JPS6237669B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aromatic polyester copolymer composition, and more specifically to improving the dry heat durability and wet heat durability of an aromatic polyester copolymer molded article made of terephthalic acid, isophthalic acid, and bisphenols. This invention relates to an aromatic polyester copolymer composition prepared by adding an epoxy compound and a specific phosphorus compound. Aromatic polyester copolymers consisting of terephthalic acid, isophthalic acid, or a mixture of their functional derivatives (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is 1:9 to 9:1) and bisphenols have been used for a long time. It is well known. It is also well known that such aromatic polyester copolymers have many excellent properties. In other words, it has good mechanical properties such as tensile strength, bending strength, bending recovery rate, and impact strength, high heat distortion temperature and thermal decomposition temperature, and electrical properties such as specific resistance, dielectric breakdown, arc resistance, and dielectric properties. General molded products, films, fibers, and coating materials made by injection molding, extrusion molding, press molding, or other molding methods have excellent properties such as properties, flammability, dimensional stability, and chemical resistance. It is expected to have a wide range of uses. Although aromatic polyester copolymers have such excellent properties and are of great utility value, they have the drawback of poor dry heat durability and wet heat durability. Conventionally, stabilizers such as organic phosphite esters and inorganic phosphorus compounds have been used to increase the dry heat durability and wet heat durability, but in reality, neither of these alone has a sufficiently satisfactory effect. However, further improvements are required. A drawback of aromatic polyester copolymers is that crazes occur in molded products when they are left in hot water or steam for a long time.
The craze phenomenon has already been described in literature and elsewhere [for example, Tomikawa: Polymer Chemistry 24 (271) 731 (1967)]
However, even in aromatic polyester copolymers, when treated with hot water or steam, turbidity occurs in part or the entire molded product. Although the reason for this phenomenon is not clear,
This not only causes the molded product to lose its transparency, but also makes the molded product brittle, resulting in lower impact strength, reduced elongation at break, and application of bending stress that can lead to the molded product breaking. Ru. The present inventors have discovered that an aromatic polyester copolymer retains its inherent mechanical strength, has little coloration, and
As a result of various studies aimed at creating molded products with excellent craze resistance, we found that the addition of epoxy compounds causes some thermal decomposition of the aromatic polyester copolymer at high temperatures during melt extrusion and molding, resulting in coloration of the molded products. , found that it has an excellent effect in preventing craze, and as a result of repeated studies, it was found that by adding a specific phosphorus compound together with an epoxy compound, coloring during molding that occurs when adding only an epoxy compound can be prevented. The inventors have discovered that a molded article with excellent dry heat durability and wet heat durability can be obtained, and have arrived at the present invention. That is, the present invention provides (A) a mixture of isophthalic acid and terephthalic acid or their functional derivatives (however, the molar ratio of isophthalic acid groups and terephthalic acid groups is 1:9 to 9:1), and a compound represented by the general formula [] Bisphenols (However, -X- is -O-, -S-, -SO
-, -SO ₂ -, -CO-, selected from the group consisting of alkylene groups and alkylidene groups having 1 to 4 carbon atoms, R ₁ , R ₂ , R ₃ , R ₄ , R′ ₁ , R′ ₂ , R′ ₃ ,
R′ ₄ is selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, and an alkyl group having 1 to 4 carbon atoms), and (B)
Epoxy compound and (C) triaryl phosphite, trialkyl phosphite, hydrogen phosphite diester, pentaerythritol type phosphite, trialkyl phosphate, triaryl phosphate, phosphonic acid derivative, a compound selected from the group consisting of phosphinite derivatives, halogenated alkyl acid phosphates, and alkyl acid phosphates,
(A) 0.01 to 3.0% by weight of (B) epoxy compound and 0.01% of phosphorus compound to aromatic polyester copolymer.
