JP2013116932A - Thermoplastic resin composition, and molded article obtained by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of providing a molded article excellent in metal mold transferability and weather resistance.SOLUTION: The thermoplastic resin composition is prepared by blending (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, and (C) a polyorganosiloxane compound, wherein the blend amount of (A) the polybutylene terephthalate resin is 80 to 20 wt.%, and the blend amount of (B) the polyethylene terephthalate resin is 20 to 80 wt.%, in 100 wt.% of the total amount of (A) the polybutylene terephthalate resin and (B) the polyethylene terephthalate resin; and the blend amount of (C) the polyorganosiloxane compound is 0.1 to 5 pts.wt. to 100 pts.wt. of the total amount of (A) the polybutylene terephthalate resin and (B) the polyethylene terephthalate resin.

Description

  The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition excellent in appearance (mold transferability) and weather resistance.

  Thermoplastic polyester resins such as polybutylene terephthalate resin (hereinafter sometimes abbreviated as PBT) and polyethylene terephthalate resin (hereinafter sometimes abbreviated as PET) are mechanical properties, electrical properties, chemical resistance, Because of its excellent heat resistance, it is widely used as a material for manufacturing various electric and electronic equipment parts, interior and exterior parts for vehicles such as automobiles, trains, and trains, and other general industrial products. Furthermore, since the mold transferability is improved by blending these PBT and PET, they are also used for parts that require an appearance such as unpainted exterior parts, and the range of use is expanded.

  Examples of parts that require an excellent appearance include interior / exterior parts for vehicles such as automobiles, trains, and trains, and interior / exterior parts for aircrafts such as aircraft. Specific examples include indoor inner mirror stays, door handles, hanging leather, handle parts, wiper parts such as outdoor wiper arms, door handles, door mirror stays, roof rails, and the like.

  In addition, the above-mentioned interior and exterior parts for vehicles, electrical and electronic equipment parts are not easily faded by ultraviolet rays or rain, the gloss is not easily lowered, the inorganic reinforcing material does not appear on the surface, the appearance The weather resistance, such as being difficult to change, is required to last for a long period of time, and in recent years, the demand for such weather resistance has become more severe. Especially for parts using thermoplastic polyester resin, many excellent performances are maintained over a long period of time even when used outdoors exposed to strong sunlight, intense temperature changes, and severe wind and rain. There is a strong demand to do this.

  For this reason, methods for making up for the mutual defects have been proposed for applications such as interior and exterior parts for vehicles and aircraft that require both good appearance (good mold transferability) and weather resistance.

  For example, as a resin composition excellent in long-term durability against an alkaline solution, a thermoplastic polyester resin, an impact imparting agent, a silicone compound and / or a fluorine compound, an inorganic filler, and a polyfunctional compound are included. Resin compositions have been proposed (see, for example, Patent Document 1). Further, as a resin composition excellent in impact resistance and appearance of a molded product, a polyester resin composition composed of a thermoplastic polyester resin, a polyorganosiloxane graft copolymer and a silane compound has been proposed (for example, Patent Document 2). reference). However, the polyester resin compositions described in Patent Documents 1 and 2 have a problem that mold transferability is insufficient.

  On the other hand, a reinforced polyester resin composition containing a polyester resin, an acrylic resin, a graft copolymer, an inorganic filler, and a colorant is proposed as a resin composition from which a molded article having excellent mechanical strength, appearance, and weather resistance can be obtained. (For example, see Patent Document 3). In addition, as a resin composition for obtaining vehicle exterior mechanism parts with excellent mechanical properties, sliding properties, surface appearance, and weather resistance, thermoplastic resins mainly composed of thermoplastic polyester resin, fibrous reinforcement having irregular cross-sectional shape A resin composition for producing a vehicle exterior mechanism component containing an agent and a coloring component has been proposed. Although the molded product obtained from the resin composition described in Patent Documents 3 to 4 has high glossiness and excellent appearance such as mold transferability, there is a problem that weather resistance is insufficient.

