JP2008280422A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent antistatic property, flame-retardancy, injection moldability and mechanical properties and keeping the antistatic effect even after aging, and to provide a molded article useful as machine mechanism parts, electric or electronic parts and automobile parts. <P>SOLUTION: The thermoplastic resin composition is produced by compounding (B) a block polyether amide produced from (B-1) a polyalkylene ether and (B-4) a polyamide, (B-2) a metal sulfonate and (B-3) a sterically hindered phenol compound to a composition composed of (A) a polyester resin, (C) a brominated polycarbonate compound and (D) an antimony compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame-retardant thermoplastic polyester resin composition imparted with antistatic properties, and relates to a molded product useful for mechanical mechanism parts, electrical / electronic parts, and automobile parts.

  Polyester resins are utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of their excellent mechanical properties.

  However, while polyester resin is excellent in electrical insulation, it has drawbacks such as easy charging and dust adhesion, so the use of polyester resin is limited especially in applications that require antistatic properties. There is.

  Conventionally, various methods have been proposed as methods for imparting antistatic properties to polyester resins. For example, the method of blending a polyetheramide block copolymer disclosed in Patent Document 1 is relatively excellent. However, in order to develop the antistatic effect, it is necessary to add a large amount of polyether block copolymer. As a result, the flame retardancy is significantly reduced. It wasn't enough to do.

Also disclosed are compositions in which an inert polyoxyalkylene ether (polyalkylene glycol) and an alkyl sulfonic acid metal salt shown in Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5 are blended in a polyester. ing. However, although these exhibit an antistatic effect after molding, the antistatic effect decreases after aging, and thus the sustainability of the antistatic effect is not sufficient.
JP 7-41652 A JP-A-53-149246 JP-A-53-149247 Japanese Patent Laid-Open No. 53-1346 JP 61-258860 A

  That is, the present invention aims to obtain a polyester resin composition having excellent antistatic properties, excellent flame retardancy, injection moldability, mechanical properties, and capable of sustaining the antistatic effect even after aging. It is an object of the present invention to provide a molded product useful for mechanical parts, electrical / electronic parts, and automobile parts.

  In order to solve the above problems, the present invention has the following configuration. That is, the present invention provides (B) block poly produced from (A) polyester resin, (C) brominated polycarbonate compound and (D) antimony compound, (B-1) polyalkylene ether and (B-4) polyamide. A composition containing ether amide, (B-2) sulfonic acid metal salt, (B-3) sterically hindered phenol compound, (A) 50-80% by weight of polyester resin, (C) brominated polycarbonate compound 10 to 20% by weight, (D) 3 to 10% by weight of the antimony compound, and a total of 5 to 15% by weight of (B-1), (B-2), (B-3) and (B-4) is contained, And when the total of (B-1) (B-2) (B-3) (B-4) is 100% by weight, (B-1) is 40 to 50% by weight, and (B-2) is 1-10 wt%, (B-3) is 1-10 wt% A thermoplastic resin composition characterized in that it consists of 40 to 50 wt% (B-4).

  According to the present invention, it is possible to obtain a molded product having a high antistatic effect, flame retardancy, injection moldability, and mechanical properties, and to exhibit antistatic properties even after aging. It is a molding material useful for electronic parts and automobile parts.

  Embodiments of the present invention will be described below. In the present invention, (B) block poly produced from (A) polyester resin, (C) brominated polycarbonate compound and (D) antimony compound, (B-1) polyalkylene ether and (B-4) polyamide. It is important that the composition contains ether amide, (B-2) sulfonic acid metal salt, and (B-3) sterically hindered phenolic compound.

  In the present invention, the (A) polyester resin is a polymer or copolymer obtained by a polycondensation reaction mainly comprising a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). Say.

  Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2 ″ -biphenyldicarboxylic acid, 3,3 '-Biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfonic dicarboxylic acid, 4,4'-diphenyl isopropyl Redene dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylene dicarboxylic acid, Aromatic dicarboxylic acids such as 2,5-pyridinedicarboxylic acid Is, terephthalic acid can be preferably used.

  These dicarboxylic acids may be used by mixing two types of abnormalities. In addition, it is possible to use a mixture of one or more alicyclic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid and the like, and cyclohexanedicarboxylic acid together with these dicarboxylic acids in a small amount. it can.

  Examples of the diol component include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol and other aliphatic diols, 1,4- Examples thereof include alicyclic diols such as cyclohexanedimethanol, and mixtures thereof. If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.