It is an aromatic polyester copolymer composition containing ~3.0% by weight. The addition of such epoxy compounds and phosphorus compounds prevents discoloration during molding, has a remarkable effect on improving the dry heat durability and wet heat durability of the aromatic polyester copolymer, and also maintains its excellent mechanical strength. It's amazing what it brings. For example, a molded article of an aromatic polyester copolymer made of terephthalic acid, isophthalic acid (the molar ratio of terephthalic acid and isophthalic acid is 1:1) and 2,2-bis-(4-hydroxyphenyl)-propane is transparent. , tensile strength of 700Kg/cm2 or ^more , 6Kg-cm/
cm (with 1/2" thickness notch) or more, bending strength of 700Kg/ ^cm2 or more, and compressive strength of 900Kg/cm2 ^or more, but if treated in a dry heat atmosphere of 170℃ for 10 days, Mechanical strength is significantly reduced.
Furthermore, if treated in boiling water at 100°C for 24 hours, the transparency will be lost due to the generation of craze, and furthermore, the above-mentioned mechanical properties will be significantly reduced. However, the transparency and mechanical properties of molded products made from compositions containing the epoxy compound and phosphorus compound of the present invention are the same as those described above, and there is no coloration during molding that occurs when the epoxy compound is used alone. It retains its mechanical properties even after being exposed to a dry heat atmosphere at 100°C for 10 days, has a good color tone, and shows no craze formation after 24 hours of hot water treatment at 100°C. was holding it. Generally, when using two or more types of additives in combination, it is difficult to even achieve an effect that corresponds to the mixing ratio, but molded products made from such compositions have excellent dry heat durability and wet heat durability, and can be left in steam or hot water for long periods of time. Not only does it not cause craze and maintain good transparency, it also has high mechanical strength such as tensile strength, bending strength, and elongation at break, and there is no coloration during molding, which is a problem when using an epoxy compound alone. It is surprising that coloration can be significantly prevented when processing in a dry heat atmosphere. In addition, even in flame retardant compositions containing flame retardants, coloring occurs during molding, resulting in decreased mechanical properties and poor dry/wet heat durability; These drawbacks can be significantly improved. Examples of methods for producing the aromatic polyester copolymer used in the present invention include interfacial polymerization, solution polymerization, and melt polymerization. The molar ratio of terephthalic acid groups and isophthalic acid groups, which are the phthalic acid components of the aromatic polyester copolymer in the present invention, can be selected from a range of 9:1 to 1:9, preferably from 7:3 to 3:7, More preferably the ratio is 1:1. In addition, as the divalent phenol component, bisphenols represented by the general formula [] are used, and the typical one is 2,2-bis-(4
-Hydroxyphenyl)-propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfoxide, 4, 4'-dihydroxydiphenyl sulfide, 2,2-bis-(4-hydroxy-3,5-dibromophenyl)-propane,
These include 2,2-bis-(4-hydroxy-3,5-dichlorophenyl)-propane, and these may be used alone or in combination of two or more. In the present invention, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(4-
