CN102775720A - High-impact and high-heat-resistance ABS alloy and its preparation technology - Google Patents
High-impact and high-heat-resistance ABS alloy and its preparation technology Download PDFInfo
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- CN102775720A CN102775720A CN2011101225865A CN201110122586A CN102775720A CN 102775720 A CN102775720 A CN 102775720A CN 2011101225865 A CN2011101225865 A CN 2011101225865A CN 201110122586 A CN201110122586 A CN 201110122586A CN 102775720 A CN102775720 A CN 102775720A
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- 239000000956 alloy Substances 0.000 title claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 29
- 238000005516 engineering process Methods 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 48
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 17
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 12
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 pentaerythritol ester Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229940095674 pellet product Drugs 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- KTHUKEZOIFYPEH-UHFFFAOYSA-N 1-benzylnaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1CC1=CC=CC=C1 KTHUKEZOIFYPEH-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 2
- RHFRJECSRHFHMO-UHFFFAOYSA-N formaldehyde methanesulfonic acid Chemical compound O=C.CS(O)(=O)=O RHFRJECSRHFHMO-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract description 30
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 30
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 230000035939 shock Effects 0.000 description 7
- 229920006827 ABS/PMMA Polymers 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920006942 ABS/PC Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
An alloy of the invention treats ABS (an acrylonitrile-butadiene-styrene copolymer) and PMMA (polymethyl methacrylate) as main raw materials, and is prepared through adding proper amounts of a compatilizer, a lubricant, a dispersant and an antioxidant, wherein the alloy comprises 60-90 parts of the ABS and 10-40 parts of the PMMA. The raw materials are weighed according to above proportions, and are blended and extruded by a double screw extruder. The novel compatilizer having a typical core-shell structure is introduced to the high-impact and high-heat-resistance ABS alloy in the invention, so the compatibility of the ABS and the PMMA is improved, and the impact performance and the heat resistance of the alloy are substantially improved, thereby the alloy can be widely applied to car fields of car meter panels, comprehensive covers, grates and the like, and household electrical appliances comprising electric water heater elements, heating household electrical appliance (hair dryer) housings and the like. Products of this kind can be produced through only suing heat and impact resistant resins which cannot be substituted by common ABS resins.
Description
Technical field
The invention discloses a kind of HI high impact, high heat-proof ABS alloy and preparation technology thereof.Relate to a kind of heat resistant type of automobile and household electric appliances, the ABS alloy and preparation technology thereof of heat shock resistance type of being applied to specifically.
Technical background
Acrylonitrile-butadiene-styrene copolymer (ABS) has excellent characteristics such as H.T., high rigidity, hardness and processing fluidity; But its thermotolerance is not high; Heat-drawn wire has only 86 ℃; Can not satisfy many application scenario needs ABS and have certain stable on heating requirement, like fascia, grid etc., it is to produce with heat-resisting, high impact resins that a considerable amount of component are also arranged aspect household electrical appliances.
The approach that obtains heat-resisting ABS resin has a lot: (1) chemical modification, but that its shortcoming is a research potential is little, heat resisting temperature improves seldom, and it is bigger to put into practice difficulty; (2) add mineral filler (glass, inorganic particle etc.), but its shortcoming is impact property decline and causes surface gloss to descend; (3) add heat-proof modifier (N-PMI etc.), but that its shortcoming is a price is higher, and must seeks appropriate compatilizer and could well play a role; (4) blend heat stable resin modification (ABS/PC, ABS/SMA etc.) is that cost improves like the shortcoming of ABS/PC, mobile decline, and the shortcoming of ABS/SMA is that cost improves, impact property descends.
To sum up can know, adopt the heat-proof ABS of above method of modifying preparation can not satisfy requirement shock-resistant, that outward appearance good and cost is low simultaneously.So, be badly in need of a kind of HI high impact of exploitation, good appearance, cost performance height and the simple heat-proof ABS of technology controlling and process on the market.
Summary of the invention
The present invention is that heat-proof ABS is ubiquitous in the market can not satisfy problems such as requirement shock-resistant, that outward appearance good and cost is low simultaneously in order to solve, and has proposed a kind of HI high impact, good appearance and cost performance high heat-proof ABS alloy and preparation technology thereof.Technical scheme of the present invention is: ABS, 60～90 parts; PMMA, 10～30 parts; Compatilizer, 0～10 part; Lubricant, 0.5～1 part; Oxidation inhibitor, 0.5～1 part; Dispersion agent, 0.5～1 part.Described ABS resin is an acrylonitrile-styrene-acrylic ester copolymer, rubber content >=30%, heat-drawn wire >=90 ℃.Described PMMA resin is a polymethylmethacrylate, melt flow rate(MFR) (MFR) between 1.2～2.0g/10min (240 ℃, 5Kg).
