Thermoplastic resin composition

Description: TECHNICAL FIELD [Detailed description of the invention]

&lt;Industrial application field&gt; The present invention relates to a thermoplastic resin composition composed of a polyarylate resin, a polyethylene terephthalate resin, a polyamide resin and an epoxy resin, which have excellent impact strength, solvent resistance and moldability. &lt;Conventional technology&gt; The composition composed of a polyarylate resin, a polyethylene terephthalate resin and a polyamide resin is excellent in heat resistance, solvent resistance and moldability, and is disclosed in, for example, Japanese Patent Publication No. 58-50260. &lt;Problems to be solved by the invention&gt; However, although polyallylate and polyethylene terephthalate are easily compatible with each other, polyamide is incompatible with the former two, so the composition obtained by melt-kneading these exhibits a phase-separated structure, and the phase of polyarylate or polyethylene terephthalate and polyamide Since the adhesive strength at the interface of the phase is weak, the impact strength is small and there is a drawback that it is brittle. In order to improve the impact strength of the resin composition, Japanese Patent Application Laid-Open No. 52-100552 has improved the manufacturing method, but it has not yet had sufficient mechanical strength. The present invention has been made in view of the above circumstances, and is characterized by excellent solvent resistance, heat resistance, moldability, and high rigidity, which are the characteristics of a thermoplastic resin composition composed of a polyarylate resin, a polyethylene terephthalate resin, and a polyamide resin. An object of the present invention is to provide a thermoplastic resin composition having significantly improved impact strength without impairing thermal stability. &lt;Means to solve problems&gt; The present inventors consider that if the bonding force between the polyester phase and the polyamide phase of the phase-separated polyarylate and polyethylene terephthalate is strengthened, the impact strength of the composition will be improved, and the amide bond of the polyamide phase A diligent search for a phase solvent having a functional group that interacts with any of the ester bonds of the polyester phase revealed that the epoxy resin obtained from bisphenol and epichlorohydrin showed a remarkable effect in improving the impact strength with the addition of a small amount. all right. That is, the present invention relates to 100 parts by weight of a resin composed of 10% by weight or more of polyarylate resin, 20% by weight or more of polyamide resin, and 3 to 60% by weight of polyethylene terephthalate resin.<img file="JPH0733467B2_D0001.tif" /><img file="JPH0733467B2_D0002.tif" />(X is a direct bond, a methylene group with 1 carbon, a lower alkylidene group with 2 to 4 carbons, a lower alkylene group with 1 to 4 carbons,<img file="JPH0733467B2_D0003.tif" />-SO₂-, -O-, -S-, and some or all of the hydrogen atoms of X may be replaced with halogen atoms, and R is a hydrogen atom, a halogen atom, and a lower group having 1 to 4 carbon atoms. Provided is a thermoplastic resin containing 0.1 to 15 parts by weight of an epoxy resin represented by (1) which is one of the alkyl groups and n is an integer of 1 or more. The present invention will be described in more detail below. The polyarylate resin used in the present invention includes terephthalic acid and isophthalic acid (and derivatives thereof), and a general formula.<img file="JPH0733467B2_D0004.tif" />Bisphenols represented by (where Y is a methylene group having 1 carbon atom, a lower alkylidene group having 2 to 4 carbon atoms, a lower alkylene group having 1 to 4 carbon atoms,<img file="JPH0733467B2_D0005.tif" /><img file="JPH0733467B2_D0006.tif" />A part or all of the hydrogen atom of Y may be replaced with a halogen atom, and R is a hydrogen atom, a halogen atom, or a lower alkyl group having 1 to 4 carbon atoms, and each other. It may be the same or different). Examples of the bisphenols represented by the above general formula include 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 4,4'-dihydroxydiphenyl ether, and bis (4-hydroxyphenyl) sulfide. Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 1,1- Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, bis (4-hydroxy) Examples thereof include phenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, and bis (4-hydroxyphenyl) difluoromethane. Of these, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A, is preferable because of the availability of raw materials. If necessary, a small amount of aromatic dihydroxy compound such as 4,4'-biphenol, 2,6-naphthalenediol, hydroquinone, chlorhydroquinone and the like can be mixed and used with the bisphenols. Derivatives of terephthalic acid and isophthalic acid include acid halide compounds such as terephthalic acid dichloride and isophthalic acid dichloride, and diesteric acid compounds such as dimethyl terephthalate, dimethyl isophthalate, diphenyl terephthalate and diphenyl isophthalate. In the terephthalic acid, isophthalic acid and derivatives thereof used in the present invention, a part or all of the hydrogen atom of the phenylene group may be substituted with a halogen atom or a lower alkyl group. The polyarylate resin used in the present invention may be synthesized by any of an interfacial polymerization method, a solution polymerization method, and a melt polymerization method. Examples of the polyethylene terephthalate resin used in the present invention include those produced from terephthalic acid (and its derivatives) and ethylene glycol by an arbitrary method. The polyamide resin used in the present invention is a general formula.<img file="JPH0733467B2_D0007.tif" /><img file="JPH0733467B2_D0008.tif" />(R₁, R₂And R₃Is represented by an alkylene group having 2 to 16 carbon atoms), and is synthesized by a condensation reaction of a diamine and a dibasic acid, self-condensation of an amino acid, or ring-opening polymerization of lactam. For example, nylon 6 synthesized from ε-caprolactam or ε-aminocaproic acid, nylon 6-6 synthesized from hexamethylenediamine and adipic acid, nylon 6-10 synthesized from hexamethylenediamine and sebacic acid, hexamethylene diami. Nylon 6-12 synthesized from nin and dodecanedic acid, nylon 11 synthesized from ω-aminoundecanoic acid, nylon 12, 1,4-diaminobutane synthesized from ω-laurolactam or ω-aminododecanoic acid Examples include nylon 4-6 synthesized from adipic acid. Nylon 6 and nylon 6-6 are preferably used because of the availability of raw materials. The epoxy resin used in the present invention is a general formula.<img file="JPH0733467B2_D0009.tif" /><img file="JPH0733467B2_D0010.tif" />(X is a direct bond, a methylene group with 1 carbon, a lower alkylidene group with 2 to 4 carbons, a lower alkylene group with 1 to 4 carbons,<img file="JPH0733467B2_D0011.tif" />-SO₂-, -O-, -S-, and some or all of the hydrogen atoms of X may be replaced by halogen atoms, and R is a hydrogen atom, a halogen atom, and a lower group having 1 to 4 carbon atoms. It is one of the alkyl groups, where n is an integer greater than or equal to 1) and is obtained from the reaction of bisphenol with epichlorohydrin. As an example of bisphenols. Bis (4-hydroxyphenyl) sulfone, 4,4'-biphenol, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane , Bis (4-Hydroxyphenyl) Phenylmethane, Bis (4-Hydroxyphenyl) Diphenylmethane, 2,2-Bis (4-Hydroxy-3,5-Dimethylphenyl) Propane, 2,2-Bis (4-Hydroxy-3) , 5-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and the like. 2,2-Bis (4-hydroxyphenyl) propane, that is, bisphenol A, is preferably used because of the availability of raw materials. N, which is the number of repeating units represented by the general formula of the epoxy resin, must be 1 or more. When n is zero, the effect of the epoxy group of the terminal group is likely to be exhibited, and the obtained resin composition is likely to be gelled, colored, or decomposed. In particular, the melting temperature and viscosity increase remarkably, making molding difficult. In order to sufficiently bring out the effect of improving the impact strength of the present invention, it is preferable that the terminal epoxy group and the repeated portion of the polyether polyol portion are present in an appropriate ratio. That is, the preferred range of n is about 6 to 20. The preferred epoxy equivalent range is about 1000 to 3000 in the case of the bisphenol A type epoxy resin. The epoxy resin used in the present invention is copolymerized with diols other than bisphenol, that is, aromatic diols such as 2,6-naphthalenediol and hydroquinone, and aliphatic diols such as 1,4-butanediol, propylene glycol, and ethylene glycol in a small amount. You may let me. The composition ratios of the polyarylate resin, the polyethylene terephthalate resin, and the polyamide resin used in the present invention are 10% by weight or more, 3 to 60% by weight, and 20% by weight or more, respectively, with respect