International Publication No. 00/078867 Japanese Patent Laid-Open No. 4-198358 JP 2008-138132 A JP 2008-280409 A

  In a conventionally known resin composition, when PBT and PET are blended in order to improve the appearance (mold transferability) of the obtained molded product, the appearance of the molded product is improved. On the other hand, when exposed to ultraviolet rays or rain for a long time, fine cracks are partially generated on the surface of the molded product, and the polka dot pattern due to the contrast between the places where the cracks exist and the places where they do not exist significantly deteriorates the appearance. There was a problem that the property was insufficient. Then, this invention makes it a subject to provide the thermoplastic resin composition which can obtain the molded article excellent in metal mold | die transferability and a weather resistance.

In order to solve the above problems, the present invention has the following configuration.
(1) A thermoplastic resin composition comprising (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, and (C) a polyorganosiloxane compound, wherein (A) a polybutylene terephthalate resin and (B) In a total of 100% by weight of the polyethylene terephthalate resin, the blending amount of (A) polybutylene terephthalate resin is 80 to 20% by weight, (B) the blending amount of polyethylene terephthalate resin is 20 to 80% by weight, and (A) A thermoplastic resin composition in which the blending amount of the (C) polyorganosiloxane compound is 0.1 to 5 parts by weight with respect to a total of 100 parts by weight of the polybutylene terephthalate resin and (B) polyethylene terephthalate resin.
(2) The thermoplastic resin composition according to (1), wherein the (C) polyorganosiloxane compound contains silicone oil.
(3) The thermoplastic resin composition according to (2), wherein the viscosity of the silicone oil at 25 ° C. is 100 to 10,000 mm ² / s.
(4) The thermoplastic resin composition according to any one of (1) to (3), further comprising (D) a fibrous filler.
(5) The thermoplastic resin composition according to (4), wherein (D) the fibrous filler contains glass fibers.
(6) The thermoplastic resin composition according to any one of (1) to (5), further comprising (E) an elastomer.
(7) The thermoplastic resin composition according to (6), wherein (E) the elastomer contains an olefin-based elastomer having an epoxy group.
(8) (F) The thermoplastic resin composition according to any one of (1) to (7), further comprising a colorant.
(9) The thermoplastic resin composition according to (8), wherein the colorant contains carbon black.
(10) A molded product obtained by molding the thermoplastic resin composition according to any one of (1) to (9).
(11) A vehicle exterior part formed by molding the thermoplastic resin composition according to any one of (1) to (9).

  According to the thermoplastic resin composition of the present invention, a molded product having excellent mold transferability and weather resistance can be obtained.

It is a SEM photograph after processing the test piece which shape | molded the thermoplastic resin composition obtained in Example 30 with a sunshine weather meter for 720 hours. It is a SEM photograph after processing the test piece which shape | molded the thermoplastic resin composition obtained in the comparative example 5 with the sunshine weather meter for 720 hours.

  The thermoplastic resin composition of the present invention includes (A) polybutylene terephthalate resin (hereinafter sometimes abbreviated as (A) component), (B) polyethylene terephthalate resin (hereinafter abbreviated as (B) component). And (C) a polyorganosiloxane compound (hereinafter sometimes abbreviated as (C) component), and (A) component and (B) component in a total of 100% by weight, The blending amount of the component A) is 80 to 20% by weight, the blending amount of the component (B) is 20 to 80% by weight, and the total amount of the component (A) and the component (B) is 100 parts by weight. ) Component content is 0.1 to 5 parts by weight.

  A thermoplastic resin composition obtained by blending only one of (A) polybutylene terephthalate resin or (B) polyethylene terephthalate resin has insufficient mold transferability of the resulting molded product. (A) The polybutylene terephthalate resin has an action of lowering the glass transition temperature, and (B) the polyethylene terephthalate resin has an action of lowering the solidification rate in the mold, the thermoplastic resin composition of the present invention has (A A molded product excellent in mold transferability can be obtained by combining and blending polybutylene terephthalate resin and (B) polyethylene terephthalate resin.