Hydroxy-3,5-dibromophenyl)-propane is particularly preferably used. Examples of the epoxy compound used in the present invention include monoglycidyl derivatives, dicrycidyl derivatives, triglycidyl derivatives, glycidyl ester derivatives, nitrogen-containing glycidyl derivatives, and halogenated glycidyl derivatives, with monoglycidyl derivatives and dicrycidyl derivatives being particularly preferred. used for. Examples of monoglycidyl derivatives include methyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, orthophenylphenol glycidyl ether, allyl glycidyl ether, 2-methyloctyl glycidyl ether, lauryl glycidyl ether, 2-ethylhexyl glycidyl ether, and the like. However, phenyl glycidyl ether, orthophenyl phenol glycidyl ether, and butyl glycidyl ether are particularly preferably used. Examples of diglycidyl derivatives include ethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol. diglycidyl ether, glycerin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A polypropylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether etc. can be mentioned. Examples of triglycidyl derivatives include diglycerin triglycidyl ether. Examples of the glycidyl ester derivative include diglycidyl phthalate, diglycidyl isophthalate, diglycidyl salicylate, diglycidyl ester of hexahydrophthalic acid, and dimer acid diglycidyl ester. Examples of nitrogen-containing glycidyl derivatives include 1,3-diglycidyl-5,5-dimethylhydantoin and isocyanuric acid triglycidyl ester. Examples of halogenated glycidyl derivatives include 2,4-dibromophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, and tetrabromobisphenol A diglycidyl ether. Examples include ether. Other epoxy compounds include glycidol, epoxidized soybean oil, butadiene epoxide,
Tetraphenyl ethylene epoxide, octyl epoxy phthalate, epoxidized polybutadiene,
3,4-epoxy-6-methylcyclohexyl-
Methyl, 3,4-epoxy-6-methylcyclohexanecarboxylate, 2,3-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, 4-(3,4-epoxy-5-methylcyclohexyl)butyl, 3, 4-
Epoxycyclohexane carboxylate, bis-epoxydicyclopentadiphenyl ether of ethylene glycol, bisepoxycyclohexyl adipate, indene oxide, cyclododecene epoxide, 3,4-epoxycyclohexylethylene oxide, di-3,4-epoxy-6-
Methyl cyclohexyl methyl adipate, cyclohexyl methyl-3,4-epoxy-cyclohexanecarboxylate, 3,4-epoxy-6-
Examples include methylcyclohexylmethyl-6-methylcyclohexylcarboxylate, epoxy resins made from bisphenol A and epichlorohydrin, polyalkylene ether epoxy resins, cycloaliphatic epoxy resins, and novolac type epoxy resins. The above epoxy compounds may be used alone or in combination. In order to exhibit the effects of the present invention, the amount of the polyester compound contained in the aromatic polyester copolymer composition of the present invention is 0.01 to 3.0% by weight, particularly preferably 0.1 to 3.0% by weight based on the aromatic polyester copolymer. It is in the range of 1.0% by weight. Even if such a small amount is used in combination with a phosphorus compound, coloring during molding can be prevented and dry heat durability and wet heat durability can be sufficiently improved. If more is used, the properties of the molded product, especially decomposition and coloration during molding, a decrease in heat resistance and durability, and a deterioration in color tone tend to occur. On the other hand, if it is less than 0.01% by weight, the improvement effect is relatively small. The phosphorus compounds used in the present invention are triaryl phosphites, trialkyl phosphites, hydrogen phosphite diesters, pentaerythritol type phosphites, trialkyl phosphates, triaryl phosphates, and phosphonic acids. derivatives, phosphinite derivatives, halogenated alkyl acid phosphates, and alkyl acid phosphates. The above phosphorus compounds can be used alone or in combination. Examples of the triaryl phosphite include trisnonyl phenyl phosphite, tricresyl phosphite, triphenyl phosphite, and triphenyl phosphite is particularly preferably used. Examples of trialkyl phosphite include tributyl phosphite, tridecyl phosphite,
Examples include tris-2-ethylhexyl phosphite, tristearylphosphite, trioleyl phosphite, etc. Tris-2-
Ethylhexyl phosphorite is particularly preferably used. Examples of hydrogen phosphite diester include dicresyl hydrogen phosphite,
