JPH0562143B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a flame-retardant polyester composition having excellent retention stability and heat resistance stability in terms of mechanical properties and electrical properties. <Conventional technology> Aromatic polyesters, represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexine dimethylene terephthalate, etc., are used to manufacture mechanical parts, electrical parts, automobile parts, etc. using their excellent properties. It is beginning to find uses in On the other hand, in addition to the general balance of chemical and physical properties, these industrial materials are also strongly required to have flame safety, that is, flame retardancy, and at present, the ability to impart flame retardance is important for industrial use. It is no exaggeration to say that this will determine the possibility of expanding the use of aromatic polyester. The use of poly(halogenated benzyl acrylate) polymers as flame retardant agents for aromatic polyesters such as polybutylene terephthalate is well known, as proposed in JP-A-52-3682, for example. It is being In addition, when aromatic polyester is made flame retardant using this method, there is a problem that the aromatic polyester decomposes due to stagnation in a molding machine, resulting in a decrease in mechanical properties. A method of adding an epoxy compound such as bisphenol A-epichlorohydrin type as shown in No. 149756 has been proposed. However, although the above method can improve the retention stability in the molding machine to some extent, there is a problem in that when the molded product is further subjected to dry heat treatment, the mechanical properties and electrical properties are significantly deteriorated. <Problems to be Solved by the Invention> Therefore, the present inventors improved the above-mentioned problem in flame retardant aromatic polyester using a poly(halogenated benzyl acrylate) flame retardant, that is, the decrease in mechanical properties during molding. As a result of extensive research, we found that the combined use of a poly(halogenated benzyl acrylate) flame retardant and a specific glycidyl group-containing copolymer significantly improves the retention stability and heat stability of mechanical and electrical properties. This discovery led to the present invention. <Means and effects for solving the problems> That is, the present invention provides, for 100 parts by weight of aromatic polyester, (A) 3 to 50 parts by weight of a halogen-containing vinyl polymer having a repeating unit of the following formula (); and (B) a flame-retardant polyester composition containing 1 to 20 parts by weight of a glycidyl group-containing copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid. . (However, in the formula, R is hydrogen or an alkyl group having 1 to 5 carbon atoms, X is chlorine or bromine, and m is 1 to
It is an integer of 5. ) The aromatic polyester used in the present invention is a polyester having an aromatic group in the polymer chain unit, and is mainly composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction as a component. The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5
-Haphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-
biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl isopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4''-p-terphenylenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, etc.
Terephthalic acid can be preferably used. Two or more of these aromatic dicarboxylic acids may be used in combination. In addition, if it is a small amount, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. I can do it. In addition, as diol components, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol,
Examples include aliphatic diols such as diethylene glycol and toluethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof. If the amount is small, one or more long-chain diols having a molecular weight of 40 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol, may be copolymerized. Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene terephthalate.
In addition to 1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, copolymerized polyesters such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polybutylene terephthalate/decanedicarboxylate, etc. can be mentioned. Among these, polybutylene terephthalate and polyethylene terephthalate, which have well-balanced mechanical properties and moldability, can be preferably used. The aromatic polyester used in the present invention is
It is preferable that the relative viscosity of a 0.5% o-chlorophenol solution measured at 25° C. is 1.15 to 2.0, particularly 1.3 to 1.85. The halogen-containing vinyl polymer used as a flame retardant in the present invention is a polymer that essentially includes a repeating unit of the following formula (). However, in the formula, R is hydrogen or an alkyl group having 1 to 5 carbon atoms, more preferably hydrogen, methyl, or ethyl, X is chlorine or bromine, and m is 1 to 5
is an integer. Monomers used in the production of the halogen-containing vinyl polymer of the present invention include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tetrabromomethylbenzyl acrylate, tribromobenzyl acrylate, dibromobenzyl acrylate, bromobenzyl acrylate, and pentabromobenzyl acrylate. Lombenzyl methacrylate, Tetrabromobenzyl methacrylate, Tetrabromomethylbenzyl methacrylate, Tribromobenzyl methacrylate, Pentabromobenzyl ethacrylate, Tetrabromobenzyl ethacrylate, Tribromobenzyl ethacrylate, Pentachlorobenzyl acrylate, Tetrachlorobenzyl acrylate , trichlorobenzyl acrylate, pentachlorobenzyl methacrylate,
These include tetrachlorobenzyl methacrylate, trichlorobenzyl methacrylate, pentachlorobenzyl ethacrylate, tetrachlorobenzyl ethacrylate, and trichlorobenzyl ethacrylate, and one or more of them can be used as a mixture.
