CN101759982A - Antistatic and ultraviolet resistant PC/ASA material composition - Google Patents
Antistatic and ultraviolet resistant PC/ASA material composition Download PDFInfo
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Abstract
The invention discloses an antistatic and ultraviolet resistant PC/ASA material composition and belongs to the field of macromolecular composition materials. The composition is characterized by consisting of the following components in part by weight: 30 to 85 parts of polycarbonate, 5 to 30 parts of acrylonitrile-styrene-acrylic ester graft copolymer, 0 to 30 parts of acrylonitrile-styrene copolymer, 5 to 15 parts of macromolecular antistatic agent, 2 to 10 parts of compatilizer, 0.2 to 2 parts of light stabilizer and 0.2 to 1 part of antioxidant. The interior plastic parts of an automobile, which are made of the PC/ASA composition of the invention, have the advantages of high weather resistance, ultraviolet resistance and heat resistance, difficult adsorption of dust and the like, and can be used for manufacturing interior-exterior parts, such as automotive door plates and shells of inner-outer view mirrors, of various automobiles.
Description
Technical field
The present invention relates to a kind of polycarbonate (PC)/acrylonitrile-styrene-acrylic ester (ASA) composition, be specially a kind of antistatic, anti-ultraviolet PC/ASA material compositions, belong to the polymer composite field.
Background technology
Polycarbonate (PC) plastics have the thermotolerance height, and transparency is good, the gloss height, and advantages such as good toughness, but it is mobile poor, difficult forming; Goods are to the breach sensitivity, and not anti-solvent is easy to generate stress cracking.
Have and manyly knownly improve these shortcomings by the method for preparing the PC polyblend, wherein the PC/ABS polyblend is modal method, for example U.S. Pat 3130177, US 4624986 etc. have obtained high impact toughness and have improved mobile low-cost PC/ABS polyblend composition by the blending technology with ABS and PC.Yet the thermostability of polycarbonate and anti-ultraviolet radiation performance are often owing to the ABS graft rubber that adds is affected.
Acrylonitrile-styrene-acrylic ester (ASA) is a kind of physical and mechanical properties and the similar engineering plastics of ABS.The ASA plastics have good dimensional stability, the characteristics that the notch shock performance is high.Simultaneously, compare with ABS, ASA improve a lot at aspects such as the weathering resistance of material, ultraviolet resistances (improving 10 times approximately), therefore the ASA engineering plastics have very big application space, market in industries such as automobile, communication, electronics, can be used for making high performance automobile exterior spare, household electrical appliances outdoor parts, communication products, as automobile rearview mirror, air-conditioner outdoor unit, outdoor satellite antenna circuit housing etc.
Therefore, if PC and ASA resin are made intermingling material, then may obtain a kind of so excellent uvioresistant performance of anti-marquis that has, favorable shock resistance has the high and processing characteristics excellent material of heat resisting temperature simultaneously concurrently.
In modern industry production and daily life, plastics gather static and the sticking dust of inhaling easily, static hazard even may cause heavy losses and disaster when serious.In general, prevent that polymer surfaces from producing the electrostatic method and mainly containing air ionization method, metallic contact electric discharge, conducting material introductory technique, surface formation moisture absorption embrane method and use static inhibitor etc.
Use maximum antistatic modes at present and be to use static inhibitor.Static inhibitor is a kind of accumulation of electrostatic charge that can prevent to produce, or the chemical additive based on tensio-active agent of the static charge that can dissipate effectively.Because the chemicals-resistant corrosive nature of polycarbonate is poor, and processing temperature can be up to 300 ℃, and therefore, for polycarbonate and composition alloy plastic goods thereof, the mode of using static inhibitor generally is to adopt the method for surface-coated.
Simultaneously, the important goal that automotive trim is pursued is to reduce the volatility of material, improves the Air quality of automotive interior, and low smell material is one of common target of pursuing of automaker and automotive material manufacturers.Conflictingly therewith be, because normally used static inhibitor generally all is the organic molecule material, under the automobile indoor air quality requirements, small molecules organic volatile in the plastics is easy to move to the surface of plastics, and evaporate in the room air, cause bad sense of smell to the occupant.