  The (A) polybutylene terephthalate resin used in the present invention is a polyester obtained by polycondensation of terephthalic acid and / or a derivative thereof and 1,4-butanediol. Examples of the terephthalic acid derivative include alkyl esters such as methyl ester and ethyl ester of terephthalic acid.

  As long as the object of the present invention is not impaired, the terephthalic acid or its derivative may be copolymerized with another dicarboxylic acid or its derivative, or the other diol may be combined with 1,4-butanediol. It may be copolymerized.

  Examples of the dicarboxylic acid or derivative thereof used as a copolymerization component include isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, and alkyl esters thereof. Can be mentioned. Examples of the diol used as the copolymer component include ethylene glycol, trimethylene glycol, propylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

  In view of improving moldability, the (A) polybutylene terephthalate resin used in the present invention preferably has an intrinsic viscosity of 0.36 to 1.60 dl / g measured with o-chlorophenol, 0.52 More preferably, it is in the range of ˜1.35 dl / g.

  The compounding quantity of (A) component in the thermoplastic resin composition of this invention is 80-20 weight% in the total 100 weight% of (A) component and (B) component. When the blending amount of the component (A) exceeds 80% by weight, the solidification rate of the thermoplastic resin composition is increased and the mold transferability of the molded product is lowered. 75 weight% or less is preferable. Moreover, the glass transition temperature of a thermoplastic resin composition will rise that the compounding quantity of (A) component is less than 20 weight%, and the metal mold | die transferability of a molded article will fall. 25 weight% or more is preferable and 30 weight% or more is more preferable.

  The (B) polyethylene terephthalate resin used in the present invention is a polyester obtained by polycondensation of terephthalic acid and / or a derivative thereof and ethylene glycol. Examples of the terephthalic acid derivative include those exemplified as the terephthalic acid derivative constituting the component (A).

  As long as the object of the present invention is not impaired, it may be a copolymer of terephthalic acid or a derivative thereof with another dicarboxylic acid or a derivative thereof, or a copolymer of ethylene glycol or another diol. There may be. Examples of the dicarboxylic acid or derivative thereof used as the copolymer component include those exemplified as the copolymer component constituting the component (A). Examples of the diol used as the copolymerization component include trimethylene glycol, propylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

  The compounding quantity of (B) component in the thermoplastic resin composition of this invention is 20 to 80 weight% in the total 100 weight% of (A) component and (B) component. When the blending amount of component (B) is less than 20% by weight, the solidification rate of the thermoplastic resin composition is increased, and the mold transferability of the molded product is lowered. 25 weight% or more is preferable. Moreover, when the compounding quantity of (B) component exceeds 80 weight%, the glass transition temperature of a thermoplastic resin composition will rise, and the metal mold | die transferability of a molded article will fall. 75 weight% or less is preferable and 70 weight% or less is more preferable.

  The (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin used in the present invention can be produced by a known polycondensation method or ring-opening polymerization method. Either a batch polymerization method or a continuous polymerization method may be applied, but a continuous polymerization method is preferred. In addition, either a transesterification reaction or a direct polymerization reaction may be applied, but a direct polymerization reaction is preferable. In order to advance the esterification reaction, transesterification reaction and / or polycondensation reaction efficiently, it is preferable to add a catalyst during the reaction. Examples of the catalyst include organic titanium compounds and tin compounds, and tetra-n-butyl ester of titanic acid is preferably used.

  As described above, by combining the component (A) and the component (B), the mold transferability of the molded product obtained by the glass transition temperature reduction effect of the component (A) and the solidification rate delay effect of the component (B) is improves. On the other hand, when the molded product obtained from the thermoplastic resin composition comprising the component (A) and the component (B) is exposed to ultraviolet rays or rain for a long time, fine cracks are generated on the surface of the molded product, It has been found that a polka dot pattern is generated due to the contrast between a location where a crack exists and a location where a crack does not exist, resulting in a new problem of deteriorating the appearance, that is, reducing the weather resistance. The thermoplastic resin composition of the present invention further suppresses an appearance defect due to a polka dot pattern when exposed to ultraviolet rays or rain for a long period of time by blending (C) a polyorganosiloxane compound. It is possible to dramatically improve the weather resistance.