Among these, pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, pentabromobenzyl methacrylate, tetrabromobenzyl methacrylate, and tribromobenzyl methacrylate are preferred, and pentabromobenzyl acrylate is more preferred. Further, other monomers may be copolymerized with the halogen-containing vinyl polymer of the present invention as long as the flame retardant effect of the polymer is not significantly reduced. These include styrene, α-methylstyrene, p-
Methylstyrene, acrylonitrile, methacrylonitrile, acrylic esters, methacrylic esters, xylylene acrylates and -methacrylates of alcohols having 1 to 6 carbon atoms, and chlorine-substituted products thereof, butadiene, isoprene, fumaric acid, and maleic acid or its anhydride. , vinyl chloride, vinylidene chloride, etc. The method for producing the halogen-containing vinyl polymer is not particularly limited, but includes, for example, a method in which a peroxide or an azo compound is used in a solution. Specific examples of the halogen-containing vinyl polymer of the present invention include poly(pentabromobenzyl acrylate), poly(pentabromobenzyl methacrylate), poly(tetrabromomethylbenzyl acrylate), poly(tetrabromomethylbenzyl methacrylate), and pentabromobenzyl Preferable examples include acrylate/styrene copolymer and pentabromobenzyl acrylate/methyl methacrylate copolymer, among which poly(pentabromobenzyl acrylate) is more preferred. The amount of the halogen-containing vinyl polymer added in the present invention is based on 100 parts by weight of the aromatic polyester.
The amount is 3 to 50 parts by weight, preferably 5 to 30 parts by weight.
If the amount added is less than 3 parts by weight, imparting flame retardance will not be sufficient, and if it exceeds 50 parts by weight, the mechanical properties of the aromatic polyester will be impaired, so both are not preferred. The flame retardant effect of a halogen-containing vinyl polymer can be enhanced by the combined addition of a flame retardant auxiliary agent. Antimony trioxide is preferably used as the flame retardant aid. In order to obtain a sufficient effect of imparting flame retardancy and a sufficient effect of maintaining the mechanical properties of the aromatic polyester, the amount added is preferably 1 to 20 parts by weight, more preferably 1 to 20 parts by weight per 100 parts by weight of the aromatic polyester. It is 3 to 15 parts by weight. More preferably, it is added in a ratio of 1 antimony atom in antimony trioxide to 2 to 5 halogen atoms in the added halogen-containing vinyl polymer. At the same time, other flame retardant adjuvants such as boron oxide, zirconium oxide,
Iron oxide etc. may also be used together. The α-olefin used in the present invention and α,
The α-olefin in the glycidyl group-containing copolymer made of glycidyl ester of a β-unsaturated acid includes ethylene, propylene, butene-1, etc., and ethylene is preferably used. Also,
Glycidyl ester of α,β-unsaturated acid has the general formula (In the formula, R is a hydrogen atom or a lower alkyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. are used, and glycidyl methacrylate is preferably used. . α, β−
The amount of copolymerization of glycidyl ester of unsaturated acid is 0.5
A range of from 1 to 50% by weight, preferably from 1 to 30% by weight, more preferably from 2 to 20% by weight is suitable. Furthermore, unsaturated monomers that can be copolymerized with the above copolymers at 40% by weight or less, such as vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acids such as methyl, ethyl, and propyl; One or more types of esters of methacrylic acid, acrylonitrile, styrene, generalized carbon, etc. may be copolymerized. Preferred examples of the glycidyl group-containing copolymer in the present invention include ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/carbon monoxide/glycidyl methacrylate copolymer, and ethylene/glycidyl methacrylate copolymer. Examples include acrylate copolymers and ethylene/vinyl acetate/glycidyl acrylate copolymers, among which ethylene/glycidyl methacrylate copolymers are most preferred. In the present invention, the amount of the glycidyl group-containing copolymer added is 1 part by weight per 100 parts by weight of the aromatic polyester.
