CN101760003A - Ultraviolet resistant nylon/acrylonitrile-styrene-acrylate resin co-mixed material - Google Patents
Ultraviolet resistant nylon/acrylonitrile-styrene-acrylate resin co-mixed material Download PDFInfo
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- CN101760003A CN101760003A CN200810203117A CN200810203117A CN101760003A CN 101760003 A CN101760003 A CN 101760003A CN 200810203117 A CN200810203117 A CN 200810203117A CN 200810203117 A CN200810203117 A CN 200810203117A CN 101760003 A CN101760003 A CN 101760003A
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- styrene
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- acrylic ester
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Abstract
The invention discloses an ultraviolet resistant nylon/acrylonitrile-styrene-acrylate resin co-mixed material. The co-mixed material comprises the following raw materials in part by weight: 35 to 85 percent of nylon resin, 10 to 30 parts of acrylonitrile-styrene-acrylate graft copolymer, 0 to 30 parts of acrylonitrile-styrene copolymer, 2 to 10 parts of maleic anhydride-grafted acrylonitrile-styrene-acrylate copolymer compatibilizer, 0.2 to 1 part of light absorber, 0.2 to 1 part of hindered amine light stabilizer and 0 to 1 part of antioxidant. The ultraviolet resistant nylon/acrylonitrile-styrene-acrylate resin co-mixed material adopting the technical scheme has the characteristics of high ultraviolet resistance, high fluidity and high heat resistant, chemical resistant and mechanical performance and can be used for manufacturing interior and exterior parts of automobiles and baffle plates of motorcycles.
Description
Technical field
The present invention relates to a kind of good uvioresistant performance that has, have nylon (PA)/acrylonitrile-styrene-acrylic ester terpolymer resin (ASA) intermingling material of higher-dimension card heat resisting temperature simultaneously.
Background technology
Nylon, it is polyamide resin, not only have excellent mechanical mechanics property and chemical reagent-resistant performance, but also have good self-lubricating property and processing characteristics, therefore be widely used in every field, as various trolley parts, power tool shell, ecommerce equipment component, sports goods or the like.Yet meanwhile, nylon also exists shortcomings such as notch shock poor performance, dimensional stability be not good, and therefore, this has limited its further application space again.In order to improve these shortcomings of nylon, people have done the improvement of a lot of aspects.As nylon and other various thermoplastic resins are formed intermingling material.These intermingling materials combine the common advantage of nylon and other blending resins usually, their original some shortcomings have been overcome simultaneously again, therefore, the intermingling material that adopts this method to obtain not only can overcome some defect problems of above-mentioned nylon, and the excellent specific property of nylon self can not be subjected to very big influence yet.Introduced a kind of vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride that adopts as CN101104732 and CN101265360 etc. and prepared the method for PA/ABS intermingling material as expanding material, Zhi Bei PA intermingling material has good shock resistance, thermotolerance and dimensional stability by this method.Yet, do not have further instruction for the uvioresistant performance of this material.
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 nylon and ASA resin are made intermingling material, then may obtain a kind of so excellent weather resisteant energy that has, favorable shock resistance and dimensional stability, chemical reagent-resistant performance excellent material simultaneously.Yet ASA resin and nylon are inconsistent substantially in theory, will obtain above-mentioned desirable material for this reason, must adopt the technology of increase-volume.
Summary of the invention
The purpose of this invention is to provide a kind of ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, it has excellent weather resisteant energy, good heat-resistant, chemical resistance and dimensional stability.
Purpose of the present invention can be achieved through the following technical solutions.
A kind of ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, it is formed and proportioning is: nylon resin 35-85 weight part; Acrylonitrile-styrene-acrylic ester graft copolymer 10-30 weight part; Acrylonitritrile-styrene resin 0-30 weight part; The acrylonitritrile-styrene resin expanding material 2-10 weight part of maleic anhydride graft; Light absorber 0.2-1 weight part; Hindered amine light stabilizer 0.2-1 weight part; Oxidation inhibitor 0-1 weight part.
Described acrylonitrile-styrene-acrylic ester graft copolymer acrylic elastomer unit content by weight percentage is 40-80%.
Described nylon is number-average molecular weight 15000-28000, and the relative viscosity index is at the nylon 6 of 2.0-4.0.
Described light absorber is the benzotriazole category light absorber.
Described photostabilizer is a hindered amine light stabilizer.
Described oxidation inhibitor is Hinered phenols antioxidant.
Adopt a kind of ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material of technique scheme, have the uvioresistant performance excellence, the characteristics of good fluidity; And good thermotolerance, chemical resistant properties and mechanical property are arranged, can be used for inner and outer decorative parts of automobile, and the making material of motorcycle plate washer etc.
Embodiment
The present invention is further illustrated below by specific embodiment, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.
The present invention is raw materials used:
Nylon 61 (PA6-1): relative viscosity 2.5, number-average molecular weight 15,000, Ube chemical industrial company;
Nylon 61 (PA6-2): relative viscosity 3.0, number-average molecular weight 24,000, German BASF AG product;
Nylon 62 (PA6-3): relative viscosity 3.6, number-average molecular weight 28,000, German BASF AG product.