  Preferable examples of these polymers and copolymers include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-. In addition to dicarboxylate, there may be mentioned copolyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate. Of these, polybutylene terephthalate can be preferably used. These thermoplastic polyester resins preferably have a relative viscosity in the range of 1.2 to 2.0 when measured with a 0.5% o-chlorophenol solution at 25 ° C. Within the above range, a composition having excellent mechanical properties and excellent moldability can be obtained.

(B) used in the present invention
The block polyether amide is a block copolymer of polyether and (B-4) polyamide, and a simple blend of polyether and (B-4) polyamide is referred to in the present invention as (B) block poly Not included in ether amide.

  (B) The polyether constituting the block polyether amide is (B-1) a polyalkylene ether, which is a polymerization product of ethylene oxide and / or propylene oxide such as polyethylene ether, polypropylene ether, polyethylene propylene ether and the like. is there. The molecular weight of these polyethers is 1000 or more, preferably 3000 to 8000, and the use of polyethylene oxide is most suitable. Within the above range, a composition having excellent mechanical properties and excellent heat resistance can be obtained.

  On the other hand, (B) the polyamide constituting the block polyether amide (B-4) includes homopolyamides such as nylon 6, nylon 8, nylon 12, nylon 66, nylon 610, or these or other copolymer components. It is a copolymer.

  (B) As a manufacturing method of block polyether amide, for example, (B-1) after cyanoethylating both ends of polyalkylene ether, hydrogenation is carried out to make polyalkylene ether diamine, and this is used as adipic acid or sebacic acid A nylon salt is synthesized by reacting with an appropriate dicarboxylic acid, and (B-4) a method of polycondensing the salt with the monomer forming the polyamide, and (B-1) amination of both ends of the polyalkylene ether. Examples of the polyalkylene ether diamine include polycondensation by the same method as described above, but the method for producing these (B) block polyether amides is not particularly limited. The weight ratio of the polyether component to the (B-4) polyamide component in the (B) block polyether amide is suitably from 30 to 70 to 70 to 30. Within the above range, a composition having excellent heat resistance and excellent antistatic effect can be obtained.

  (B) The polycondensation method of the block polyether amide is not particularly limited, and is employed in the usual known polycondensation method of polyamide, for example, atmospheric pressure polymerization method often used for nylon 6 or nylon 66 or the like. The pressure polymerization method can be employed regardless of batch type or continuous type.

  The resin composition of the present invention needs to contain (B-2) a sulfonic acid metal salt and (B-3) a sterically hindered phenol compound. Here, (B-2) sulfonic acid metal salt refers to sulfonic acid such as dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid, hexadecylsulfonic acid, dodecylsulfonic acid and the like, sodium, potassium, lithium and the like. There are alkali metal salts of sulfonic acids formed from alkali metals, alkali metal salts of phosphoric acids such as distearyl sodium phosphate, and other alkali metal salts of carboxylic acids. Among them, such as sodium dodecylbenzene sulfonate The metal salt of sulfonic acid is good.

  (B-3) Examples of the sterically hindered phenol compound include 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,2 Examples thereof include phenolic derivatives containing a substituent having a steric hindrance at a position adjacent to a phenolic hydroxyl group such as' -methylenebis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol.

  In the present invention, when the total of (B-1), (B-2), (B-3), and (B-4) is 100% by weight, (B-1) is 40 to 50% by weight, (B-2 ) Is 1 to 10% by weight, (B-3) is 1 to 10% by weight, and (B-4) is 40 to 50% by weight. (B-2) The sulfonic acid metal salt is particularly preferably in the range of 3 to 7% by weight. If it is less than 1% by weight, the effect of improving the antistatic property is insufficient, and if it exceeds 10% by weight, the antistatic property is lowered due to the deterioration of the muscle forming ability due to the decrease in the melt viscosity of the block polyetheramide composition. (B-3) The sterically hindered phenolic compound is particularly preferably in the range of 3 to 7% by weight, and if it is less than 1% by weight, the deterioration of the antistatic property due to the thermal oxidation deterioration in the compound process, the molding process, etc. is sufficiently suppressed. Even if it exceeds 10% by weight, the effect of suppressing thermal oxidation is saturated and it is difficult to recognize any further effect.

  In the present invention, it is necessary that the total amount of (B-1), (B-2), (B-3), and (B-4) is 5 to 15% by weight, preferably 6 to 14%. It is weight. If the blending amount is less than 5% by weight, sufficient antistatic properties cannot be expressed. On the other hand, if the blending amount exceeds 15% by weight, the flame retardancy is remarkably lowered.