Summary of the invention
The object of the invention provides a kind of antistatic, anti-ultraviolet PC/ASA material compositions, has both had the excellent uvioresistant performance of anti-marquis, has had a polycarbonate compositions of excellent antistatic energy and low volatility, low smell simultaneously.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of antistatic, anti-ultraviolet PC/ASA material compositions is made up of polycarbonate, acrylonitrile-styrene-acrylic ester graft copolymer, acrylonitritrile-styrene resin, polymer static inhibitor, compatilizer, photostabilizer and oxidation inhibitor; Described polycarbonate is 30～85 weight parts, the acrylonitrile-styrene-acrylic ester graft copolymer is 5～30 weight parts, acrylonitritrile-styrene resin is the 0-30 weight part, the polymer static inhibitor is 5～15 weight parts, compatilizer is 2～10 weight parts, photostabilizer is 0.2～2 weight part, and oxidation inhibitor is 0.2～1 weight part.
Described polycarbonate is the bisphenol A-type aromatic copolycarbonate.
In preferred embodiments, polycarbonate resin component of the present invention is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.
The weight-average molecular weight of polycarbonate resin of the present invention is 20000-40000g/mol, and polycarbonate resin of the present invention is known and can obtains by a plurality of commercial source.
Described acrylonitrile-styrene-acrylic ester graft copolymer acrylic elastomer content by weight percentage is 40-80%.
Described polymer static inhibitor is the one or more combination in polyether ester amides, polyetheramides and the polyether ester.
Described compatilizer is vinylbenzene N-phenylmaleimide-copolymer-maleic anhydride.
Described photostabilizer is the benzotriazole category light absorber.
Described antioxidant stabilizer is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant.
Described composition also can comprise tinting material, filler, thermo-stabilizer, lubricant etc.
The PC/ASA material compositions that technical scheme of the present invention is prepared from has good antistatic performance and low volatility, hangs down smell.Automobile plastic interior trim goods by polycarbonate compositions of the present invention is made have the uvioresistant performance of anti-marquis excellence, high-impact, are not easy the sticking advantage such as dust of inhaling, and can be used for making various inner and outer decorative parts of automobile, as automobile door plate, inside and outside the housing etc. of showing on trial.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.
Embodiments of the invention adopt following material:
Polycarbonate-1, U.S. Dow chemical company, weight-average molecular weight is about 27,000, trade mark Calibre 201-10;
Polycarbonate-2, U.S. Dow chemical company, weight-average molecular weight is about 32,000, trade mark Calibre 301-5
ASA-1: the acrylic elastomer percentage composition is about 45%, and Mitsubishi Li Yang company produces, W-450A;
ASA-2: the acrylic elastomer percentage composition is about 60%, and U.S. GE company produces, 960A;
ASA-3: the acrylic elastomer percentage composition is about 80%, and Japanese UMG company produces MUX-80;
SAN: its U.S. company of acrylonitritrile-styrene resin Taiwan produces PN-127H;
Vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride (SMI): NEC chemistry, MS-NA;
ABS, LG chemical company, trade mark HI-130;
Static inhibitor-1, the agent of polyether ester amides type polymer anti static, Japanese Sanyo company, Pelestat NC6321;
Static inhibitor-2, the agent of polyetheramides type polymer anti static, Arkema company, Pebax MV-1074;
Photostabilizer UV-5411: benzotriazole category light absorber, U.S. Cytec company;
Oxidation inhibitor, the mixture of hindered phenol antioxygen and phosphite ester kind antioxidant, Cytec company, Cyanox 2777.
Tinting material: pigment yellow 13 8, BASF AG produces, K0961HD.
The product performance testing method:
Tensile strength: press ISO 527 methods, draw speed 50 mm/min.
Bending property: press ISO 178 methods, trial speed 2 mm/min.
Notched Izod impact strength: press ISO 179 methods, IeA type notched specimen.
Vicat softening temperature: press ISO 306 methods, 50 ℃/hour of temperature rise rates are tested under 5 kilograms of load.