~2 parts by weight, preferably 2 to 10 parts by weight. If the amount added is less than 1 part by weight, the retention stability and heat resistance stability will not be improved sufficiently, and if it exceeds 20 parts by weight, the flame retardance of the aromatic polyester will tend to be impaired, so both are not preferred. In addition to the glycidyl group-containing copolymer used in the present invention, an ethylene-based copolymer consisting of ethylene and an α-olefin having 3 or more carbon atoms and/or a tertiary copolymer consisting of ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated diene If the original copolymer is used in combination, the impact resistance can be further improved. Specific examples of these copolymers include ethylene/propylene copolymer, ethylene/butene-1 copolymer,
Ethylene/pentene-1 copolymer, ethylene/propylene/butene-1 copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, ethylene/propylene/1,4-hexadiene copolymer, ethylene/ These include propylene/dicyclopentadiene copolymers, among which ethylene/propylene copolymers and ethylene/butene-1 copolymers are preferred. The amount of the ethylene copolymer added is 1 to 70 parts by weight, preferably 2 to 40 parts by weight, per 100 parts by weight of the aromatic polyester, and the total amount with the glycidyl group-containing copolymer is 80 parts by weight. It is preferable that it is below. Incidentally, when a compound that promotes the reaction between the epoxy compound and the carboxylic acid is further added to the composition of the present invention, it is possible to obtain the effect that the impact resistance can be further improved. These compounds include tertiary amines such as triphenylamine and 2,4,6-tris(dimethylaminomethyl)phenol;
Phosphite esters such as triphenylphosphite and triisodecylphosphite, phosphonium compounds such as triphenylallylphosphonium bromide, tertiary phosphines such as triphenylphosphine, carboxylic acid metal salts such as lithium stearate and calcium stearate, Examples include sulfonic acid metal salts such as sodium dodecylbenzenesulfonate and sodium 3,5-dicarbomethoxybenzenesulfonate, and sulfuric acid ester salts such as sodium lauryl sulfate.
It is preferable to add 0.001 to 5 parts by weight per 100 parts by weight. In order to improve the heat distortion temperature and rigidity of the composition of the present invention, an inorganic filler may be added. Examples of fillers include glass fiber, carbon fiber, metal fiber, glass beads, glass flakes, mica, wollastenite, talc, clay, asbestos, sericite, calcium carbonate, magnesium carbonate,
Examples include barium sulfate and titanium oxide. Two or more of these may be used in combination. Among the inorganic fillers, glass fiber can be preferably used. As the glass fiber, ordinary tipped strands or roving types are used, but tipped strands with a length of 3 to 6 mm are preferred from the viewpoint of ease of handling and surface gloss of the molded product. Furthermore, glass fibers treated with ordinary coupling agents such as silane-based or titanium-based, or ordinary binding agents such as epoxy resin or vinyl acetate are particularly preferably used. In addition, conventional additives such as a mold release agent, an ultraviolet absorber, a pigment, a dye, and a nucleating agent can also be added to the composition of the present invention. The method for producing the composition of the present invention is not particularly limited, but preferably aromatic polyester,
A method of melt-mixing a halogen-containing vinyl polymer, a glycidyl group-containing copolymer, and other necessary additives in an extruder or kneader;
Other methods include a method in which the particulate materials are uniformly mixed mechanically and then directly mixed and molded using an injection molding machine, and a method in which additives are directly introduced into a resin polymerization pot and mixed. The composition of the present invention is subsequently made into molded products by extrusion molding, injection molding, compression molding, etc., and these molded products have excellent flame retardancy, heat resistance, and electrical insulation properties in addition to mechanical properties. Since it has a good surface appearance, it is useful as mechanical parts, electrical parts, and automobile parts. <Example> The effects of the present invention will be explained below with reference to Examples. Moreover, relative viscosity is a value measured at 25° C. of a 0.5% polymer solution using o-chlorophenol as a solvent. Examples 1 to 6, Comparative Examples 1 to 8 Polybutylene terephthalate with a relative viscosity of 1.71
100 parts by weight of poly(pentabromobenzyl acrylate), 7 parts by weight of antimony trioxide and Table 1
A glycidyl group-containing copolymer was added to the mixture in the proportions shown in Table 1, mixed with a Henschel mixer, and then mixed with a solvent and pelletized at 250°C using a 40 mmφ extruder.
