CN102108176B - ABS material with low gloss, high shock resistance, and high fluidity - Google Patents
ABS material with low gloss, high shock resistance, and high fluidity Download PDFInfo
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- CN102108176B CN102108176B CN 200910200855 CN200910200855A CN102108176B CN 102108176 B CN102108176 B CN 102108176B CN 200910200855 CN200910200855 CN 200910200855 CN 200910200855 A CN200910200855 A CN 200910200855A CN 102108176 B CN102108176 B CN 102108176B
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Abstract
The invention discloses an ABS material with low gloss, high shock resistance, and high fluidity, which comprises a styrene-based resin, an ethane-acrylate copolymer elastomer, and a copolymer of gelated styrene and acrylonitrile; the amounts by weight of the components are 85-97 parts of the styrene-based resin, 1-10 parts of the ethane-acrylate copolymer elastomer, and 1-5 parts of the copolymer of gelated styrene and acrylonitrile. The ABS material prepared according to the ratio of the invention has low gloss, high shock resistance, and good processing fluidity, facilitates the filling and forming of large-size moulds, and is widely applicable to various automobile interior trimming parts and the like.
Description
Technical field
The present invention relates to a kind of ABS material, be specially a kind of low gloss, high-impact, the high ABS material that flows.Belong to the modified plastics field.
Background technology
In the various application scenarios of ABS material, the products appearance that often requires to be made by this material has low gloss.For example the gloss appearance of automobile plastic inner-decoration component is very large on performance and the sensation impact of automotive upholstery, and in general, automobile original equipment manufacturer (OEM) is ready to arrange the glossiness target of 60 degree.
One of method that reduces ABS material gloss is the size of rubber grain in the control ABS resin, for example US Patent No. 4677162 and US 4526926 pass through the use mass polymerization, and the ABS resin that contains larger rubber grain reaches the purpose that reduces ABS material gloss.Adopt this method limited for the reduction effect of gloss.
Other method that reduces ABS material gloss comprises introduces polyepoxides or the vinylbenzene of gelation and the multipolymer of vinyl cyanide etc.For example US Patent No. 4761463, US 4835215 and US 5026277 disclose the method for having used the method that contains unsaturated acid glycidyl ester (GMA) and other epoxy compounds to obtain low gloss ABS material, but the shortcoming that adopts these methods is the melt viscosity that has increased composition, and is very unfavorable to the forming process of material.
Summary of the invention
The objective of the invention is to have enclosed provides a kind of low gloss, high-impact, the high ABS material that flows.ABS material of the present invention has low gloss, high-impact and good processing fluidity, is easy to filling shaping large size mould.Can be used for various automotive upholsteries etc.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of low gloss, high-impact, the high ABS material that flows comprise styrene base resin, ethylene-acrylate copolymer elastomerics, and the multipolymer of the vinylbenzene of gelation and vinyl cyanide; Described styrene resin is 85～97 weight parts, and the ethylene-acrylate copolymer elastomerics is 1～10 weight part, and the vinylbenzene of gelation and the multipolymer of vinyl cyanide are 1～5 weight part.
Described styrene base resin is one or more the miscellany in acrylonitrile-butadiene-styrene copolymer (ABS), Acrylate-styrene bipolymer-acrylonitrile copolymer (ASA) and the styrene-acrylonitrile copolymer (SAN).
Described acrylonitrile-butadiene-styrene copolymer can be the ABS that continuous bulk polymerization method or emulsion grafting polymerization method are produced, perhaps their mixture.ABS resin of the present invention is known and can obtains by a plurality of commercial source.
It is in 16～30% ethylene-acrylate copolymers one or more that described ethylene-acrylic acid ester elastomer is selected from acrylate content.
The used typical example of ethylene-acrylate copolymer elastomerics of the present invention comprises ethylene-methyl acrylate multipolymer (EMA), ethylene-acrylate butyl ester multipolymer (EBA), ethylene-methyl methacrylate butyl ester-carbonyl multipolymer (EBA-CO), and their miscellany.
Described composition also can comprise tinting material, filler, thermo-stabilizer, static inhibitor, lubricant etc.
By the ABS material that proportioning of the present invention prepares, have low gloss, high-impact and good processing fluidity, be easy to filling shaping large size mould, can be widely used in various automotive upholsteries etc.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but described embodiment only is used for explanation the present invention rather than restriction the present invention.
Embodiments of the invention adopt following material:
ABS-1, the continuous bulk polymerization method is produced, U.S. Dow chemical company, trade mark Magnum 3513;
ABS-2, the emulsion grafting polymerization method is produced, BASF chemical company, trade mark GP22;
Ethylene-acrylate butyl ester multipolymer EBA, ARKAMA company, trade mark 17BA04, acrylate content is 16%;
Ethylene-methyl acrylate multipolymer EMA, Dupont company, trade mark AC1820, acrylate content is 20%;
Ethylene-methyl methacrylate butyl ester-carbonyl multipolymer EBA-CO, Dupont company, trade mark HP4051, acrylate content is about 25%;
The multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT
Carbon black colorant, Cabot company, trade mark BP800.
