JPH0116860B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a flame-retardant polyester resin composition, and more particularly to a flame-retardant glass fiber reinforced polyester resin composition with significantly improved impact resistance. [Technical background of the invention and its problems] Glass-reinforced polyester resin has excellent heat resistance, chemical resistance, mechanical properties, electrical properties, etc.
OA, electronic field connectors, coil bobbins,
Used in CRT sockets, etc. However, problems often occur such as cracks occurring when press-fitting terminals into molded products such as connectors, and the collar breaking during winding of the coil bobbin. Therefore, it is possible to improve the performance by blending various other polymers, but in order to improve the impact resistance, it is necessary to blend a large amount of polycarbonate, polyester elastomer, etc. Therefore, the resulting resin has drawbacks such as poor moldability and a significantly lower heat distortion temperature. [Object of the Invention] An object of the present invention is to provide a flame-retardant polyester resin composition that has improved impact resistance without impairing such poor moldability and high heat distortion temperature. [Structure of the Invention] As a result of intensive studies in order to eliminate the above-mentioned drawbacks, the present inventors found that a polymeric flame retardant having a specific structure was used, and a specific monoepoxy compound, an olefin, and acrylic acid or methacrylic acid were copolymerized. It was discovered that by simultaneously blending a combined sodium salt or potassium salt (ionomer), impact resistance could be greatly improved with a relatively small amount of blending without impairing heat resistance, and the present invention was completed. I reached it. That is, the flame-retardant polyester resin composition of the present invention comprises (A) polybutylene terephthalate resin or polyethylene terephthalate resin 20 to 85% by weight (B) glass fiber 5 to 60% by weight (C) polyester elastic body 1 to 85% by weight 20% by weight (D) Sodium salt or potassium salt of copolymer of olefin and acrylic acid or methacrylic acid
1 to 20% by weight (E) A polymeric brominated flame retardant with a brominated aromatic ring in the side chain of the polymer 2 to 20% by weight (F) Antimony oxide 0.5 to 10% by weight, (A) The total amount of each component in ~(F) is 100% by weight
This is a flame-retardant polyester resin composition. The polybutylene terephthalate resin in component (A) used in the present invention is a diol containing a dicarboxylic acid component in which at least 40 mol% of the dicarboxylic acid component is terephthalic acid and 40 mol% or more of 1,4-butanediol. It is a copolymer consisting of the following components. The dicarboxylic acid components other than terephthalic acid include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as azelaic acid, sebacic acid, adipic acid, and dodecane dicarboxylic acid, aromatic dicarboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid, or cyclohexane. Alicyclic dicarboxylic acids such as dicarboxylic acids may be used alone or in mixtures. Further, the intrinsic viscosity [η] of this polybutylene terephthalate is preferably in the range of 0.4 to 2.5. In addition, [η] is phenol/tetrachloroethane
This value is determined from the solution viscosity measured at 25°C in a 50/50 (weight ratio) solvent. In addition, the polyethylene terephthalate resin used in the present invention refers to a homopolymer of linear polyethylene terephthalate having ethylene terephthalate as a constituent unit; a copolymer of this unit component and other copolymerizable components; or a homopolymer of these It refers to mixed resins with copolymers, but is not particularly limited to these. As the component that can be copolymerized here, conventionally known acid components and glycol components can be used, and specifically, for example, phthalic acid, isophthalic acid, adipic acid, sebacic acid, naphthalene-1,4- or - Acid components such as 2,6-dicarboxylic acid and diphenyl ether-4,4'-dicarboxylic acid; propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis(4-hydroxyphenyl)propane Glycol components such as p
-oxybenzoic acid, p-hydroxybenzoic acid, p