Described compatilizer is MBS (MBS), SMA resin (styrene-maleic anhydride copolymer) or ABS-g-MAH (maleic anhydride grafted ABS); Described lubricant is EBS (vinyl bis-stearamides), silicone oil or Cast (calcium stearate); Described oxidation inhibitor is four [methyl-β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic ester] pentaerythritol ester, the β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid or three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester; Described dispersion agent is methylsulphonic acid formaldehyde condensation products (MF) or benzyl naphthalene sulfonic formaldehyde condensation compound (CNF).
The preparation technology of HI high impact of the present invention, high heat-proof ABS alloy is following:
Adopt " second order blending method " batch mixing; At first ABS resin, PMMA resin, lubricant are mixed by the proportioning weighing; Add compatilizer and other processing aid then and carry out the secondary mixing; Mix the back discharging and join in the twin screw extruder, mixing, extrude, cooling, pelletizing, the cylindrical pellet product.Barrel temperature: 180～200 ℃ of back segments, 190～215 ℃ in stage casing, 200～230 ℃ of leading portions, screw slenderness ratio 35～40, screw speed 300～450r/min.
The present invention adopts ABS and PMMA to carry out blend; Improve the thermotolerance of ABS; Be compatilizer with MBS (MBS) simultaneously, MBS has typical nucleocapsid structure, has not only improved the consistency of ABS and PMMA; Improve the shock strength of ABS/PMMA alloy, also improved the thermotolerance of ABS/PMMA alloy.Than the ABS/PMMA/SMA alloy, the impact property of ABS/PMMA/MBS alloy and thermotolerance are all high, and this is because SMA (styrene-maleic anhydride copolymer) is flexible little, and its introducing can make the notched Izod impact strength of alloy reduce.Can make superior heat resistance and have both good mechanical property and the high heat-proof ABS of cost performance simultaneously so in ABS, introduce PMMA and MBS simultaneously, this is a kind of more promising heat-proof ABS alloy.
Embodiment:
To further explain of the present invention, but the present invention is not limited to each example of following enforcement below in conjunction with specific embodiment:
This embodiment is doubly grand twin screw extruder of use section and sea day injection moulding machine all; Main raw material is mainly the import material, and ABS originates in Jilin Chemical Industry Company, and PMMA and MBS originate in U.S. Rhom and Hass.Oxidation inhibitor, dispersion agent all originate in the refined treasured in Nanjing.
The preparation technology of HI high impact of the present invention, high heat-proof ABS alloy is following:
Adopt " second order blending method " batch mixing; At first ABS resin, PMMA resin, lubricant are mixed by the proportioning weighing; Add compatilizer then and carry out the secondary mixing with other processing aid; Mix the back discharging and join in the twin screw extruder, mixing, extrude, cooling, pelletizing, the cylindrical pellet product.Barrel temperature: 180～200 ℃ of back segments, 190～215 ℃ in stage casing, 200～230 ℃ of leading portions, screw slenderness ratio 35～40, screw speed 300～450r/min.
The ABS alloy material of gained in the various embodiments of the present invention is injection molded into test bars by following injecting condition, injecting condition: injection temperature 210-240 ℃, and injection pressure 30-50MPa, injection speed: 30-60mm/s.
Each embodiment physicals is all tested by DIN and China's national standard, and concrete examination criteria is following:
Simple beam impact strength: ISO 179 standards
Tensile strength: ISO 527 standards
Flexural strength: ISO 178 standards
Ball-indentation hardness: ISO 2039 standards
Melt flow rate(MFR): ISO 1133 standards (240 ℃, 5Kg)
Heat-drawn wire: GB/T-1634-2004 standard
The corresponding prescription of each embodiment of table 1
Each embodiment sample corresponding physical performance of table 2
Can find out that from table 2 along with the adding of MBS, the shock strength and the heat-drawn wire of alloy material all significantly improve, when the amount of MBS be increased to a certain amount of after, the shock strength of alloy material and heat-drawn wire change little, other performances do not have considerable change yet.Though the adding of SMA has improved the thermotolerance of alloy, its shock strength seriously reduces.So the ABS/PMMA/MBS alloy is a kind of HI high impact, height is heat-resisting, cost performance is high and the simple heat-proof ABS material of technology controlling and process, also is a kind of alloy material that has very much market outlook.