Examples include dilauryl hydrogen phosphorite, diphenyl hydrogen phosphorite, and diphenyl hydrogen phosphorite, and diphenyl hydrogen phosphorite is particularly preferably used. Examples of the diarylalkyl phosphite include diphenyldecyl phosphorite and diphenyl tridecyl phosphorite. Examples of pentaerythritol type phosphites include distearyl pentaerythrityl diphosphite,
Examples include dicyclohexylpentaerythrityl diphosphite, dilaurylpentaerythrityl diphosphite, diphenylpentaerythrityl diphosphite, and phenylpentaerythrityl diphosphite, and distearylpentaerythrityl diphosphite is particularly preferred. used for. Examples of trialkyl phosphate esters include trimethylphosphate, tributylphosphate, trioctylphosphate, triethylphosphate, tributoxyethylphosphate, trischlorethylphosphate, and trisdichloropropylphosphate. Among them, trimethylphosphite is particularly preferably used. Examples of the triaryl phosphate include triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, etc., and triphenyl phosphate is particularly preferably used. Examples of the monoaryl diaryl phosphate include cresyl diphenyl phosphate. An example of the monoalkyl diaryl phosphate is octyl diphenyl phosphate. Examples of phosphonic acid derivatives include methylphosphonic acid dimethyl ester, phenylphosphonic acid, phenylphosphonic acid dimethyl ester, phenylphosphonic acid monomethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid phenyl ester, and phenylphosphonic acid diphenyl ester. It is particularly suitable for use. Examples of phosphinite derivatives include ethyldiphenylphosphinite,
P-nonyl phenyl diphenyl phosphinite,
Examples include phenyldiphenylphosphinite, and ethyldiphenylphosphinite is particularly preferably used. Examples of the organic phosphine include phenyldibutylphosphine, tributylphosphine, triphenylphosphine, methylphenyl-P-methoxyphosphine, and diphenylphosphine.
Examples of phosphorus halides include phosphorus trichloride. Examples of the halogenated alkyl acid phosphate include (2-chloroethyl)-acid phosphate, di-(2-bromoethyl)-acid phosphate, and di-(3-bromoethyl)-acid phosphate.
-chloropropyl) acid phosphonate, di-(3-bromopropyl) acid phosphonate, (2,3-bromopropyl-2-bromo-3
-chloropropyl)-acid phosphonate,
Examples include mono(2-chloroethyl) acid phosphate, mono(2-bromoethyl) acid phosphate, and di(2-chloroethyl) acid phosphate is particularly preferably used. Examples of alkyl acid phosphonates include butyl acid phosphonates,
2-ethylhexyl acid phosphonate, isodecyl acid phosphonate, isopropyl acid phosphonate, tridecanol acid phosphonate, dioctyl phosphonate,
Examples include dibutyl phosphonate, monobutyl phosphonate, monoisodecyl phosphonate, and butyl acid phosphonate is particularly preferably used. In order to exhibit the effects of the present invention, the amount of the phosphorus compound to be contained in the aromatic polyester copolymer composition of the present invention is 0.01 to 3.0% by weight, particularly preferably 0.1 to 3.0% by weight, based on the aromatic polyester copolymer.
It is in the range of 1.0% by weight. Even if such a small amount is used in combination with an epoxy compound, coloring during molding can be prevented and dry heat durability and wet heat durability can be significantly improved. If more is used, the properties of the molded article, especially the mechanical properties, tend to deteriorate. On the other hand, if it is less than 0.01% by weight, the improvement effect is relatively small. In the present invention, the method of adding the epoxy compound and the phosphorus compound to the aromatic polyester copolymer is not particularly limited, and they can be added in various steps. For example, both granules or powders are mixed in a V-type blender, Henschel mixer, super mixer, kneader, etc., and the mixture is directly molded, or mixed in a molten state in an extruder, co-kneader, etc. to form chips. May be molded. There is also a method in which a solution of an epoxy compound or a phosphorus compound dissolved in water or an organic solvent is