Next, the obtained pellets were molded using a 2 oz screw in-line injection molding machine set at 250°C with a mold temperature of 80°C and a molding cycle (injection time/cooling time/intermediate time) of 10 seconds/15 seconds/ Molded for 10 seconds (molding cycle (a)), ASTM-1 dumbbell, square plate (80mm x 80mm x 1mm) and combustion test piece (1/16″ x
1/2″×5″) was obtained. In addition, the molding cycle (injection time/cooling time/intermediate time) is set to 10 seconds/15 seconds/40 seconds (molding cycle (b)).
Three types of test pieces were obtained in the same manner as above, with the other conditions being the same. Vertical combustion tests were conducted using combustion test pieces in accordance with the UL94 standard. In addition, we conducted a tensile test using a tensile test piece according to the ASTM-D638 standard, and a dielectric breakdown test using a square plate according to the UL standard. I asked for it. These results are shown in Table 1.

【table】

[Table] As shown in Table 1, the composition containing the glycidyl group-containing copolymer of the present invention has excellent heat resistance stability of mechanical properties and electrical properties, and also has excellent thermal stability when molding residence time becomes long. It is clear that these properties are further improved. Examples 7-10, Comparative Examples 9-13 Polybutylene terephthalate with relative viscosity 1.45
7 parts by weight of antimony trioxide per 100 parts by weight,
60 parts by weight of glass fibers (epoxy resin treated, 3 mm long chopped strands) or glass beads (epoxy resin treated, average particle size 30μ), poly(pentabromobenzyl acrylate) used in Example 1 and glycidyl group-containing copolymer. Polymer (α) was added in the proportions shown in Table 2, dry-blended in a tumbler, and then melt-kneaded and pelletized. moreover,
In the same molding cycle as in Example 1, two conditions were used.
ASTM No. 1 dumbbells, square plates, and combustion test pieces were molded and subjected to combustion tests, tensile tests, and dielectric breakdown tests. The results are shown in Table 2.

[Table] Note: *1 Filler
GF: Glass fiber
GB: Glass beads Even when a filler is added as shown in Table 2,
The composition containing the glycidyl group-containing polymer of the present invention has excellent heat resistance stability in mechanical properties and electrical properties, and these properties are further improved when the molding residence time becomes longer. is clear. Example 11 Polybutylene terephthalate with relative viscosity of 1.71
7 parts by weight of antimony trioxide per 100 parts by weight;
25 parts by weight of poly(pentabromobenzyl acrylate) used in Example 1, 5 parts by weight of glycidyl group-containing copolymer (α), and ethylene/butene-1
After mixing 5 parts by weight of the copolymer (90/10 molar ratio, MI=3.0) using a Henschel mixer, the mixture was melt-kneaded and pelletized in the same manner as in Example 1, and molded articles were prepared and evaluated. As a result, the flammability was V-0 in both molding cycles (a) and (b), and the tensile strength and dielectric breakdown voltage were also ◎ in both molding cycles (a) and (b). As can be seen by comparing these results with Example 2, it is clear that the effects of the present invention are synergistically improved by the combined use of the ethylene/butene-1 copolymer. <Effects of the present invention> The flame-retardant polyester composition of the present invention synergistically improves the retention stability of mechanical properties and electrical properties, and can also significantly improve heat resistance stability.

Claims (1)

[Scope of Claims] 1. Based on 100 parts by weight of aromatic polyester, (A) 3 to 50 parts by weight of a halogen-containing vinyl polymer having a repeating unit of the following formula () and (B) α-olefin and α,β - A flame-retardant polyester composition containing 1 to 20 parts by weight of a glycidyl group-containing copolymer consisting of a glycidyl ester of an unsaturated acid. (However, in the formula, R is hydrogen or an alkyl group having 1 to 5 carbon atoms, X is chlorine or bromine, and m is 1 to
It is an integer of 5. )