  The (C) brominated polycarbonate compound used in the present invention is a brominated polycarbonate compound generally used as a flame retardant for thermoplastic polyesters, and those having a bromine content of 50% or more are particularly preferred. (C) The compounding quantity of brominated polycarbonate is 10 to 20 weight% of the whole composition, Preferably it is 11 to 19 weight%, More preferably, it is 12 to 18 weight%. The amount required to develop flame retardancy varies depending on the amount of thermoplastic polyester resin, but if it is less than 10% by weight, sufficient combustibility cannot be exhibited. On the other hand, when the blending amount exceeds 20% by weight, the mechanical properties are greatly deteriorated, which is not preferable.

  As the antimony compound (D) used in the present invention, it is possible to synergistically improve the flame retardancy by using in combination with an organic bromine compound. Antimony trioxide, antimony pentoxide, sodium antimonate and phosphoric acid Antimony compounds such as antimony are exemplified, and antimony compounds that have been surface-treated can also be used. Of these, antimony trioxide is suitable.

  (D) The compounding quantity of an antimony compound is 3 to 10 weight% of the whole composition, More preferably, it is 4 to 9 weight%. If it is less than 3% by weight, sufficient combustibility cannot be exhibited. On the other hand, when the blending amount exceeds 10% by weight, the mechanical properties are remarkably lowered, which is not preferable.

  The polyester-based resin composition of the present invention includes an antioxidant, a stabilizer, an ultraviolet absorber, a colorant, a release agent, a flame retardant, a colorant, a matting agent, a fluorescent substance, as long as the effects of the present invention are not impaired. Conventional additives such as additives, anti-mold agents, pigments and small amounts of other polymers can be added.

  Examples of antioxidants include 2,6-di-t-butyl-4-methylphenol, tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, tris Phenol compounds such as (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, sulfur such as dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate And phosphorous compounds such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite.

  Stabilizers include benzotriazole compounds including 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, and benzophenone compounds such as 2,4-dihydroxybenzophenone, mono- or distearyl phosphate, trimethyl phosphate And phosphoric acid esters.

  These various additives may have a synergistic effect by combining two or more kinds, and may be used in combination.

  For example, the additive exemplified as the antioxidant may act as a stabilizer or an ultraviolet absorber. Some of those exemplified as stabilizers also have an antioxidant action and an ultraviolet absorption action. In other words, the classification is for convenience and does not limit the action.

Release agents include plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax, petroleum waxes such as paraffin wax and polyethylene wax, castor oil and its Derivatives, fatty acids and oil-based waxes such as derivatives thereof, and higher fatty acid derivatives include higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, montanic acid and monohydric or dihydric or higher alcohols. Esters, partial saponification of these higher fatty acid esters partially with metal oxides such as Ca (OH) ₂ , NaOH, Mg (OH) ₂ , Zn (OH) ₂ , LiOH, Al (OH) ₃ Saponification obtained from esterified esters, higher fatty acids and metal oxides or metal hydroxides Products, higher fatty acids and polyhydric alcohol esters, which are condensed with a dicarboxylic acid such as adipic acid as a binder, mono- or diamides obtained from higher fatty acids and monoamines or diamines.

  Examples of the method for producing the resin composition of the present invention include a method of supplying and kneading from the upstream side of the extruder at a cylinder temperature of 230 to 300 ° C. using a twin screw extruder. It may be melt-kneaded at a temperature of 200 to 350 ° C. using a known melt mixer such as a shaft extruder, Banbury mixer, kneader or mixing roll, and the components are mixed together in advance. Then, it may be melt kneaded. Furthermore, for a small amount of additive component such as 1% by weight or less with respect to 100% by weight of the total amount of components (A), (B1), (B2), (C), (D), other components May be added before molding after kneading and pelletizing by the above-mentioned method. In addition, although it is better that the water | moisture content adhering to each component is less and it is desirable to dry beforehand, not all the components need to be dried.

  The resin composition of the present invention is generally molded by a known thermoplastic resin molding method such as injection molding, extrusion molding, blow molding, transfer molding, vacuum molding, etc., and among them, it is preferably used for injection molding.

  Since the polyester resin of the present invention is excellent in moldability, antistatic property of molded products, and flame retardancy, it is preferably applied to electric and electronic parts or automobile parts. Specific examples of electrical / electronic parts or automobile parts include cases, covers, lighting parts, electrical parts, and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples. Moreover, all the addition mixture ratios shown in the Examples and Comparative Examples are% by weight.

  The material property evaluation method of an Example and a comparative example is shown below.

(1) Flame retardancy Using an injection molding machine (Nissei 60E9ASE), injection molding of a test piece for flame retardancy was performed under conditions of a molding temperature of 260 ° C and a mold temperature of 80 ° C. The flame retardancy was evaluated according to the evaluation criteria. Flame retardancy falls and ranks in the order of V-0>V-1>V-2> HB. The thickness of the test piece was 1/32 inch (about 0.75 mm, hereinafter abbreviated as 1/32 ").