Surface resistivity: press IEC 60093 methods, adopt 80 millimeters of diameters, thick 3 millimeters sample.
The xenon lamp accelerated deterioration: by the PV1303 of Volkswagen method, irradiation time is 10 cycles, measures aberration Δ E value.
Embodiment 1-3 and comparative example 1:
After mixing by proportion of composing in the table 1, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, ASA, SAN, SMI, static inhibitor, auxiliary agent and tinting material etc.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.The said products is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result sees Table 1.
Table 1:
| Form | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| ??PC-1 | ??65 | ??30 | ??45 | ??65 | ??82 |
| ??ASA-2 | ??30 | ??15 | ??5 | ??5 | |
| ??SAN | ??30 | ??25 | ??5 | ||
| Static inhibitor-1 | ??15 | ??5 | ??10 | ??15 | ??10 |
| ??ABS | ??19 | ||||
| ??SMI | ??4 | ??4 | ??9 | ??2 | |
| ??UV-5411 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 |
| Oxidation inhibitor 2777 | ??0.4 | ??0.4 | ??0.4 | ??0.4 | ??0.4 |
| Tinting material | ??0.05 | ??0.05 | ??0.05 | ??0.05 | ??0.05 |
| Test result | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Form | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength (MPa) | ??55.1 | ??47.2 | ??52.6 | ??58.7 | ??62.1 |
| Modulus in flexure (MPa) | ??2170 | ??2310 | ??2380 | ??2210 | ??2320 |
| Notched Izod impact strength (kJ/m 2) | ??63.2 | ??24.8 | ??51.2 | ??56.1 | ??57.4 |
| Vicat softening temperature (℃) | ??122 | ??107 | ??111 | ??126 | ??135 |
| Surface resistivity (Ω) | ??1011 | ??1012 | ??1010 | ??1011 | ??1011 |
| The xenon lamp aging performance, Δ E | ??12.1 | ??1.95 | ??1.86 | ??1.89 | ??1.82 |
By table 1 as seen, antistatic, the anti-ultraviolet PC/ASA composition material surface resistivity by the present invention's preparation can reach 10
10～10
12(it is generally acknowledged that the surface resistivity of plastics is 10 between the Ω
12Has certain antistatic property when Ω is following); Simultaneously aberration Δ E≤2 behind the xenon lamp aging show that this alloy material has excellent anti-ultraviolet radiation performance, can meet the harshest uvioresistant requirement of the interior material PV1303 of Volkswagen illumination 10 all after date colour fastness 〉=4 grades.
Embodiment 4-8:
After mixing by proportion of composing in the table 2, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, ASA, SAN, SMI, static inhibitor, auxiliary agent and tinting material etc.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.The said products is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result sees Table 2.
Table 2:
| Form | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| ??PC-2 | ??50 | ??50 | ??50 | ??50 | ??50 |
| ??ASA-1 | ??20 | ??20 | ??20 | ||
| ??ASA-3 | ??15 | ??15 | |||
| ??SAN | ??18.8 | ??15 | ??15 | ??20 | ??18.5 |
| Static inhibitor-2 | ??10 | ??10 | ??10 | ??10 | ??10 |
| ??SMI | ??3.8 | ??3.8 | ??4 | ??4 |
| Form | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| ??UV-5411 | ??0.2 | ??0.2 | ??1 | ??0.6 | ??2 |
| Oxidation inhibitor 2777 | ??1 | ??1 | ??0.2 | ??0.4 | ??0.5 |
| Tinting material | ??0.05 | ??0.05 | ??0.05 | ??0.05 | ??0.05 |
| Test result | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Tensile strength (MPa) | ??54.1 | ??53.6 | ??53.8 | ??51.6 | ??51.2 |
| Modulus in flexure (MPa) | ??2380 | ??2370 | ??2340 | ??2250 | ??2210 |
| Notched Izod impact strength (kJ/m 2) | ??24.4 | ??41.3 | ??42.2 | ??63.4 | ??61.8 |
| Vicat softening temperature (℃) | ??113 | ??116 | ??115 | ??113 | ??112 |
| Surface resistivity (Ω) | ??1011 | ??1011 | ??1011 | ??1011 | ??1011 |
| The xenon lamp aging performance, Δ E | ??2.89 | ??2.91 | ??1.75 | ??1.87 | ??1.41 |
Can find out from the test result of last table comparative example and embodiment, the composition (comparative example 2) that PC, ASA and the agent of polyetheramides type polymer anti static are independent, its notched Izod impact strength is not high.And add weight percent in the composition of PC, ASA and the agent of polyetheramides type polymer anti static is the SMI resin (embodiment 1-8) of 2-10%, and notched Izod impact strength promptly is improved largely.The applicant thinks that the SMI resin has the effect of compatilizer in the composition of PC, ASA and the agent of polyetheramides type polymer anti static, is because SMI contains the result of the maleic acid anhydride group with reactive behavior.Thereby the maleic acid anhydride group can improve the interface binding power of polyetheramides polymer anti static agent and PC/ASA matrix with the end amido generation chemical reaction of polyetheramides polymkeric substance, it is more even that the agent of polyetheramides polymer anti static is disperseed in composition substrate, so notched Izod impact strength can increase substantially.