Claims (9)
1. a kind of HI high impact according to claim 1, high heat-proof ABS alloy and preparation technology thereof is characterized in that HI high impact, high heat-resisting, and its component and content are following: ABS, 60～90 parts; PMMA, 10～30 parts; Compatilizer, 0～10 part; Lubricant, 0.5～1 part; Oxidation inhibitor, 0.5～1 part; Dispersion agent, 0.5～1 part.
2. a kind of HI high impact according to claim 1, high heat-proof ABS alloy and preparation technology thereof is characterized in that described ABS resin is an acrylonitrile-styrene-acrylic ester copolymer, rubber content >=30%, heat-drawn wire >=90 ℃.
3. a kind of HI high impact according to claim 1, high heat-proof ABS alloy and preparation technology thereof is characterized in that described PMMA resin is a polymethylmethacrylate, melt flow rate(MFR) (MFR) between 1.2～2.0g/10min (240 ℃, 5Kg).
4. a kind of HI high impact according to claim 1, high heat-proof ABS alloy and preparation technology thereof is characterized in that described compatilizer is one or more among MBS (MBS), SMA resin (styrene-maleic anhydride copolymer) or the ABS-g-MAH (maleic anhydride grafted ABS).
5. a kind of HI high impact according to claim 1, high heat-proof ABS alloy and preparation technology thereof is characterized in that described lubricant is one or more among EBS (vinyl bis-stearamides), silicone oil or the Cast (calcium stearate).
6. a kind of HI high impact according to claim 1, high heat-proof ABS alloy and preparation technology thereof; It is characterized in that described oxidation inhibitor is four [methyl-β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, β-(3; The 5-di-tert-butyl-hydroxy phenyl) one or more in the positive octadecanol ester of propionic acid or three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester.
7. a kind of HI high impact according to claim 1, high heat-proof ABS alloy and preparation technology thereof is characterized in that described dispersion agent is one or more in methylsulphonic acid formaldehyde condensation products (MF) or the benzyl naphthalene sulfonic formaldehyde condensation compound (CNF).
8. the preparation technology of a kind of HI high impact according to claim 1, high heat-proof ABS alloy; It is characterized in that: adopt " second order blending method " batch mixing; At first ABS resin, PMMA resin, lubricant are mixed by the proportioning weighing, add compatilizer and other processing aid then and carry out the secondary mixing, mix the back discharging and join in the twin screw extruder; Mixing, extrude, cooling, pelletizing, the cylindrical pellet product.
9. the preparation technology of a kind of HI high impact according to claim 1, high heat-proof ABS alloy; It is characterized in that: barrel temperature is: 180～200 ℃ of back segments, 190～215 ℃ in stage casing, 200～230 ℃ of leading portions; Screw slenderness ratio 35～40, screw speed 300～400r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101225865A CN102775720A (en) | 2011-05-12 | 2011-05-12 | High-impact and high-heat-resistance ABS alloy and its preparation technology |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101225865A CN102775720A (en) | 2011-05-12 | 2011-05-12 | High-impact and high-heat-resistance ABS alloy and its preparation technology |
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| CN102775720A true CN102775720A (en) | 2012-11-14 |
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| CN2011101225865A Pending CN102775720A (en) | 2011-05-12 | 2011-05-12 | High-impact and high-heat-resistance ABS alloy and its preparation technology |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351572A (en) * | 2013-07-14 | 2013-10-16 | 上海秋橙新材料科技有限公司 | Aging-resistant ABS (Acrylonitrile Butadiene Styrene)-PMMA (Polymethyl Methacrylate) plastic alloy |
| CN104629246A (en) * | 2013-11-11 | 2015-05-20 | 黑龙江鑫达企业集团有限公司 | Toughening wear-resistance alloy material and preparation method thereof |