  The polyorganosiloxane compound (C) used in the present invention is preferably a polyorganosiloxane composed of at least one siloxane unit selected from the group consisting of units represented by the following general formulas (1) to (4). In the following general formulas (1) to (4), R may be the same or different and each represents a saturated or unsaturated monovalent hydrocarbon, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl group or an allyl group. . Two or more of these may be blended.

Among these polyorganosiloxane compounds, silicone oil is preferable and dimethyl silicone oil is more preferable from the viewpoint of further improving the weather resistance of the molded product. The dimethyl silicone oil preferably has a viscosity of 100 to 10,000 mm ² / s at 25 ° C. measured according to JISZ8803 (2011). When the viscosity is 100 mm ² / s or more, gas generation during injection molding can be suppressed, and the mold transferability of the molded product can be further improved. 200 mm < ² > / s or more is more preferable. On the other hand, when the viscosity is 10,000 mm ² / s or less, the weather resistance of the molded product can be further improved. 1000 mm ² / s or less is more preferable.

Examples of the dimethyl silicone oil whose viscosity at 25 ° C. measured according to JIS Z8803 is 100 to 10,000 mm ² / s are SH200-200cs (manufactured by Toray Dow Corning), SH200-300cs (manufactured by Toray Dow Corning), SH200-500cs (made by Toray Dow Corning), SH200-1000cs (made by Toray Dow Corning) etc. are marketed.

  In the thermoplastic resin composition of the present invention, the amount of the component (C) is 0.1 to 5 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). When the blending amount of component (C) is less than 0.1 parts by weight, appearance defects due to a polka dot pattern occur in the molded product when exposed to ultraviolet rays or rain for a long period of time, resulting in insufficient weather resistance. 0.3 parts by weight or more is preferable. On the other hand, if the amount of component (C) exceeds 5 parts by weight, the amount of gas generated at the time of injection molding increases, and the mold transferability of the molded product decreases. From the viewpoint of reducing the amount of gas generated during injection molding, it is preferably 3 parts by weight or less.

  The thermoplastic resin composition of the present invention preferably further contains (D) a fibrous filler (hereinafter sometimes abbreviated as (D) component), and improves the mechanical strength of the molded product. Can do. Examples of the component (D) include glass fiber, wollastonite, potassium titanate whisker, zinc oxide whisker, carbon fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, and metal fiber. Glass fiber is preferred. Two or more of these may be blended. These fibrous fillers are preferably pretreated with a coupling agent such as silane, epoxy, or titanate, and can further improve the mechanical strength of the molded product.

  As the glass fiber subjected to such pretreatment, for example, CSF3PE941H (manufactured by Nittobo), ECS03T120H (manufactured by Nippon Electric Glass), ECS03T747H (manufactured by Nippon Electric Glass), etc. are commercially available.

  In the thermoplastic resin composition of the present invention, the blending amount of the component (D) is 10 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of improving the mechanical strength of the molded product. The above is preferable, and 15 parts by weight or more is more preferable. On the other hand, from the viewpoint of maintaining the mold transferability of the molded product at a higher level, it is preferably 100 parts by weight or less, more preferably 70 parts by weight or less with respect to 100 parts by weight of the total of the component (A) and the component (B).

  The thermoplastic resin composition of the present invention preferably further contains (E) elastomer (hereinafter sometimes abbreviated as (E) component), and can further improve the mechanical strength of the molded product. . Examples of the component (E) include an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, and an ethylene / propylene / conjugated diene copolymer. Polymer, ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) butyl acrylate copolymer, ethylene / ethyl acrylate-g-methyl methacrylate / Butyl acrylate copolymer, ethylene / ethyl acrylate-g-methyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer, ethylene / methyl methacrylate-g-maleic anhydride copolymer Polymer, ethylene / ethyl acrylate-g-maleimide copolymer, ethylene / propylene-g-maleic anhydride Acid copolymers, ethylene / butene -1-g- maleic anhydride copolymer, and the like. Two or more of these may be blended.