(2) Antistatic property Using an injection molding machine (Nissei 60E9ASE), a molded product on a square plate was molded under conditions of a molding temperature of 260 ° C and a mold temperature of 80 ° C, and the surface resistivity of the molded product was measured. did. Moreover, it put into the hot air dryer "HighTempOven" PVH210 by Tabai company adjusted to 120 degreeC, and the antistatic property after 200 hours processing was evaluated by the same method as the above. In addition, a material having a lower surface resistivity is a material having better antistatic properties.

Examples 1-5
Using the following materials, materials were charged according to the combinations shown in Table 1, and extruded using a twin screw extruder with a screw diameter of 57 mmΦ at a barrel set temperature of 260 ° C. and a screw rotation speed of 200 rpm to produce resin composition pellets. .

(A) Polybutylene terephthalate resin Intrinsic viscosity 0.85 PBT resin “Toraycon” 1100S manufactured by Toray Industries, Inc.

(B) Block polyether amide, (B-2) sulfonic acid metal salt, (B-3) a composition containing a sterically hindered phenol compound (B-1) Polyethylene glycol as a polyalkylene ether in the presence of an alkali catalyst In this way, acrylonitrile is reacted with, and further hydrogenation reaction is performed to synthesize polyethylene glycol diamine (number average molecular weight 4000) with 97% or more of both ends being amino groups, and this is salted with adipic acid in a conventional manner. Gave a 45% aqueous solution of polyethylene glycol ammonium adipate.

200 kg of the 45% polyethylene glycol diammonium adipate aqueous solution, 120 kg of 85% caprolactam aqueous solution as polyamide (B-4), and 1.6 kg of 40% hexamethylene diammonium isophthalate aqueous solution were placed in a 2 cm ³ concentration canister, The mixture was heated for about 2 hours at normal pressure until the internal temperature reached 110 ° C., and concentrated to 80% concentration. Subsequently, the concentrated liquid was transferred to a polymerization can having a capacity of 800 L, and heating was started while flowing nitrogen at 25 L / min into the polymerization can. When the internal temperature reaches 120 ° C., (B-2) 5.2 kg of dodecylbenzenesulfonic acid sodium salt as the sulfonic acid metal salt and (B-3) 1,3,5-trimethyl-2 as the sterically hindered phenol compound , 4,6-tri (3,5di-tert-butyl-4-hydroxybenzene) benzene was added and heated for 18 hours until stirring was started and the internal temperature reached 245 ° C. to complete the polymerization. I let you. After completion of the polymerization, a pressure of 7 kg / cm ² (G) is applied to the can with nitrogen, and the molten polymer is extruded onto a rotating endless belt in a belt shape having a width of about 15 cm and a thickness of 1.5 mm. Pelletized. (When (B-1) (B-2) (B-3) (B-4) is 100% by weight, (B-1) is 45% by weight and (B-2) is 5% by weight. (B-3) is 5 wt%, and (B-4) is 45 wt%).

(C) Brominated polycarbonate compound “Fireguard G7100” manufactured by Teijin Chemicals Ltd.

(D) Antimony compound “Fire-cut AT-3” manufactured by Suzuhiro Chemical Co., Ltd.

  The obtained pellets were dried with a hot air dryer at 130 ° C. for 3 hours, and then molded and evaluated. The evaluation results are shown in Table 1.

  The molded article of the resin composition obtained in this example was excellent in initial antistatic property, antistatic property after treatment at 120 ° C. for 200 hours, and flame retardancy. On the other hand, the resin compositions obtained in Comparative Examples 1 to 7 were insufficient in any of these characteristics.

Claims (2)

  (B) block polyether amide produced from (A) polyester resin, (C) brominated polycarbonate compound and (D) antimony compound, (B-1) polyalkylene ether and (B-4) polyamide, (B -2) A sulfonic acid metal salt, (B-3) a composition containing a sterically hindered phenol compound, (A) 50-80% by weight of a polyester resin, (C) 10-20% by weight of a brominated polycarbonate compound , (D) 3 to 10% by weight of an antimony compound, containing a total of 5 to 15% by weight of (B-1), (B-2), (B-3) and (B-4), and (B- 1) When the total of (B-2), (B-3), and (B-4) is 100% by weight, (B-1) is 40 to 50% by weight, and (B-2) is 1 to 10% by weight. , (B-3) is 1 to 10% by weight, (B-4) The thermoplastic resin composition characterized in that it consists of 40 to 50 wt%.   (A) The thermoplastic resin composition according to claim 1, wherein the polyester resin is a polybutylene terephthalate resin.