mixed with a solution of an aromatic polyester copolymer dissolved in an organic solvent such as methylene chloride, and then these solvents are removed. In order to improve the heat resistance, weather resistance, and oxidation resistance of the aromatic polyester copolymer composition of the present invention, a thermal decomposition inhibitor, an ultraviolet absorber, an antioxidant, etc. may be appropriately present in the composition. . For these purposes, for example, benzotriazole compounds, benzophenone compounds or phenolic compounds are used. Furthermore, plasticizers, pigments, lubricants, flame retardants, etc. can also be used, and glass fibers can also be added to strengthen the material. The flame retardants include hexabromobenzene, hexachlorobenzene, tetrabromobenzene, tetrachlorobenzene, tribromobenzene, trichlorobenzene, pentabromotoluene, pentachlorotoluene, pentabromoethylbenzene, pentabromophenyl allyl ether, 2, 4,6-tribromophenyl allyl ether, 2,4,6-tribromophenyl-2-methyl-2,3-dibromopropyl ether decabromodiphenyl sulfide, octabromodiphenyl sulfide, tetra Chlordiphenyl sulfide, tetrachlordiphenyl sulfone, 3,5-dichlor-3',5'-dibromodiphenyl sulfone, 2,4-dichloro-
3′,4′,5′-tribromodiphenylmethane, decachlordiphenyl sulfone, decabromodiphenyl sulfone, bis(tribromophenoxy)methylene, bis(tribromophenoxy)ethylene,
Bis(pentabromophenoxy)ethylene, hexachlordiphenyl, hexabromodiphenyl,
Octabromodiphenyl, octachlordiphenyl, decabromodiphenyl, decachlordiphenyl, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-
hydroxy-3,5-dichlorophenyl)propane, 2,2-bis[4-(2',3'-dibromopropoxy)-3,5-dibromophenyl]propane, bis(4-hydroxy-3,5-dibromo phenyl) sulfone, 2,2-bis(4-ethoxy-3,5-dichlorophenyl)propane, bis(4-hydroxy-3,5-dichlorophenyl)
Sulfone, 2,2-bis(4-ethoxy-3,5
- dibromophenyl) propane, decabromodiphenyl ether, brominated diphenyl ether, tetrabromophthalic anhydride, tris(2,3 dibromopropyl) isocyanate, etc.
These can be used alone or in combination. In addition, the composition of the present invention can be used, for example, with polyethylene terephthalate (JP-A No. 48-54159, JP-A No. 49-Sho.
23844, JP-A-15834), polybutylene terephthalate (JP-A-50-23447, JP-A-1983-
34342), polyethylene oxybenzoate (Japanese Patent Publication No. 34342), etc.
50-5443), polycarbonate (Japanese Unexamined Patent Publication No. 1973)
- Publication No. 54158), polyethylene (Japanese Patent Application Laid-Open No. 1973-
51948, JP-A-50-84653), polypropylene (JP-A-48-51946), polyamide (JP-A-50-4146, JP-A-51-15292, JP-A-Sho 51)
-41635), polyurethane (JP 49-21453), polystyrene (JP 48-51049), ABS (JP 48-25053), EVA (JP 48-51947) ), polyacrylic acid ester (JP-A-49-21452), polytetrafluoroethylene (JP-A-50-5444), methyl methacrylate (JP-A-49-21452), polyphenylene sulfide (Patent Application 1973-101873, Patent Application 51
140342) or rubber (Japanese Unexamined Patent Publication No. 48-51945) depending on the purpose. That is, in the present invention, a mixture of an aromatic polyester copolymer and other polymers such as those mentioned above can be used, and the combination of the epoxy compound and phosphorus compound used in the present invention has a remarkable effect even in this case. shows. The aromatic polyester copolymer composition of the present invention can be manufactured into various useful products by using commonly known plastic molding methods such as press molding, injection molding, and extrusion molding using powder, chips, or other forms. can do. The molded product obtained in this way has excellent dry heat durability and
Even when exposed to hot water or steam at 100°C for a long time, no craze occurs, there is little decrease in mechanical strength or molecular weight, and it maintains transparency. Next, the present invention will be explained by examples. Example 1 2.03 kg of terephthalic acid dichloride and 2.03 kg of isophthalic acid dichloride were dissolved in methylene chloride 50 at 20°C.