  Among these, an olefin elastomer having an epoxy group is preferable. Examples of the olefin elastomer having an epoxy group include ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer, and ethylene / acrylic. Examples thereof include butyl acrylate / glycidyl methacrylate copolymer and ethylene / vinyl acetate / glycidyl methacrylate copolymer.

  As the olefin elastomer having an epoxy group, for example, BF-7M (manufactured by Sumitomo Chemical Co., Ltd.), Rotader AX8900 (manufactured by Arkema Japan), Rotader AX8840 (manufactured by Arkema Japan) and the like are commercially available.

  In the thermoplastic resin composition of the present invention, the blending amount of the component (E) is 1 part by weight with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of improving the impact strength of the molded product. The above is preferable, and 3 parts by weight or more is more preferable. On the other hand, from the viewpoint of maintaining a higher level of mold transferability of the molded product, it is preferably 15 parts by weight or less and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the component (A) and the component (B).

  The thermoplastic resin composition of the present invention preferably further contains (F) a colorant (hereinafter sometimes abbreviated as (F) component), which makes the appearance of the molded product beautiful and weather resistant. It functions to improve the sex. Examples of the component (F) include inorganic pigments, organic pigments, and organic dyes. Two or more of these may be blended. From the viewpoint of further improving the weather resistance of the molded article, a colorant mainly composed of an inorganic pigment is preferable. Further, a dispersing agent for assisting the dispersion of these colorants can be blended.

  Examples of the inorganic pigment include carbon black, metal powder, metal oxide or hydroxide, sulfide, silicate, carbonate, chromate, and metal powder. Examples of the metal oxide include zinc white, titanium oxide, antimony white, iron black, red rose, red lead, chromium oxide, nickel titanium yellow, chromium titanium yellow, and swinel green. Examples of the metal hydroxide include alumina white, satin white, and yellow iron oxide. Examples of the metal sulfide include zinc sulfide, lithopone, male yellow, silver vermilion, cadmium red, cadmium orange, cadmium yellow, antimony vermilion, barium sulfate, gypsum, and lead sulfate. Examples of the metal silicate include ultramarine blue. Examples of the metal carbonate include barium carbonate, lime carbonate powder, lead white, and magnesium carbonate. Examples of the metal chromate include chrome lead, zinc yellow, and barium chromate. Examples of the metal powder include metal powder pigments such as aluminum powder, bronze powder, and copper powder.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green, azo dyes such as nickel azo yellow, thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone, anthraquinone, heterocyclic, and methyl dyes.

  Among these, carbon black is particularly preferable because it has a high effect of improving weather resistance. The carbon black may be any one produced by a furnace method, a channel method, or an acetylene method. Examples of carbon black include “Mitsubishi Carbon Black” # 650 (manufactured by Mitsubishi Chemical Corporation), “Mitsubishi Carbon Black” # 850 (manufactured by Mitsubishi Chemical Corporation), “Toka Black” # 8500 (manufactured by Tokai Carbon Co., Ltd.), “Toka Carbon” Black "# 7360SB (manufactured by Tokai Carbon Co., Ltd.) is commercially available.

  In the thermoplastic resin composition of the present invention, the content of the component (F) depends on the type, but from the viewpoint of further improving the weather resistance of the molded product, a total of 100 components (A) and (B) 0.1 parts by weight or more is preferable with respect to parts by weight, and 0.5 parts by weight or more is more preferable. On the other hand, from the viewpoint of further improving the mold transferability of the molded product, the amount is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, with respect to 100 parts by weight of the total of the component (A) and the component (B). Furthermore, from the viewpoint of improving the mechanical strength of the molded product, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.