PC/ASA composition of the present invention has good antistatic property, the characteristics such as the excellent uvioresistant performance of anti-marquis and low volatility, low smell. By the automobile plastic interior trim goods that PC/ASA composition of the present invention is made, have the uvioresistant performance of anti-marquis excellent, high heat-resisting, be not easy the sticking advantage such as dust of inhaling, can be used for making various inner and outer decorative parts of automobile, as automobile door plate, inside and outside the housing etc. of showing on trial.
Claims (7)
1. antistatic a, anti-ultraviolet PC/ASA material compositions is characterized in that: be made up of polycarbonate, acrylonitrile-styrene-acrylic ester graft copolymer, acrylonitritrile-styrene resin, polymer static inhibitor, compatilizer, photostabilizer and oxidation inhibitor; Described polycarbonate is 30～85 weight parts, the acrylonitrile-styrene-acrylic ester graft copolymer is 5～30 weight parts, acrylonitritrile-styrene resin is the 0-30 weight part, the polymer static inhibitor is 5～15 weight parts, compatilizer is 2～10 weight parts, photostabilizer is 0.2～2 weight part, and oxidation inhibitor is 0.2～1 weight part.
2. a kind of antistatic, anti-ultraviolet PC/ASA material compositions according to claim 1, it is characterized in that: described compatilizer is vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride.
3. a kind of antistatic, anti-ultraviolet PC/ASA material compositions according to claim 1, it is characterized in that: the weight-average molecular weight of described polycarbonate is 20000-40000g/mol.
4. a kind of antistatic, anti-ultraviolet PC/ASA material compositions according to claim 1, it is characterized in that: described acrylonitrile-styrene-acrylic ester graft copolymer acrylic elastomer content by weight percentage is 40-80%.
5. a kind of antistatic, anti-ultraviolet PC/ASA material compositions according to claim 1, it is characterized in that: described polymer static inhibitor is the one or more combination in polyether ester amides, polyetheramides and the polyether ester.
6. a kind of antistatic, anti-ultraviolet PC/ASA material compositions according to claim 1, it is characterized in that: described light absorber is the benzotriazole category light absorber.
7. a kind of antistatic, anti-ultraviolet PC/ASA material compositions according to claim 1, it is characterized in that: described antioxidant stabilizer is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant.
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| CN107082981B (en) * | 2017-05-09 | 2019-08-27 | 台州博尔特塑胶电子有限公司 | A kind of antistatic cushion of persistence and preparation method thereof |
| CN111138823A (en) * | 2019-12-25 | 2020-05-12 | 江苏金发科技新材料有限公司 | Noise-reduction permanent antistatic polycarbonate styrene resin alloy and preparation method thereof |
| CN112251009A (en) * | 2020-10-20 | 2021-01-22 | 江苏金发科技新材料有限公司 | Low-gloss permanent antistatic polycarbonate/styrene resin alloy and preparation method thereof |
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Application publication date: 20100630 |