| CN105038094A (en) * | 2015-08-21 | 2015-11-11 | 滁州晨润工贸有限公司 | Novel air-conditioner panel material and preparation method thereof |
| CN105153629A (en) * | 2015-08-21 | 2015-12-16 | 滁州晨润工贸有限公司 | Manufacturing method of antibacterial air-conditioning panel |
| WO2016107004A1 (en) * | 2014-12-31 | 2016-07-07 | 四维尔丸井(广州)汽车零部件有限公司 | Highlight piano black mirror injection moulding method and injection system therefor |
| CN107189331A (en) * | 2017-07-01 | 2017-09-22 | 上海小糸车灯有限公司 | ABS/PMMA alloy composites and its production and use |
| CN108099158A (en) * | 2017-06-15 | 2018-06-01 | 青岛依诺达化工科技有限公司 | A kind of preparation method and equipment of low smell PC/ABS wear resistant alloy materials |
| CN109486078A (en) * | 2018-12-14 | 2019-03-19 | 安徽环嘉天再生资源有限公司 | A kind of heat-insulating flame-retardant ABS plate |
| CN110003608A (en) * | 2019-04-25 | 2019-07-12 | 苏州博驰新材料有限公司 | A kind of dedicated high glaze self-lubricating high molecular material of cosmetic pencil packaging |
| CN110317427A (en) * | 2019-07-03 | 2019-10-11 | 南宁珀源能源材料有限公司 | Novel special backing plate of photovoltaic buddha's warrior attendant wire-electrode cutting |
| CN111607188A (en) * | 2020-07-03 | 2020-09-01 | 宁波恒拓高分子材料有限公司 | An oil-resistant ABS modified material |
| CN114874581A (en) * | 2022-06-21 | 2022-08-09 | 贵州省材料产业技术研究院 | ABS/PMMA micro-foaming composite material and preparation method thereof |
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| CN101475727A (en) * | 2008-11-28 | 2009-07-08 | 上海锦湖日丽塑料有限公司 | ABS/PMMA composite material |
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Patent Citations (2)
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| CN1986634A (en) * | 2005-12-22 | 2007-06-27 | 佛山市顺德区汉达精密电子科技有限公司 | Metho of raising compatibility between ABS and polymethyl methacrylate |
| CN101475727A (en) * | 2008-11-28 | 2009-07-08 | 上海锦湖日丽塑料有限公司 | ABS/PMMA composite material |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351572B (en) * | 2013-07-14 | 2015-11-18 | 上海秋橙新材料科技有限公司 | anti-aging ABS-PMMA plastic alloy |
| CN103351572A (en) * | 2013-07-14 | 2013-10-16 | 上海秋橙新材料科技有限公司 | Aging-resistant ABS (Acrylonitrile Butadiene Styrene)-PMMA (Polymethyl Methacrylate) plastic alloy |
| CN104629246A (en) * | 2013-11-11 | 2015-05-20 | 黑龙江鑫达企业集团有限公司 | Toughening wear-resistance alloy material and preparation method thereof |
| WO2016107004A1 (en) * | 2014-12-31 | 2016-07-07 | 四维尔丸井(广州)汽车零部件有限公司 | Highlight piano black mirror injection moulding method and injection system therefor |
| CN105038094A (en) * | 2015-08-21 | 2015-11-11 | 滁州晨润工贸有限公司 | Novel air-conditioner panel material and preparation method thereof |
| CN105153629A (en) * | 2015-08-21 | 2015-12-16 | 滁州晨润工贸有限公司 | Manufacturing method of antibacterial air-conditioning panel |
| CN108099158A (en) * | 2017-06-15 | 2018-06-01 | 青岛依诺达化工科技有限公司 | A kind of preparation method and equipment of low smell PC/ABS wear resistant alloy materials |
| CN107189331A (en) * | 2017-07-01 | 2017-09-22 | 上海小糸车灯有限公司 | ABS/PMMA alloy composites and its production and use |
| CN109486078A (en) * | 2018-12-14 | 2019-03-19 | 安徽环嘉天再生资源有限公司 | A kind of heat-insulating flame-retardant ABS plate |
| CN110003608A (en) * | 2019-04-25 | 2019-07-12 | 苏州博驰新材料有限公司 | A kind of dedicated high glaze self-lubricating high molecular material of cosmetic pencil packaging |
| CN110317427A (en) * | 2019-07-03 | 2019-10-11 | 南宁珀源能源材料有限公司 | Novel special backing plate of photovoltaic buddha's warrior attendant wire-electrode cutting |
| CN111607188A (en) * | 2020-07-03 | 2020-09-01 | 宁波恒拓高分子材料有限公司 | An oil-resistant ABS modified material |
| CN114874581A (en) * | 2022-06-21 | 2022-08-09 | 贵州省材料产业技术研究院 | ABS/PMMA micro-foaming composite material and preparation method thereof |
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Application publication date: 20121114 |