- Oxyacids such as hydroxyethoxybenzoic acid are included. The resin can be obtained by ordinary polymerization methods such as polycondensation of terephthalic acid and ethylene glycol through transesterification or direct esterification, but in this case, the intrinsic viscosity [η] of the resin is It is preferable to set it in the range of 0.4 to 1.4. Here, as a method for obtaining a resin having a high intrinsic viscosity, it is also possible to obtain a resin having a relatively low intrinsic viscosity by a conventional solid phase polymerization method. The blending ratio of these components (A) is in the range of 20 to 85% by weight, particularly preferably in the range of 35 to 75% by weight, in the resin composition composed of each component (A) to (F). lower limit
If it is less than 20% by weight, heat resistance and flow processability will deteriorate, and if it exceeds the upper limit of 85% by weight, it will not be possible to improve the impact resistance, which is the objective of the present invention. Next, as the component (B) glass fiber used in the present invention, any type of glass fiber such as a roping type or chopped strand type can be used.
From the viewpoint of productivity, a chopped strand type is preferable. In addition, considering workability during mixing of the resin composition of the present invention, wear of the molding machine, and cutting during the molding process, glass fibers having a length of approximately 0.4 to 6 mm may be used during mixing, and the Preferably, the length is in the range of about 0.2 to 2 mm.
As such glass fibers, commercially available products that have been subjected to various treatments can be used as they are, and the mixing method is not particularly limited. Incidentally, the glass fiber is blended in an amount of 5 to 60% by weight in the total resin composition. If the blending amount exceeds 60% by weight, flow processability will decrease, and if the blending amount is less than 5% by weight, the glass fiber reinforcing effect will be insufficient. The polyester elastomer (C) used in the present invention refers to residues of polyalkylene glycol such as polytetramethylene glycol, polyethylene glycol, polyethylene glycol/polypropylene glycol block copolymer, and polyhydric alcohol/alkylene oxide adduct. Polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate isophthalate, polyethylene paraoxybenzoate, polyethylene terephthalate adipate, polyethylene terephthalate sebacate, polyethylene naphthalate, polybutylene terephthalate adipate, polybutylene terephthalate isophthalate, Examples include aromatic polyester/polyether elastic resins in which hard segments are residues of aromatic polyesters such as butylene terephthalate and ethylene terephthalate. The elastic resin uses polyalkylene glycol with a molecular weight of 650 or more, preferably 800 to 6000, and the polyalkylene glycol portion is 20
% by weight or more, preferably from 30 to 80% by weight, and usually has a glass transition temperature of 10°C or less, preferably -15°C
~-60℃, molecular weight 10000 or more, preferably 30000
The above aromatic polyester/polyalkylene glycol block copolymer. The polyester elastomer is blended in an amount of 1 to 20% by weight, preferably 2 to 15% by weight, based on the total resin composition. If the amount is more than 20% by weight, the heat distortion temperature will be significantly lowered, and if it is less than 1% by weight, the effect of improving impact resistance will not be noticeable. Furthermore, component (D) constituting the present invention is a sodium or potassium salt of a copolymer of olefin and acrylic acid or methacrylic acid, and olefin is usually 50 to 98% by weight, preferably 80 to 98% by weight of the copolymer. 30% or more of the total carboxylic acid residues are neutralized with sodium or potassium, and a particularly preferred substance is the sodium salt of ethylene/methacrylic acid copolymer. The blend amount is 1 to 20% by weight, preferably 2 to 10% by weight of the total resin composition. If the blending amount exceeds 20% by weight, the flame retardancy and heat distortion temperature will decrease significantly, and the compatibility with the polybutylene terephthalate resin will decrease, resulting in a decrease in strength. Further, if it is less than 1% by weight, the effect of improving impact resistance will not be noticeable. Further, a polymeric brominated flame retardant constituting the present invention
