JPH0585582B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention provides a flame-retardant aromatic polyester resin composition that is characterized by having excellent hydrolysis resistance, retention stability during molding, and fluidity as well as good heat cycle resistance. Regarding. <Prior Art> Aromatic polyester resins, represented by polybutylene terephthalate and polyethylene terephthalate, are being used in a wide range of applications, including electronic and electrical parts and automobile parts, due to their excellent properties. When used as materials for these industrial applications, it has become extremely important to have flame safety, that is, flame retardancy, in addition to chemical and physical properties, and aromatic polyester resins have Since it does not have sufficient flame retardancy on its own, various flame retardant technologies are being considered. Among various methods, a method using an organic bromine compound and antimony oxide in combination has been studied in many cases from the viewpoint of cost performance. However, when these methods are applied, the aromatic polyester deteriorates due to the effects of halogen radicals, water, antimony oxide, etc. generated during melt processing, resulting in a decrease in mechanical strength and coloring. In addition, when used in automobile electrical components such as distributor caps, hydrolysis resistance is increasingly required, but when organic bromine compounds or antimony oxide are added, teeth,
It has been pointed out that the hydrolysis resistance of aromatic polyesters, which are originally poor, becomes even worse. In order to suppress the deterioration and improve the hydrolysis resistance of such flame-retardant aromatic polyester resins, there is a method of adding an epoxy compound such as bisphenol A diglycidyl ether, for example, to suppress the deterioration of the aromatic polyester. Japanese Patent Application Publication No. 1973-1 corresponding to
Many methods of adding epoxy compounds have been proposed, such as in Japanese Patent Application Laid-open No. 149756 and Japanese Patent Application Laid-open No. 161452/1983, which purport to improve hydrolysis resistance. <Problems to be Solved by the Invention> However, the above-mentioned method does not have a very large effect on improving the hydrolysis and deterioration of flame-retardant aromatic polyester, and it also causes problems such as a significant decrease in the fluidity of the resin during molding. However, a method for improving these functions of flame-retardant aromatic polyester resins has not yet been found. <Means for Solving the Problems> Therefore, the present inventors set out to obtain a flame-retardant aromatic polyester resin composition that has excellent thermal deterioration characteristics and satisfies both good hydrolysis resistance and molding fluidity. As a result of intensive studies, we found that when a specific epoxy compound is added to aromatic polyester and an organic bromine compound in combination, not only is the above objective achieved, but surprisingly heat cycle resistance is also significantly improved. This discovery led to the present invention. That is, the present invention provides (A) an epoxy compound represented by the following general formula () based on 100 parts by weight of aromatic polyester (B)
0.01-10 parts by weight