  The thermoplastic resin composition of the present invention includes various kinds of crystal nucleating agents, plasticizers, ultraviolet absorbers, antibacterial agents, stabilizers, mold release agents, lubricants, antistatic agents and the like as long as the effects of the present invention are not impaired. Additives can be blended.

  Although the manufacturing method of the resin composition of this invention is not specifically limited as long as the requirements prescribed | regulated by this invention are satisfy | filled, For example, (A) component, (B) component, and (C) component, as needed A method of melting and kneading the component (D), the component (E), the component (F) and other components, a method of removing the solvent after mixing in a solution, and the like are preferably used. From the viewpoint of productivity, a melt kneading method is preferred. Examples of the melt-kneading include a single-screw or twin-screw extruder. In view of obtaining a thermoplastic resin composition having excellent fluidity and mechanical properties of a molded product, a method of uniformly melt-kneading with a twin-screw extruder is more preferable. Among them, a method of melt kneading using a twin screw extruder where L / D> 30 when the screw length is L and the screw diameter is D is particularly preferable. The L / D of the twin screw extruder is preferably more than 30 and 100 or less.

  Moreover, as a screw structure of a twin-screw extruder, the structure which combined the full flight and the kneading disk is preferable. From the viewpoint of efficiently performing uniform kneading with a screw, the ratio of the total length of the kneading disk (kneading zone) to the total length of the screw is preferably 10 to 40%.

  Moreover, when melt-kneading using a twin-screw extruder, (A) component, (B) component and (C) component, (D) component, (E) component, (F) component and others as needed The components may be supplied to the twin screw extruder at the same time, or by using an extruder having a plurality of input ports, the (A) component and the (B) component from the main input port installed on the screw root side, if necessary (E ) Component, (F) component and other components may be supplied, and the component (C) and, if necessary, the component (D) may be supplied from a sub-inlet installed between the main inlet and the tip of the extruder. In addition, (A) component, (B) component and (C) component, and (E) component, (F) component and other components are supplied from the main input port installed on the screw root side, and the main input port and extrusion If necessary, component (D) may be supplied from a sub-inlet installed between the machine tips.

  Next, the molded product of the present invention will be described. Various molded products can be obtained by molding the thermoplastic resin composition of the present invention by an arbitrary method such as generally known injection molding, extrusion molding, blow molding or press molding. Examples of the molded product include injection molded products, extrusion molded products, blow molded products, and press molded products. These various molded articles can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, daily life goods and sanitary goods.

  Specific uses of the molded article of the present invention include, for example, wiper parts, torque control levers, safety belt parts, register blades, washer levers, window regulator handles, window regulator handle knobs, passing light levers, sun visor brackets, Vehicle interior parts such as various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, door handles and other vehicle exterior parts, wire harness connectors, SMJ connectors , PCB connectors, door grommets connectors and other vehicle connectors, electrical connectors, relay cases, coil bobbins, optical pickups Chassis, motor case, laptop housing and internal parts, CRT display housing and internal parts, printer housing and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers and handheld mobiles, recording media (CD, DVD) , PD, FDD, etc.) Drive housing and internal parts, copier housing and internal parts, facsimile housing and internal parts, parabolic antenna, electronic musical instrument, home game machine, portable game machine housing and internal parts, Various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, metamorphosis , Plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, transformer members, coil bobbins, etc. VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, video equipment parts such as video cameras, projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs, CDs -R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Household / office electrical product parts, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, heat insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs Building materials such as doors and floors, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other fishery related parts, vegetation nets, vegetation mats, grass protection bags, grass protection nets, curing sheets, slope protection sheets, fly ash Presser sheet, drain sheet, water retention sheet, sludge / sludge dewatering bag, concrete-related members such as concrete formwork, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, fans, Mechanical parts such as Tegs, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches, etc. Multi-film, tunnel film, bird-proof sheet, vegetation protection nonwoven, seedling pot, vegetation pile, seed string tape, germination sheet, house lining sheet, farm-bi stopper, slow-release fertilizer, root-proof sheet, Horticulture net, insect net, young tree net, print laminate, fertilizer bag, sample bag, sandbag, animal damage prevention net, inducement string, windbreak net and other agricultural materials, tubes, plastic cans, pouches, containers, tanks, baskets, etc. Container, golf tee, stationery, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, kitchen cabinet, pen cap, and the like. Among these various uses, the molded product of the present invention makes use of the excellent mold transferability and weather resistance, and wiper parts such as door handles and wiper arms, vehicle exterior parts such as door mirror stays and roof rails, especially unpainted. It is particularly preferably used for vehicle exterior parts.