(E) is a polymer with a brominated aromatic ring in its side chain, specifically polypentabromobenzyl acrylate, polypentabromobenzyl methacrylate, polytetrabromo Examples include poly(2,4,6 tribromo)styrene, poly(2,4,5 tribromo)styrene, and the like. The polymeric brominated flame retardant is blended in an amount of 2 to 20% by weight in the total resin composition. If it is less than 2% by weight, almost no flame retardant effect can be expected. Moreover, if it exceeds 20% by weight, the mechanical strength of the molded product obtained will decrease. Antimony oxide (F) constituting the present invention functions as a flame retardant aid for the flame retardant component (E), and specifically includes antimony trioxide and antimony pentoxide. In order to exhibit the effect as a flame retardant aid in the entire resin composition, a blending amount of 0.5% by weight or more is required, and in order not to reduce the mechanical strength of the resulting molded product, the blending amount is 10% by weight or less. It is necessary to The flame-retardant polyester resin composition of the present invention may contain fillers such as wollastonite, mica, glass foil, clay or kaolin, ultraviolet absorbers, antioxidants, and thermal deterioration within the scope of the purpose of the present invention. Various additives such as stabilizers such as inhibitors, dyes and pigments, and matting agents can be blended. An example of preparing the flame-retardant polyester resin composition of the present invention as described above is as follows. Polybutylene terephthalate or polyethylene terephthalate (A), a predetermined amount of glass fiber (B), a polyester elastomer (C), a sodium salt or potassium salt of a copolymer of olefin and acrylic acid or methacrylic acid (D), and a high After adding the molecular type brominated flame retardant (E) and antimony oxide (F) and mixing in a suitable mixer such as a tumbler, the mixture is fed to an extruder or the like and melt-kneaded and extruded to form pellets. The present invention will be explained in more detail below with reference to Examples and Comparative Examples. [Embodiments of the Invention] Examples 1 to 10 Various substances of the present invention consisting of components (C), (D), (E), and (F) and 3 mm chips were used for polybutylene terephthalate with [η] of 1.0. The glass fibers of the strands were blended in the proportions shown in Table 1, and blended in a V-type blender for 50 minutes.
Mix uniformly for a minute. This mixture was processed using a 65mmφ vented melt extruder at a cylinder temperature of 240℃~
The polyester resin composition of the present invention was obtained by extruding and pelletizing at 250°C. Using the above resin composition, the Izotsu test described in ASTM D-256 was carried out using a screw type injection molding machine with a 3 oz. A specimen (1/8 inch thick) and a non-notched isot specimen (1/8 inch thick) were molded and subjected to an impact test according to ASTM D-256. In addition, a strip specimen of 12.7 x 127 x 3.2 mm was molded under the same molding conditions and passed ASTM D-648 (1/8 inch,
18.6Kg/cm ² ) was measured. Comparative Examples 1 to 5 Compositions (Comparative Example 1
~5) was obtained. The obtained composition was subjected to the same measurements as in the examples. The results are shown in Table 1. Examples 11-12 [η] 0.72 polyethylene terephthalate homopolymer, 3 mm long chopped strand glass fiber, and the above components (C), (D), (E), and (F) were added in the proportions shown in Table 1. Mixed and homogenized. Diameter the resulting mixture
The mixture was put into a 65 mm vented melt extruder and extruded at a cylinder temperature of 260°C to 280°C to obtain pellets. Using the resulting resin composition, 3 oz.
Using a 30 mm screw type injection molding machine, the cylinder temperature was 280°C, the mold temperature was 140°C, and the molding cycle was 30 seconds. Molding a non-notched isot specimen (1/8 inch thick),
An impact test was conducted in accordance with ASTM D-256. In addition, a strip specimen of 12.7 x 127 x 3.2 mm was molded under the same molding conditions and passed ASTM D-648 (1/8 inch,
264 psi) was measured. Comparative Examples 6 to 8 Compositions were produced in the same manner as in Examples 11 to 12, except that the compositions and blending ratios shown in Table 1 were used, and the same tests were conducted on similar specimens using the obtained compositions. Summer. These results are shown in Table 1.

【table】

【table】

〔Effect of the invention〕

As detailed above, the flame-retardant polyester resin composition of the present invention has greatly improved impact resistance without impairing heat resistance, and its industrial value is extremely large.

Claims (1)

[Claims] 1 (A) Polybutylene terephthalate resin or polyethylene terephthalate resin
20-85% by weight (B) Glass fiber 5-60% by weight (C) Polyester elastomer 1-20% by weight (D) Sodium salt or potassium salt of copolymer of olefin and acrylic acid or methacrylic acid
1 to 20% by weight (E) A polymeric brominated flame retardant with a brominated aromatic ring in the side chain of the polymer 2 to 20% by weight (F) Antimony oxide 0.5 to 10% by weight, (A) The total amount of each component in ~(F) is 100% by weight
A flame-retardant polyester resin composition.