The product performance testing method:
Melting index: press ASTM D1238 method, 220 ℃, test under 10 kilograms of load
Bending property: press 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.
Gloss: press ASTM D2457 method, 60 °, diameter is 80 millimeters disk.
Embodiment 1-3 and comparative example 1-2:
After the multipolymer of the styrene copolymer resin of super-dry, ethylene-acrylate copolymer elastomerics, gelation styrene-acrylonitrile and tinting material mix by proportion of composing in the table 1, joining in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel.Each section of main barrel control temperature (exporting from charging opening to head) is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, and the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product.The said products is injection molded into standard batten with plastic-injection moulding machine in 80 ℃ of dryings after 3 hours in convection oven, 230 ℃ 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 |
| ABS-1 | 95 | 97 | 95 | 90 | 89 |
| EMA | 1 | 3 | 5 | ||
| EBA | 10 | ||||
| BMAT | 5 | 2 | 2 | 5 | 1 |
| Carbon black colorant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Test result | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Melting index (g/10min) | 3.9 | 8.2 | 9.1 | 7.1 | 10.8 |
| Flexural strength (MPa) | 65.3 | 66.5 | 63.6 | 62.1 | 59.5 |
| Modulus in flexure (MPa) | 2310 | 2301 | 2279 | 2202 | 1964 |
| Notched Izod impact strength (J/m) | 189 | 245 | 338 | 387 | 373 |
| Vicat softening temperature (℃) | 98.8 | 97.1 | 96.1 | 95.2 | 90.6 |
| Gloss | 20 | 28 | 20 | 12 | 22 |
By as seen from Table 1, when reaching more low gloss, still kept excellent mechanics and processing characteristics by the ABS alloy material of the present invention's preparation; Contrast is disclosed technology (comparative example 1), and when independent use gelation styrene-acrylonitrile copolymer BMAT, although can reach low luster effect, the melting index of composition sharply reduces, and shows that the processing flowability of material worsens.
Embodiment 4-7 and comparative example 3:
After the multipolymer of the styrene copolymer resin of super-dry, ethylene-acrylate copolymer elastomerics, gelation styrene-acrylonitrile and tinting material mix by proportion of composing in the table 2, joining in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel.Each section of main barrel control temperature (exporting from charging opening to head) is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, and the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product.The said products is injection molded into standard batten with plastic-injection moulding machine in 80 ℃ of dryings after 3 hours in convection oven, 230 ℃ 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.Actual test result sees Table 2.
Table 2:
| Form | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| ABS-2 | 95 | 97 | 95 | 90 | 85 |
| EBA-CO | 1 | 5 | |||
| EMA | 5 | 2.5 | 10 | ||
| BMAT | 2 | 2.5 | 5 | 5 | |
| Carbon black colorant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Test result | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Melting index (g/10min) | 22.7 | 18.4 | 20.2 | 15.3 | 17.2 |
| Flexural strength (MPa) | 62.9 | 64.4 | 63.1 | 64.1 | 59.8 |
| Modulus in flexure (MPa) | 2160 | 2245 | 2190 | 2200 | 1983 |
| Notched Izod impact strength (J/m) | 317 | 286 | 332 | 368 | 372 |
| Vicat softening temperature (℃) | 91.3 | 95.2 | 93.3 | 92.9 | 90.1 |
| Gloss | 46 | 34 | 27 | 22 | 20 |
By as seen from Table 2, when reaching more low gloss, still kept excellent mechanics and processing characteristics by the ABS alloy material of the present invention's preparation; When ethylene-acrylate copolymer elastomerics EMA is used in independent interpolation, can not reach low luster effect (comparative examples 2 and embodiment 6).
The object of the invention provides a kind of low gloss, high-impact, the high ABS material that flows.Low gloss ABS composition of the present invention has low gloss, high-impact and good flowability properties, is easy to filling shaping large size mould, can be used for various automotive upholsteries etc.