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;
ABS-3: the acrylic elastomer percentage composition is about 80%, and Japanese UMG company produces MUX-80;
SAN: acrylonitritrile-styrene resin, its U.S. company of Taiwan produces PN-127H;
SAN-g-MAH: the acrylonitritrile-styrene resin of maleic anhydride graft, Japanese UMG company produces, S601N;
UV-5411: the benzotriazole category light absorber, U.S. Cytec company produces;
UV-770: hindered amine light stabilizer, Switzerland Ciba company produces;
Oxidation inhibitor 1098: Hinered phenols antioxidant, Switzerland Ciba company, Irganox 1098;
Tinting material: Cabot Co.,Ltd produces, carbon black DL-430.
The product performance testing method:
Tensile property is pressed ASTM D638 method, draw speed 50 mm/min.
Bending property is pressed ASTM D790 method, trial speed 2 mm/min.
Izod notched Izod impact strength: press ASTM D256 method, the sample of 3.2 mm thick.
Vicat softening temperature: press ASTM D1525 method, 50 ℃/minute of temperature rise rates are tested under 5 kilograms of load.
The xenon lamp accelerated deterioration: press SAE J1885 method, irradiation energy is 600kJ/m
2, measure aberration Δ E value.
Embodiment 1-4 and comparative example 1
Proportion of composing mixes back continuous twin screw extruder (the screw diameter 35mm that evenly adds of twin screw feeder in the table 1 pressing through exsiccant Nylon 62, ASA-1, SAN-g-MAH resin, auxiliary agent and tinting material, length-to-diameter ratio L/D=36) in the main barrel, it is 180 ℃, 200 ℃, 220 ℃, 240 ℃, 240 ℃, 245 ℃, 240 ℃ that main barrel divides ten sections controlled temperature (exporting from charging opening to head), 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, 240 ℃ of injection temperatures.The batten of injection formed is put into the glass moisture eliminator immediately and carry out performance test after room temperature is placed at least 24 hours.Test result sees Table 1.
The composition and the performance of table 1PA/ASA composition
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| ??PA6-1 | ??35 | ??55 | ??70 | ??82 | ??70 |
| ??ASA-2 | ??30 | ??25 | ??20 | ??10 | ??20 |
| ??SAN | ??30 | ??15 | ??5 | ??10 | |
| ??SAN-g-MAH | ??4 | ??4 | ??9 | ??2 | |
| ??UV-5411 | ??0.4 | ??0.4 | ??0.4 | ??0.4 | ??0.5 |
| ??UV-770 | ??0.4 | ??0.4 | ??0.4 | ??0.4 | ??0.5 |
| Oxidation inhibitor 1098 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.3 |
| Tinting material | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| Performance | |||||
| Tensile strength, MPa | ??45.5 | ??56.4 | ??62.6 | ??71.2 | ??61.3 |
| Modulus in flexure, MPa | ??2060 | ??2010 | ??2270 | ??2480 | ??2240 |
| The Izod notched Izod impact strength, J/m | ??208 | ??260 | ??276 | ??210 | ??128 |
| Vicat softening temperature, ℃ | ??102 | ??122 | ??148 | ??172 | ??151 |
| The xenon lamp aging performance, Δ E | ??1.04 | ??1.11 | ??1.38 | ??0.96 | ??1.08 |
Can find out from the test result of last table comparative example and embodiment, the Izod notched Izod impact strength of the composition (comparative example 1) that PA6 and ASA the are independent not high 2-3 of pure nylon resin (be approximately doubly), and add weight percent in the composition of PA6 and ASA is the SAN-g-MAH resin (embodiment 1-4) of 5-10%, and the Izod notched Izod impact strength promptly is improved largely.The applicant thinks that the SAN-g-MAH resin has a compatilizer in the PA6/ASA composition effect is because SAN-g-MAH contains the result of the maleic acid anhydride group with reactive behavior, thereby the maleic acid anhydride group can change the interface binding power of PA6 and ASA with the macromolecular end amido of PA6 generation chemical reaction, it is more even that ASA is disperseed in PA6, so the Izod notched Izod impact strength can increase substantially.In addition, can find out also that PA/ASA composition of the present invention has excellent uvioresistant performance (Δ E≤3 after the xenon lamp aging accelerated deterioration), and higher dimension card heat resisting temperature (〉=100 ℃) from table 1.
Embodiment 5-8 and comparative example 2
Employing is with complete processing and the testing method of embodiment 1-4, just use the nylon 6 of different molecular weight and the ASA resin of different rubber contents respectively, and different auxiliary agent content, having prepared the PA/ASA resin combination by the proportion of composing of table 2, performance test is as shown in table 2.