  Next, the present invention will be described in more detail by way of examples. The present invention can be implemented by modifying the embodiments.

Abbreviations and main contents of main raw materials used in Examples and the like are summarized below.
(A) Polybutylene terephthalate resin A-1: Polybutylene terephthalate “Toraycon” (registered trademark) 1200M manufactured by Toray Industries, Inc. Inherent viscosity 0.97 dl / g.
(B) Polyethylene terephthalate resin B-1: T-900E manufactured by Toray Industries, Inc.
(C) Polyorganosiloxane compound C-1: SH200 C FLUID 300 cs (dimethyl silicone oil, viscosity 300 mm ² / s measured at 25 ° C. according to JIS Z8803) manufactured by Toray Dow Corning Co., Ltd.
C-2: SH200 C FLUID 10 cs manufactured by Toray Dow Corning Co., Ltd. (dimethyl silicone oil, viscosity 10 mm ² / s at 25 ° C. measured according to JISZ8803)
C-3: Toray Dow Corning Co., Ltd. SH200 C FLUID 30000 cs (dimethyl silicone oil, viscosity 30000 mm ² / s at 25 ° C. measured according to JISZ8803: 2011)
(D) Fibrous filler D-1: Nippon Electric Glass Co., Ltd. ECS 03 T-120H (glass fiber)
(E) Elastomer E-1: Arkema Japan Co., Ltd. Rotader AX8840 (olefinic elastomer having an epoxy group)
(F) Colorant F-1: “Mitsubishi Carbon Black” # 650 (carbon black) manufactured by Mitsubishi Chemical Corporation

  Characteristic evaluation in each example and comparative example was performed by the following method.

(1) Mold transferability (= glossiness)
After drying the pellets of the thermoplastic resin compositions obtained in each Example and Comparative Example for 3 hours or more with a hot air dryer at 130 ° C., the cylinder temperature was 260 ° C. using an injection molding machine SE75DU manufactured by Sumitomo Heavy Industries, Ltd. Injection molding was performed at a mold temperature of 80 ° C. to produce a 60 mm square square and a 3.0 mm thick test piece. About the obtained test piece, glossiness was measured with the digital variable angle gloss meter UGV-5D by Suga Test Instruments Co., Ltd. Those having a glossiness of 90 or more were judged to have good mold transferability. However, since the glossiness tends to decrease when the fibrous filler is blended, when the fibrous filler is blended, those having a glossiness of 70 or more were determined to have good mold transferability.

(2) Weather resistance The test piece prepared in the same manner as in (1) above was treated for 120 hours, 480 hours and 720 hours according to the JIS A1415 (1999) WV-A exposure method using a sunshine weather meter. Went. Gold and palladium vapor deposition (deposition thickness = 8-12 nm) is performed on the test piece after the treatment, and the surface state is observed using a scanning electron microscope (SEM) under the conditions of acceleration voltage = 20 kV and magnification = 500 times. The presence or absence of a polka dot pattern was determined visually.
○: No polka dots ×: Polka dots

(3) Tensile strength After the pellets of the thermoplastic resin compositions obtained in each of the examples and comparative examples were dried for 3 hours or more in a 130 ° C hot air dryer, the cylinder temperature was 260 ° C and the mold temperature was 80 ° C. The tensile strength of the injection-molded dumbbell test piece was evaluated according to ISO527-1,2.