to the total amount of the three components. When the polyarylate resin is less than 10% by weight, the heat resistance and impact strength of the obtained resin composition are low, and when the polyamide resin is less than 20% by weight, the moldability and solvent resistance are lowered. Further, when the polyethylene terephthalate resin is less than 3% by weight, the moldability and rigidity (elastic modulus) of the obtained resin composition are lowered, and when it exceeds 60% by weight, the heat resistance and impact strength are lowered. When the polyarylate component increases, the impact strength and heat resistance of the obtained resin composition increase, when the polyamide component increases, the moldability and solvent resistance improve, and when the polyethylene terephthalate component increases, the moldability improves and the rigidity increases. Increase. Preferably, the composition ratio in which heat resistance, impact resistance, moldability, rigidity, and solvent resistance are balanced is 15 to 45% by weight of polyarylate resin, 45 to 65% by weight of polyamide resin, and 7 to 35% by weight of polyethylene terephthalate resin. Is. The amount of the epoxy resin used as the phase solvent is preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the mixture of the polyarylate resin, the polyamide resin and the polyethylene terephthalate resin. If it is less than 0.1 parts by weight, the effect of improving the impact resistance is small, and if it exceeds 15 parts by weight, the heat resistance of the obtained composition is lowered, and the melting temperature and viscosity increase, which makes molding difficult, which is not preferable. The preferred addition amount is 2 to 10 parts by weight. The method for producing the composition of the present invention can be used as long as it can melt and knead a polyarylate resin, a polyamide resin, a polyethylene terephthalate resin and an epoxy resin. For example, there are a two-roll mill, a Banbury mixer, a single-screw extractor, a twin-screw extruder, and the like, and molding may be performed while kneading in an injection molding machine. A high kneading type single-screw or twin-screw extruder is preferable. The kneading order for obtaining the composition of the present invention may be any order. The four components of polyarylate, polyamide, polyethylene terephthalate and epoxy resin may be kneaded at the same time, or two or more of the four components may be kneaded in advance and then the other components may be kneaded. The optimum kneading sequence is a method in which polyarylate and polyethylene terephthalate are melt-kneaded in advance, and the mixture is melt-kneaded with the polyamide and epoxy resin. Additives, fillers and the like may be added to the resin composition in the present invention. Additives include antioxidants such as copper halide and hindered phenols, heat stabilizers; phosphorus-based processing stabilizers; benzotriazole-based and hindered amine-based light-resistant stabilizers; paraffins, higher fatty acids and their esters. , Plasticizers such as metal salts, lubricants such as silicone resins, fluororesins; decabromodiphenyl ether, tetrabromodiphenyl ether, tetrabromobisphenol A, tetrachlorobisphenol A, aluminum hydroxide, antimony trioxide, ammonium phosphate, tricresylphosphate, triethyl Flame retardants such as phosphorate; pigments; dyes and the like. Examples of the filler include talc, calcium carbonate, mica, wollastonite, ferrite, rare earth magnet powder, glass fiber, carbon fiber, asbestos fiber, metal fiber, aramid fiber, potassium titanate whisker and the like. &lt;Example&gt; Hereinafter, the present invention will be specifically described based on Examples. First, the raw materials used in Examples and Comparative Examples will be shown. (Ingredient 1) Polyarylate resin (PAR) obtained from a 1/1 mixture of terephthalic acid / isophthalic acid and bisphenol A (U-polymer U-100 manufactured by Unitika Ltd.). Logarithmic viscosity is 0.65 dl / g (measured at a concentration of 0.25 g / dl at 23 ° C with a phenol / tetrachloroethane = 60/40 weight ratio as a solvent). (Ingredient 2) Polyethylene terephthalate resin (PET) (PET resin TR-4550BH manufactured by Teijin Limited) Tolerance viscosity 0.70 (same as the measurement method for raw material 1) (Raw material 3) Nylon 6 (PA6) (Amiran CM1017 manufactured by Toray Industries, Inc.) (Ingredient 4) Nylon 6-6 (PA6-6) (Alamine CM3001 manufactured by Toray Industries, Inc.) (Ingredients 5 ~ 10) Epoxy resin (manufactured by Dainippon Ink and Chemicals Co., Ltd.)