It was dissolved in On the other hand, 2,2-bis(4-hydroxyphenyl)-propane 4.56Kg, caustic soda 1.68
Kg, paratertiary butylphenol 60g, trimethylbenzylammonium chloride 23g in water
100 at 20°C. Both solutions were placed in a 200 reaction tank equipped with a homomixer, and vigorously mixed and stirred at 20°C for 5 hours. Stop stirring, separate the methylene chloride phase, wash with ion-exchanged water until the washing water becomes neutral, then add an equal amount of acetone and dry.
A flaky polymer was obtained. The logarithmic viscosity of the obtained polymer (25°C, phenol/tetrachloroethane 6/4 weight ratio, polymer concentration 1 g/dl is 0.65
It was hot. Various epoxy compounds and phosphorus compounds shown in Table 1 were added to the polymer flakes, and after chipping, test pieces were injection molded. Part of it at 170℃
Exposure to air atmosphere for 10 days and heat the remaining specimen to 80℃95
%RH atmosphere for 5 days, and the tensile impact strength, logarithmic viscosity, and occurrence of craze of the test pieces were examined. The results were as shown in Table 1. The color tone of the test piece and the presence or absence of craze were determined visually, and the indications were as follows. Color display No craze occurs Color 1 No craze occurs 〇Pale yellow 3 Slightly craze occurs △ Yellow 5 A small amount of craze occurs × Brown 7 A medium amount of craze occurs ×× Brown 9 A large amount of craze occurs ××× Note that addition The amount of the agent added is the value relative to the aromatic polyester copolymer. As is clear from Table 1, the composition of the present invention was more colored during molding than when no additive was used (control example) or when an epoxy compound or phosphorus compound was used alone (comparative example). , coloring during dry heat atmosphere treatment is prevented, craze generation is effectively prevented, there is little decrease in average molecular weight expressed by logarithmic viscosity, and little decrease in mechanical strength expressed by tensile impact. However, when the amount added is small, the effect is small, and on the other hand, when the amount added is increased, the craze prevention effect is obtained, but the mechanical strength and dry heat durability are reduced.

【table】

【table】

[Table] Example 2 1218 parts by weight of terephthalic acid dichloride, 812 parts by weight of isophthalic acid dichloride, methylene chloride
2, a methylene chloride solution consisting of 30,000 parts by weight;
2-bis(4-hydroxyphenyl)-propane
2052 parts by weight, 2,2-bis(4-hydroxy-
An aqueous solution consisting of 544 parts by weight of 3,5-dibromophenyl)-propane, 850 parts by weight of caustic soda, 34 parts by weight of orthophenylphenol, 10 parts by weight of trimethylbenzylammonium chloride, and 40,000 parts by weight of water was vigorously mixed at 20°C for 4 hours. Stirred. Then, the methylene chloride phase was separated, and after washing with water until the washing liquid became neutral, the methylene chloride was distilled off to obtain a polymer solid. Table 2 shows the flaky polymer after drying and pulverization.
Various epoxy compounds and phosphorus compounds shown in Table 1 were added and melt-extruded to make chips, and test pieces were injection molded. Some of these specimens were heated to 170℃
exposed to air atmosphere for 10 days at 80°C.
The specimens were exposed to a 95% RH atmosphere for 10 days, and their logarithmic viscosity, tensile impact strength, and craze formation were examined. The results were as shown in Table 2. In the case of the composition of the present invention, both dry heat durability,
Excellent heat and humidity durability.

【table】

[Table] Example 3 An aromatic polyester copolymer powder was obtained in the same manner as in Example 1. To 85 parts by weight of this powder, 15 parts by weight of polyethylene terephthalate powder was added, and various epoxy compounds and phosphorus compounds shown in Table 3 were further added, melt-extruded into chips, and test pieces were injection molded. A part of it was exposed to air atmosphere for 10 days at 150℃, and the remaining specimen was exposed to 80℃95%RH.
