atoms.
It is preferable to use a polyester having an alkylene group and an acyloxy aromatic carboxylic acid represented by the above formula (2).

A more preferable melt anisotropic polyester has a logarithmic viscosity at 30°C of a solution with a concentration of 0.5 g/dl using a mixture of phenol and tetrachloroethane at a ratio of 1:1 (weight ratio) as a solvent. It is 0.2 or more, preferably 0.4 to 2.0.

As for the polymeric flame retardant which is the component (B).

There is no particular restriction as long as it is an oligomer compound or polymer compound into which a halogen atom and/or a phosphorus atom is introduced, and examples thereof include brominated epoxy resin, brominated polycarbonate, and brominated polystyrene. Among these, preferred are linear formulas; show,
) is a polymer or oligomer having a tetrabromobisphenol skeleton represented by
Mention may be made of polyglycidyl ethers, polyethers and oligomers thereof.

(Essential, blank below) (1) Polycarbonate (However, n represents a real number of 2 or more, and the terminal group may or may not be blocked with a phenol compound.) (However, n is the same as above. ) (3) Polyester (where n represents the same meaning as above, a taste) (4) Polyglycidyl ether (however, n represents the same meaning as above) (5) Polyether (However, n represents the same meaning as above.) Among these materials having a tetrabromobisphenol skeleton, polycarbonates, polyglycidyl ethers, and oligomers thereof are preferably used because of their particularly good thermal stability.

The polymeric flame retardant may be other flame retardants (phosphorus-based flame retardants, etc.)
It has a higher flame retardant effect and less deterioration in mechanical properties.

The amount of the polymeric flame retardant added is 5 to 60 parts by weight per 100 parts by weight of the melting anisotropic polyester (A) I & min.
Selected from a range of parts by weight. If the amount added is less than 1 part of type 5, flame retardancy may become insufficient. On the other hand, if it exceeds 60 parts by weight, the fluidity may be significantly reduced.

When the flame-retardant polyester composition of the present invention contains the components (A) and (B), it has excellent flame retardancy that achieves v-0 in the UL94 standard, and has low mechanical strength. There is little decline.

In this invention, when a flame retardant adjuvant is used in combination with the polymeric flame retardant, the added amount of the polymeric flame retardant is V-0 according to UL94 standard even if it is less than
flame retardance is achieved.

Examples of such flame retardant aids include antimony trioxide, stannic oxide, aluminum oxide, and zirconium oxide.

The addition amount of the flame retardant aid is preferably 1 to 15 parts by weight per 100 parts by weight of component (A).

In addition, in this invention, an inorganic filler can be contained as long as it does not impede the object of this invention. The inorganic fillers to be included are not particularly limited, but examples include glass fibers, carbon fibers, metal whiskers such as aluminum, titanium, magnesium, iron, etc., and silica, clay, talc, monosaccharide calcium, mica, calcium silicate, etc. Inorganic powders can be used.

The amount of filler added is preferably 100 parts by weight or less per 100 parts by weight of component (A).

The flame-retardant polyester composition of the present invention comprises the melt anisotropic polyester [component (A)] and a polymeric flame retardant [(B
) and component 1 by a conventionally known method.

This manufacturing method includes, for example, melt-mixing the melt anisotropic polyester, polymeric flame retardant, and other necessary additives in an extruder or Nigu, or after uniformly mechanically mixing the particulate materials. Examples include a method in which additives are mixed and molded simultaneously with a direct injection molding machine, and a method in which additives are directly introduced into a resin polymerization pot and mixed.

[Effects of the Invention] According to the present invention, a novel flame-retardant polyester composition having excellent flame retardancy and mechanical properties can be provided.

[Examples] Examples and comparative examples of the present invention will be shown below to further specifically explain the present invention.

Production side of melt anisotropic polyester [component (A)] 25.0 kg of polyethylene terephthalate with logarithmic viscosity aO06
A mixture of 32.4 kg of p-acetoxybenzoic acid, and 3.0 kg of 1,4-diacetoxybenzene was charged into a batch polymerization machine having an internal volume of 190 mm and equipped with a stirrer and a distillation column.

This mixture was then heated to a temperature of 275°C in a nitrogen gas atmosphere.
The mixture was stirred at ℃.

Through this operation, acetic acid was gradually distilled out from the reaction tank, and a polyester fragment with a low melt viscosity was obtained. After that, it was heated at 300°C under a vacuum of 0.7 H, for 12 hours.
By stirring for hours, a white, opaque polyester with high melt viscosity was obtained.

The logarithmic viscosity of the obtained polyester was 0.61.

Here, the logarithmic viscosity number indicates the viscosity at 30° C. of a solution having a concentration of 0.5 g/dll using a mixture of phenol and tetrachloroethane at a ratio of 1=1 (weight ratio) as a solvent.

Furthermore, observation using a polarized m-microscope revealed that this polyester exhibited melting anisotropy at temperatures of about 240° C. or higher. That is, this polyester was a melt anisotropic polyester.

(Examples 1 to 6, Comparative Example 1) The polyester resin [(A) component], polymeric flame retardant [(B) component], filler (chopped glass fiber) [(G)], flame retardant Auxiliary agent (antimony trioxide)
Prepare [component (11)], and add component (B), component (C), and component (D) to 100 parts by weight of component (A).
They were blended in the amounts shown in the table.

Next, the mixture was melt-kneaded at a temperature of 270°C and pelletized.

After drying the resulting pellet, it is injection molded.

The characteristics of these test pieces were measured based on the following specifications. In addition, the flame test: complied with UL94 (thickness: l/16″).

Bending test was conducted in accordance with ASTM 11790.

Izotsu impact strength (with notch): Compliant with ASTM 0256.

Heat distortion temperature (18.6kg/cm2): ASTM
Compliant with 0648.

The results are shown in Table 1.

In addition, as each component (B), (C), and (D), the following were used.

(B) Ingredient brominated epoxy resin: “Puratherm E!P-0” manufactured by Dainippon Ink ■
30” Polytribromostyrene: “Ferro Stabilizer 68-PB” manufactured by Nissan Ferro Organic Chemical ■ (C) Component: Antimony trioxide: “Patox-L” manufactured by Nippon Seito Co., Ltd. (D)
r&min GF-Chopped glass fiber...Nitto Boseki "G53J-941SP" (
Essence, below margin)

Claims (1)

[Claims] (1) A flame-retardant polyester characterized by adding 5 to 60 parts by weight of a polymeric flame retardant [component (B)] to 100 parts by weight of the melt anisotropic polyester [component (A)]. Composition. (2) The melt anisotropic polyester [(A)
The flame-retardant polyester composition according to claim 1, wherein the component] has an alkylene group in its main chain.