<img file="JPH0733467B2_D0012.tif" /><img file="JPH0733467B2_D0013.tif" /><img file="JPH0733467B2_D0014.tif" /><img file="JPH0733467B2_D0015.tif" /><img file="JPH0733467B2_D0016.tif" />(Raw material 11) Phenoxy resin (Phenoxy PKHH manufactured by Union Carbide)<img file="JPH0733467B2_D0017.tif" /><img file="JPH0733467B2_D0018.tif" />(Ingredient 12) The terminal epoxy group of Epicron 9055 is modified with diethanolamine.<img file="JPH0733467B2_D0019.tif" /><img file="JPH0733467B2_D0020.tif" /><img file="JPH0733467B2_D0021.tif" />Next, the physical properties and evaluation methods performed in Examples and Comparative Examples of the present invention will be shown. 1) Tensile test: According to ASTM D-638, the measurement was performed at a tensile speed of 50 mm / min, and the tensile breaking strength, tensile elastic modulus, and tensile breaking energy (the amount of work required to break) were determined. 2) Izod impact test: Measured according to ASTM D-256 with a thickness of 1/8 inch and a notch. 3) Thermal deformation temperature: After annealing at 150 ° C for 3 hours, 1/8 inch thick, load 18.6 kg / cm according to ASTM D-648.²Measured at. 4) Temperature when the melt viscosity reaches 10,000 poise: Shimadzu Corporation's high-load flow tester CFT-500 uses a nozzle with a diameter of 0.5 x 1.0 mm, a load of 10 kg, and a temperature rise of 6 ° C / min. The viscosity of the resin was measured sequentially at a rate, and the temperature at which the melt viscosity reached 10,000 poise was determined. It serves as a guide for the moldability of the resin and the progress of the gelation reaction. That is, the lower the temperature, the less the gelation progresses, and the easier it is to mold. (Examples 1 to 6, Comparative Examples 1 to 2) 60 parts by weight of polyarylate resin (raw material 1) and 40 parts by weight of polyethylene terephthalate resin (raw material 2) are mixed, dried at 110 ° C for 5 hours, and then melted in a twin-screw extruder with a cylinder temperature of 300 ° C. It was kneaded and pelletized. 50 parts by weight of the mixture of this polyarylate resin and polyethylene terephthalate resin and 50 parts by weight of nylon 6 (raw material 3) were mixed, and the amount of epoxy resin (raw material 9) shown in Table 1 was added to 100 parts by weight of this mixture. After drying at 110 ° C for 5 hours, the mixture was melt-kneaded in a twin-screw extruder with a cylinder temperature of 270 ° C and pelletized. These pellets were molded into a 1/2 × 1/5 × 1/8 inch strip-shaped test piece and a dumbbell for tensile test using an injection molding machine, and their physical properties were evaluated. The results are shown in Table 1. From Table 1, it can be seen that the addition of a small amount of epoxy resin significantly increases the Izod impact strength and tensile breaking energy. However, if the amount of the epoxy resin added exceeds 15 parts by weight, the impact strength and the thermal deformation temperature decrease, and the moldability deteriorates. (Examples 7 to 11, Comparative Examples 3 to 8) Polyarylate resin (raw material 1), polyethylene terephthalate resin (raw material 2), nylon 6 (raw material 3) and epoxy resin (raw material 9) having the composition ratios shown in Table 2 were kneaded in the same order and kneading method as in Example 1. It was pelletized, injection molded, and evaluated for physical properties. The results are shown in Table 2. (Examples 12 to 18, Comparative Examples 9 to 13) Using the raw materials and composition ratios shown in Table 3, pelletization is performed using the same method as in Example 1, that is, a method in which a polyarylate resin and a polyethylene terephthalate resin are melt-kneaded in advance, and the other two components are added and melt-kneaded. , Injection molding, and physical property evaluation. The results are shown in Table 3.<img file="JPH0733467B2_D0022.tif" /><img file="JPH0733467B2_D0023.tif" /><img file="JPH0733467B2_D0024.tif" />&lt;Effect of invention&gt; The present invention provides an excellent resin composition having excellent moldability, heat resistance, impact resistance, solvent resistance, and high rigidity and well-balanced physical characteristics, and is used in an application utilizing these features, that is, Ideal for housings of electronic and electrical equipment exposed to high heat, slitches, knobs, various containers that take advantage of solvent resistance, and daily necessities.