(4) Impact strength After drying the pellets of the thermoplastic resin compositions obtained in each Example and Comparative Example for 3 hours or more with a hot air dryer at 130 ° C., a test piece (80 mm × 80 mm) prepared according to ISO 179-1: 2000 10 mm × 4.0 mm), notches were left so that 8 mm remained, and the impact strength was measured.

(5) Loss on heating The thermoplastic resin composition pellets obtained in each of the examples and comparative examples were pre-dried in an atmosphere at 130 ° C. for 3 hours, and then weighed 10 g in an aluminum cup. Thereafter, the pellet weight was measured again after heat treatment in an atmosphere of 260 ° C. for 1 hour, and the weight loss before and after the heat treatment was calculated by dividing the weight loss before and after the heat treatment by the weight of the pellet. The smaller the loss on heating, the better the low gas properties.

[Examples 1 to 30]
In accordance with the composition shown in Tables 1 to 3, the components (A), (B), and (C) are supplied from the main inlet of a twin screw extruder TEX44α manufactured by Nippon Steel Works with a cylinder diameter of 47 mmφ set at a cylinder temperature of 260 ° C. The component (E) and the component (F) were supplied as necessary, and the component (D) was supplied as needed from a sub-inlet installed between the main inlet and the tip of the extruder, and melt kneading was performed. The strand discharged from the die was cooled in a cooling bath and then pelletized with a strand cutter to obtain a thermoplastic resin composition pellet. About the obtained thermoplastic resin composition, the result evaluated by the said method was described in Tables 1-3. All of the obtained thermoplastic resin compositions were excellent in mold transferability and weather resistance of molded products.

  The SEM photograph after processing the test piece which shape | molded the thermoplastic resin composition obtained in Example 30 with the sunshine weather meter for 720 hours is shown in FIG.

[Comparative Examples 1-5]
Except having changed into the compounding composition shown in Table 4, the pellet of the thermoplastic resin composition was obtained like Example 1-29. The results of evaluating the obtained thermoplastic resin composition by the above method are shown in Table 4. In either case, either mold transferability or weather resistance of the molded product was inferior.

  The SEM photograph after processing the test piece which shape | molded the thermoplastic resin composition obtained in the comparative example 5 with the sunshine weather meter for 720 hours is shown in FIG. A polka dot pattern with a contrast between a portion where a crack exists and a portion where a crack does not exist was recognized in a portion surrounded by an elliptical broken line.

Claims (11)

A thermoplastic resin composition comprising (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, and (C) a polyorganosiloxane compound, wherein (A) a polybutylene terephthalate resin and (B) a polyethylene terephthalate resin The blending amount of (A) polybutylene terephthalate resin is 80 to 20% by weight, (B) the blending amount of polyethylene terephthalate resin is 20 to 80% by weight, and (A) polybutylene terephthalate. The thermoplastic resin composition whose compounding quantity of (C) polyorganosiloxane compound is 0.1-5 weight part with respect to a total of 100 weight part of resin and (B) polyethylene terephthalate resin. (C) The thermoplastic resin composition according to claim 1, wherein the polyorganosiloxane compound contains silicone oil. The thermoplastic resin composition according to claim ^{2, wherein the} silicone oil has a viscosity at 25 ° C. of 100 to 10,000 mm ² / s. (D) The thermoplastic resin composition according to any one of claims 1 to 3, further comprising a fibrous filler. (D) The thermoplastic resin composition according to claim 4, wherein the fibrous filler contains glass fibers. (E) The thermoplastic resin composition according to any one of claims 1 to 5, further comprising an elastomer. (E) The thermoplastic resin composition of Claim 6 in which an elastomer contains the olefin type elastomer which has an epoxy group. (F) The thermoplastic resin composition according to any one of claims 1 to 7, further comprising a colorant. (F) The thermoplastic resin composition according to claim 8, wherein the colorant contains carbon black. A molded product formed by molding the thermoplastic resin composition according to claim 1. The vehicle exterior component formed by shape | molding the thermoplastic resin composition in any one of Claims 1-9.

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