[C] (In the formula, Ar represents an aromatic group or alicyclic group having 6 to 20 carbon atoms, and n represents an integer of 0 or 1 to 20.) (C) 1 to 50 parts by weight of an organic bromine compound. The object of the present invention is to provide a low-temperature aromatic polyester resin composition. The aromatic polyester (A) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is 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 polycondensation reaction containing as the main component. The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,
5-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-
Biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid, 4 , 4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4″-p-terphenylenedicarboxylic acid,
These include 2,5-pyridinedicarboxylic acid, and terephthalic acid is preferably used. Two or more of these aromatic dicarboxylic acids may be used in combination. In addition, if the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. can do. 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 triethylene 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 400 to 6,000, such as polyethylene glycol, poly1,3-propylene glycol, and polytetramethylene glycol, may be copolymerized. Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate,
In addition to polyethylene-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 preferably has a relative viscosity of 1.15 to 2.0, particularly 1.3 to 1.85, as measured in a 0.5% o-chlorophenol solution at 25°C. The epoxy compound (B) used in the present invention is represented by the above general formula (). Specific examples of Ar include 1,4-phenylene,
1,3-phenylene, 1,2-phenylene, 2-
Methyl-1,4-phenylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,2'-biphenylene, 3,4'-biphenylene, 1,4-naphthylene, 1,5-naphthylene, 2, 6-naphthylene,
2,7-naphthylene, 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, 4,4'-bicyclohexylene, 2,
Preferred examples include 6-decahydronaphthylene and the like, with 1,4-phenylene, 1,3-phenylene and 2,6-naphthylene being particularly preferred. The value of the degree of polymerization n of the compound of formula () is 0 or an integer of 1 to 20, preferably 0 or an integer of 1 to 10, and may be a mixture of compounds having various degrees of polymerization. Particularly preferred are those in which the average degree of polymerization is in the range of 0 to 2, and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), Mw/Mn, is in the range of 1.0 to 3.0. The method for producing the epoxy compound represented by the formula () is not particularly limited, but for example, hydroxycarboxylic acid and epihalohydrin are
React at 40°C to 150°C in the presence of a catalyst such as a grade ammonium salt, a tertiary amine, or a tertiary phosphine,
Examples include a method in which halohydrin ester is etherified and then an alkali metal salt is added to dehydrohalogenate. A product with a high degree of polymerization can be obtained by further reacting a hydroxycarboxylic acid in the presence of a catalyst while changing the ratio. The amount of the epoxy compound represented by the formula () in the present invention is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight based on 100 parts by weight of the aromatic polyester. is desirable. If the amount added is less than 0.01 part by weight,
The effect of improving the hydrolysis resistance of the aromatic polyester is not sufficient, and on the other hand, if the amount exceeds 10 parts by weight, the mechanical properties of the aromatic polyester are impaired, which is not preferable. The organic bromine compound (C) used in the present invention refers to a known organic bromine compound that has a bromine atom in its molecule and is usually used as a retardant, particularly with a bromine content of 20% by weight or more. Preferably. Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromobiphenyl) low molecular weight organic bromine compounds such as enoxy)ethane, ethylene bis-(tetrabromophthalimide), and tetrabromobisphenol A, brominated polycarbonates (e.g., polycarbonate oligomers made from brominated bisphenol A), brominated epoxy Alternatively, brominated phenoxy compounds (for example, diepoxy compounds, brominated epoxy oligomers, brominated epoxy polymers, brominated phenoxy polymers produced by the reaction of brominated bisphenol A and epichlorohydrin), poly(brominated benzyl acrylate) ), brominated polyphenylene ether, brominated bisphenol A/cyanuric chloride/brominated phenol condensate, brominated polystyrene, and other halogenated polymers and oligomers, or mixtures thereof. Epoxy oligomers and polymers (average degree of polymerization 4~
100), brominated polystyrene (average degree of polymerization 20~
200), brominated polyphenylene ether (average degree of polymerization 10 to 200), brominated polycarbonate (average degree of polymerization 3 to 30), and polycondensates of cyanuric chloride/brominated bisphenol/brominated phenol (average degree of polymerization 3 ~30) are preferred, particularly brominated polycarbonate with an average degree of polymerization of 3 to 30 made from tetrabromobisphenol A end-capped with a monovalent phenol such as p-tert-butylphenol or tribromophenol, or its bisphenol A. Copolymers with polycarbonate can be preferably used. The amount of these organic bromine compounds (C) added is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the aromatic polyester. If the amount added is less than 1 part by weight, the flame retardance will not be sufficient, and if it exceeds 50 parts by weight, the physical properties of the composition will deteriorate, which is not preferable. The antimony oxide that can be used in the present invention is not particularly limited as long as it is normally used as a flame retardant aid for polyester, but antimony trioxide is preferable. In addition to antimony trioxide, zirconium oxide, zinc sulfide, barium sulfate,
Sodium antimonate, triphenylstevin, etc. may be used in combination. The amount of antimony oxide added in the present invention is 1 to 40 parts by weight per 100 parts by weight of aromatic polyester.
It is preferably added in an amount of 3 to 20 parts by weight, particularly preferably at a ratio of 1 antimony atom per 2 to 5 bromine atoms in the composition. The composition of the present invention exhibits sufficient performance without a filler, but by adding a filler, it is possible to improve the heat distortion temperature and rigidity, and reduce the molding shrinkage rate, and the performance is further improved. The filler used in the present invention includes glass fiber,
Carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, poron whisker fiber, mica, talc, silica, calcium carbonate, glass beads, glass flakes, clay, straw Examples include fibrous, granular, powder, or plate-like inorganic fillers such as stenite and titanium oxide. Among them, fibrous inorganic fillers are preferred, and glass fibers are particularly preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resins, and can be selected from long fiber type, short fiber type chop strand, milled fiber, etc., for example. Additionally, the glass fibers may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, a coupling agent such as a silane type or a titanate type, or other surface It may be treated with a processing agent. The amount of the filler added is 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, per 100 parts by weight of the aromatic polyester. The composition of the present invention may contain conventional additives, such as ultraviolet absorbers, lubricants, mold release agents, colorants including dyes and pigments, antioxidants, and other thermoplastic resins, to the extent that the objects of the present invention are not impaired. (e.g. polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/propylene/diene terpolymer, ethylene/butene-1 copolymer, ethylene/
The composition may further contain a glycidyl methacrylate copolymer, an ethylene/vinyl acetate/glycidyl methacrylate copolymer, and the like. These additives may be used alone or in combination of two or more. The method for producing the composition of the present invention is not particularly limited, but preferably aromatic polyester,
Examples include a method of melt-kneading a specific epoxy compound, an organic bromine compound, and, if necessary, antimony oxide and a filler using an extruder. The resin composition of the present invention can be easily molded by conventional methods such as injection molding and extrusion molding, and the resulting molded product exhibits excellent properties. <Example> Hereinafter, the effects of the present invention will be described in further detail with reference to Examples. Note that parts in the examples mean parts by weight. Examples 1 to 5, Comparative Examples 1 to 4 Polybutylene terephthalate with a relative viscosity of 1.65
For 100 parts, the following epoxy compound, brominated polycarbonate (FG-7500 manufactured by Teijin Kasei Ltd.) 24
1 part and 8 parts of antimony trioxide were blended in the combinations and proportions shown in Table 1, kneaded in a V-blender, and melt-kneaded into pellets at 250°C using a 40 mmφ extruder. After drying the pellets, a 5-ounce screw-in-line injection molding machine set at 250°C was used, the mold temperature was 80°C, and the molding cycle (injection time/cooling time/intermediate time) was 10 seconds/15 seconds/10 seconds. seconds (molding cycle (a)), 10 seconds/15 seconds/185 seconds (molding cycle (b))
to obtain an ASTM No. 1 dumbbell, and the minimum pressure required to fill the resin into the mold (lower limit pressure for molding) was measured. A 1/8" impact test piece and a combustion test piece (1/16" x 1/2" x 5") were also obtained. These specimens were subjected to a combustion test according to the UL-94 standard, a tensile test according to ASTM D638,
An Izot impact test was conducted according to ASTM D256. For the tensile test pieces of molding cycle (a), a heat cycle test was conducted for 30 days (test ( A)) and hot water treatment at 100°C for 15 days (test (B)), the treated specimens were subjected to a tensile test. The results are shown in Table-1. [Epoxy compounds a to e]