Claims (8)
1. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-1 97 weight parts, EMA 1 weight part, BMAT2 weight part, carbon black colorant 0.5 weight part; Its preparation method is:
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature, outlet is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃ from charging opening to head, the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product;
Wherein:
Described ABS-1 is that the continuous bulk polymerization method is produced U.S. Dow chemical company, trade mark Magnum3513; Described EMA is Dupont company, trade mark AC1820, and acrylate content is 20%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
2. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-1 95 weight parts, EMA 3 weight parts, BMAT2 weight part, carbon black colorant 0.5 weight part; Its preparation method is:
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature, outlet is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃ from charging opening to head, the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product;
Wherein:
Described ABS-1 is that the continuous bulk polymerization method is produced U.S. Dow chemical company, trade mark Magnum3513; Described EMA is Dupont company, trade mark AC1820, and acrylate content is 20%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
3. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-1 90 weight parts, EMA 5 weight parts, BMAT5 weight part, carbon black colorant 0.5 weight part; Its preparation method is:
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature, outlet is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃ from charging opening to head, the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product;
Wherein:
Described ABS-1 is that the continuous bulk polymerization method is produced U.S. Dow chemical company, trade mark Magnum3513; Described EMA is Dupont company, trade mark AC1820, and acrylate content is 20%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
4. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-1 89 weight parts, EBA 10 weight parts, BMAT1 weight part, carbon black colorant 0.5 weight part; Its preparation method is:
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature, outlet is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃ from charging opening to head, the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product;
Wherein:
Described ABS-1 is that the continuous bulk polymerization method is produced U.S. Dow chemical company, trade mark Magnum3513; Described EBA is ARKAMA company, trade mark 17BA04, and acrylate content is 16%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
5. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-2 97 weight parts, EBA-CO 1 weight part, BMAT2 weight part, carbon black colorant 0.5 weight part; Its preparation method is:
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature export from charging opening to head and is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, and the twin screw rotating speed is 300 rev/mins, and pelletizing obtains product after extruding material strip and cooling off through tank; Wherein:
Described ABS-2 is that the emulsion grafting polymerization method is produced BASF chemical company, trade mark GP22; Described EBA-CO is Dupont company, trade mark HP4051, and acrylate content is 25%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
6. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-2 90 weight parts, EBA-CO 5 weight parts, BMAT5 weight part, carbon black colorant 0.5 weight part; Its preparation method is:
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature export from charging opening to head and is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, and the twin screw rotating speed is 300 rev/mins, and pelletizing obtains product after extruding material strip and cooling off through tank; Wherein:
Described ABS-2 is that the emulsion grafting polymerization method is produced BASF chemical company, trade mark GP22; Described EBA-CO is Dupont company, trade mark HP4051, and acrylate content is 25%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
7. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-2 95 weight parts, EMA 2.5 weight parts, BMAT2.5 weight part, carbon black colorant 0.5 weight part;
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature export from charging opening to head and is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, and the twin screw rotating speed is 300 rev/mins, and pelletizing obtains product after extruding material strip and cooling off through tank; Wherein:
Described ABS-2 is that the emulsion grafting polymerization method is produced BASF chemical company, trade mark GP22; Described EMA is Dupont company, trade mark AC1820, and acrylate content is 20%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
8. a low gloss, high-impact, the high ABS material that flows, it is characterized in that: the raw material by following weight part forms: ABS-2 85 weight parts, EMA 10 weight parts, BMAT5 weight part, carbon black colorant 0.5 weight part;
After mixing through the above-mentioned raw materials of super-dry, join screw diameter 35mm, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature export from charging opening to head and is respectively 170 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, and the twin screw rotating speed is 300 rev/mins, and pelletizing obtains product after extruding material strip and cooling off through tank; Wherein:
Described ABS-2 is that the emulsion grafting polymerization method is produced BASF chemical company, trade mark GP22; Described EMA is Dupont company, trade mark AC1820, and acrylate content is 20%; Described BMAT is the multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT; Described carbon black colorant is Cabot company, trade mark BP800.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103232679B (en) * | 2013-04-18 | 2015-03-04 | 苏州旭光聚合物有限公司 | Low-glossiness ABS (acrylonitrile-butadiene-styrene) resin |
| CN103740041A (en) * | 2013-12-28 | 2014-04-23 | 重庆普利特新材料有限公司 | Low-gloss and low-odor ABS (acrylonitrile butadiene styrene) material for automotive interior parts and preparation method thereof |
| CN104910539A (en) * | 2015-05-18 | 2015-09-16 | 中国石油天然气股份有限公司吉林石化分公司 | High-impact while household electrical appliance ABS composite material and preparation method therefor |
| CN107955567A (en) * | 2017-11-08 | 2018-04-24 | 天津金发新材料有限公司 | A kind of antistatic ABS compound and preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250314A (en) * | 2007-11-30 | 2008-08-27 | 上海锦湖日丽塑料有限公司 | Heat-proof ABS resin composition for blow-molding and preparation method thereof |
| CN101469120A (en) * | 2007-12-25 | 2009-07-01 | 上海普利特复合材料股份有限公司 | Low brightness, high impact and high flowablity polycarbonate composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250314A (en) * | 2007-11-30 | 2008-08-27 | 上海锦湖日丽塑料有限公司 | Heat-proof ABS resin composition for blow-molding and preparation method thereof |
| CN101469120A (en) * | 2007-12-25 | 2009-07-01 | 上海普利特复合材料股份有限公司 | Low brightness, high impact and high flowablity polycarbonate composition |
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Address after: 201703 12th Floor, Lane 1, 2855, Shanghai Qingping Highway, Zhaoxiang Town, Qingpu District, Shanghai Patentee after: Shanghai Pret Compound Material Co., Ltd. Address before: 200081 2nd Floor, 421 Lane, Siping Road, Hongkou District, Shanghai Patentee before: Shanghai Pret Compound Material Co., Ltd. |