The specimens were exposed to an atmosphere of The results were as shown in Table 3. As is clear from these results, even when polyethylene terephthalate is added, dry heat durability and wet heat durability are improved by adding an epoxy compound and a phosphorus compound in combination.

[Table] Example 4 An aromatic polyester copolymer powder was obtained in the same manner as in Example 1. 75 parts by weight of this powder is powdered with polycarbonate (Panlite L1250)
25 parts by weight and various epoxy compounds and phosphorus compounds shown in Table 4 were added and melt-extruded to make chips, which were then injection molded into test pieces. some of it
The test piece was exposed to an air atmosphere at 150°C for 10 days, and the remaining test piece was exposed to an atmosphere at 80°C and 95% RH for 10 days, and the logarithmic viscosity, tensile impact strength, and craze generation of the test piece were investigated. The results were as shown in Table 4. As is clear from these results, even when polycarbonate is added, the dry heat durability and wet heat durability are improved by adding the epoxy compound and the phosphorus compound.

[Table] Example 5 An aromatic polyester copolymer powder was obtained in the same manner as in Example 1. To 68 parts by weight of this powder, 17 parts by weight of polyethylene terephthalate powder and 15 parts by weight of flame retardant decabromodiphenyl ether were added,
Furthermore, the epoxy compound and phosphorus compound shown in Table 5 were added, melt-extruded into chips, and test pieces were injection molded. A part of the specimen was exposed to an air atmosphere at 170°C for 10 days, and the remaining specimen was exposed to an atmosphere of 80°C and 95% RH for 10 days, and the logarithmic viscosity, tensile impact strength, and craze occurrence of the specimen were investigated. The results were as shown in Table-5. As is clear from these results, even when a flame retardant is added, coloring during molding can be effectively prevented by adding an epoxy compound and a phosphorus compound together, and dry heat durability and wet heat durability are improved. ing.

[Table] Example 6, Comparative Example 3 Various epoxy compounds and phosphorous esters shown in Table 6 were added to the flaky polymer of Example 1 in the proportions shown in Table 6, and the mixture was vacuum dried. death,
The mixture was then extruded using an extruder at 270°C to form chips. After vacuum-drying the pellets prepared above, a tensile impact test piece was injection molded at 270°C, and this test piece was treated under the same conditions as in Example 1. Tensile impact strength before and after,
Logarithmic viscosity, color tone, and presence or absence of craze were evaluated. The results were as shown in Table 6. Further, the color tone and the presence or absence of craze were evaluated in the same manner as the evaluation method shown in Example 1. As can be seen from Table 6, the polyarylate composition of the present invention showed no discoloration after being treated at 170°C for 10 days and no craze after being treated at 80°C and 95% RH for 5 days, compared to the polyarylate composition of the cited example. It's better than anything else.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) A mixture of isophthalic acid and terephthalic acid or functional derivatives thereof (provided that the molar ratio of isophthalic acid groups to terephthalic acid groups is 1:9 to 9:1), and the general formula [] Bisphenols represented by (However, -X- is -O-, -SO ₂ -, -SO
-, -S-, -CO-, selected from the group consisting of alkylene groups and alkylidene groups having 1 to 4 carbon atoms, R ₁ , R ₂ , R ₃ , R ₄ , R' ₁ , R' ₂ , R′ ₃ , R′ ₄
is hydrogen atom, chlorine atom, bromine atom and carbon number 1
(B) an epoxy compound; (C) a triaryl phosphite;
Trialkyl phosphite, hydrogen phosphite diester, pentaerythritol type phosphite, trialkyl phosphate, triaryl phosphate, phosphonic acid derivative, phosphinite derivative, halogenated alkyl acid phosphonate and alkyl consisting of a phosphorus compound selected from the group consisting of acid phosphonates,
(A) 0.01 to 3.0% by weight of (B) epoxy compound and 0.01% of phosphorus compound to aromatic polyester copolymer.
An aromatic polyester copolymer composition containing ~3.0% by weight.