[ka]

[ka]

[ka]

[ka]

[ka]

[Table] As is clear from the results in Table 1, when the specific epoxy compound of the present invention is used in combination with both the aromatic polyester and the organic bromine compound, molding fluidity, mechanical properties, especially impact strength are excellent. It can be seen that a flame-retardant aromatic polyester resin composition with extremely excellent heat cycle properties and hydrolysis resistance can be obtained. On the other hand, when something other than the specific epoxy compound of the present invention is added (Comparative Examples 2 and 3), not only the retention stability and mechanical properties during molding are inferior, but also the fluidity during molding is significantly reduced. . Examples 6-8, Comparative Examples 5-7 Polybutylene terephthalate with relative viscosity 1.47
100 parts, 50 parts of glass fiber (3 mm length, chopped strand type), 24 parts of brominated polycarbonate (FG-7000 manufactured by Teijin Kasei Ltd.), 8 parts of antimony trioxide, and a table of epoxy compounds a to e. 2. After dry blending the stated amounts in a tumbler, melt mixing and injection molding were carried out in the same manner as in Example 1 (however, the molding temperature was
260℃) and characteristics were evaluated. These results are shown in Table-2.

[Table] As is clear from the results in Table 2, even when glass fiber is used in combination, the composition of the present invention has good fluidity during molding.
It can be seen that a hard aromatic polyester resin composition can be obtained which not only has significantly improved mechanical properties such as tensile strength and impact resistance, but also has excellent hydrolysis resistance and heat cycle resistance. Examples 9 to 13, Comparative Examples 8 to 12 All compositions were the same except that the brominated polycarbonate of Example 2 was changed to the following organic bromine compounds f to i, and melt mixing, injection molding and Characteristic evaluations were conducted (Examples 9 to 13).
Further, specific epoxy-free compositions were similarly evaluated (Comparative Examples 8 to 12). These results are shown in Table 3. [Organic bromine compounds]

[ka]

[ka]

[ka]

[ka]

[ka]

The epoxy-free compositions shown in [Table] not only have significantly lower retention stability but also poor hydrolysis resistance and heat cycle resistance. <Effects of the Invention> The refractory aromatic polyester resin composition of the present invention has good fluidity and retention stability during molding, and the molded products obtained have good refractoriness, mechanical properties such as tensile strength, and hydrolysis resistance. Because it not only has excellent properties but also extremely high heat cycle resistance, it can be widely used not only in electrical and electronic applications but also in automotive electrical equipment applications.

Claims (1)

[Claims] 1 (A) Based on 100 parts by weight of aromatic polyester resin (B) An epoxy compound represented by the following general formula ()
0.01 to 10 parts by weight (In the formula, Ar represents an aromatic group or alicyclic group having 6 to 20 carbon atoms, and n represents an integer of 0 or 1 to 20.) (C) Organic bromine compound A flame-retardant aromatic polyester resin composition containing 1 to 50 parts by weight.