The composition and the performance of table 2PA/ASA composition
| Form | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| ??PA6-1 | ??65 | ??65 | ??65 | ||
| ??PA6-2 | ??65 | ||||
| ??PA6-3 | ??65 | ||||
| ??ASA-1 | ??25 | ??25 | |||
| ??ASA-2 | ??25 | ??25 | |||
| ??ASA-3 | ??25 | ||||
| ??SAN | ??5 | ??4 | ??4 | ??4 | ??4 |
| ??SAN-g-MAH | ??4.5 | ??4.5 | ??4.5 | ??4.5 | ??4.5 |
| ??UV-5411 | ??0.5 | ??0.2 | ??0.8 | ??1 | |
| ??UV-770 | ??1 | ??0.8 | ??0.2 | ??0.5 | |
| Oxidation inhibitor 1098 | ??0.5 | ??0.5 | ??0.5 | ||
| Tinting material | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| Performance | |||||
| Tensile strength, MPa | ??57.4 | ??59.7 | ??60.8 | ??58.7 | ??55.3 |
| Modulus in flexure, MPa | ??2210 | ??2400 | ??2380 | ??2200 | ??2040 |
| The Izod notched Izod impact strength, | ??280 | ??210 | ??278 | ??280 | ??320 |
| ??J/m |
| Form | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Vicat softening temperature, ℃ | ??136 | ??142 | ??145 | ??135 | ??132 |
| The xenon lamp aging performance, Δ E | ??4.05 | ??0.76 | ??0.68 | ??1.78 | ??1.05 |
Can find out from the test result of the foregoing description, use nylon 6 (P A6-1,2 of different molecular weight, 3) and the acrylic elastomer rubber content at the ASA of 45-80% resin (ASA-1,2,3), the PA/ASA intermingling material that adopts method of the present invention all to prepare to have high impact; Can find out that also the PA/ASA composition that adopts high molecular weight nylon 6 resins has higher I zod notched Izod impact strength (embodiment 5 and embodiment 6) than the composition that adopts the preparation of lower molecular weight Nylon 6.In addition, when using independent Hinered phenols antioxidant as stablizer, resulting PA/ASA composition uvioresistant performance relatively poor (Δ E sees comparative example 2 greater than 3 after the xenon lamp aging accelerated deterioration).
A kind of ultraviolet resistant nylon of the present invention/acrylonitrile-styrene-acrylic ester resin alloy material has the uvioresistant performance excellence, the characteristics of good fluidity; And good thermotolerance, chemical resistant properties and mechanical property are arranged, can be used for inner and outer decorative parts of automobile, and the making material of motorcycle plate washer etc.
Claims (6)
1. ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, its prescription by weight is: nylon resin 35-85 weight part; Acrylonitrile-styrene-acrylic ester graft copolymer 10-30 weight part; Acrylonitritrile-styrene resin 0-30 weight part; The acrylonitritrile-styrene resin expanding material 2-10 weight part of maleic anhydride graft; Light absorber 0.2-1 weight part; Hindered amine light stabilizer 0.2-1 weight part; Oxidation inhibitor 0-1 weight part.
2. ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, it is characterized in that: described acrylonitrile-styrene-acrylic ester graft copolymer acrylic elastomer unit content by weight percentage is 40-80%.
3. ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, it is characterized in that: described nylon is number-average molecular weight 15000-28000, the relative viscosity index is at the nylon 6 of 2.0-4.0.
4. ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, it is characterized in that: described light absorber is the benzotriazole category light absorber.
5. ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, it is characterized in that: described photostabilizer is a hindered amine light stabilizer.
6. ultraviolet resistant nylon/acrylonitrile-styrene-acrylic ester resin alloy material, it is characterized in that: described oxidation inhibitor is Hinered phenols antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200810203117A CN101760003A (en) | 2008-11-21 | 2008-11-21 | Ultraviolet resistant nylon/acrylonitrile-styrene-acrylate resin co-mixed material |
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|---|---|---|---|
| CN200810203117A CN101760003A (en) | 2008-11-21 | 2008-11-21 | Ultraviolet resistant nylon/acrylonitrile-styrene-acrylate resin co-mixed material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880459A (en) * | 2010-07-14 | 2010-11-10 | 广州市合诚化学有限公司 | Toughened nylon 66 for hair dryer shell and preparation method thereof |
| EP2719728A1 (en) | 2012-10-10 | 2014-04-16 | LANXESS Deutschland GmbH | Moulding material |
| CN107513268A (en) * | 2017-08-14 | 2017-12-26 | 上海长伟锦磁工程塑料有限公司 | A kind of high heat-resisting PA/ASA alloy materials |
-
2008
- 2008-11-21 CN CN200810203117A patent/CN101760003A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880459A (en) * | 2010-07-14 | 2010-11-10 | 广州市合诚化学有限公司 | Toughened nylon 66 for hair dryer shell and preparation method thereof |
| CN101880459B (en) * | 2010-07-14 | 2012-07-04 | 广州市合诚化学有限公司 | Toughened nylon 66 for hair dryer shell and preparation method thereof |
| EP2719728A1 (en) | 2012-10-10 | 2014-04-16 | LANXESS Deutschland GmbH | Moulding material |
| EP2719726A1 (en) * | 2012-10-10 | 2014-04-16 | LANXESS Deutschland GmbH | Moulding material |
| CN107513268A (en) * | 2017-08-14 | 2017-12-26 | 上海长伟锦磁工程塑料有限公司 | A kind of high heat-resisting PA/ASA alloy materials |
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Application publication date: 20100630 |