CN101914243B - Polypropylene composition for injection molding of automotive part with good appearance and preparation method thereof - Google Patents
Polypropylene composition for injection molding of automotive part with good appearance and preparation method thereof Download PDFInfo
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- CN101914243B CN101914243B CN2010102568707A CN201010256870A CN101914243B CN 101914243 B CN101914243 B CN 101914243B CN 2010102568707 A CN2010102568707 A CN 2010102568707A CN 201010256870 A CN201010256870 A CN 201010256870A CN 101914243 B CN101914243 B CN 101914243B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a polypropylene composition for the injection molding of an automotive part with a good appearance and a preparation method thereof. The composition comprises the following components in percentage by weight: 50 to 78 percent of polypropylene resin, 2 to 20 percent of elastomer, 2 to 10 percent of ethylene-propylene block copolymer and the balance of assistant. The automotive part prepared by the polypropylene composition meets use requirements in terms of all properties, avoids a tiger skin appearance defect and has high low-temperature performance and rigidity. The high difference between the melting viscosity of the elastomer and the melting viscosity of the polypropylene makes the elastomer fail to disperse in the polypropylene desirably, so the dispersion particle size of the elastomer in the polypropylene is large, the rigidity is lowered, and the injection molded part has a tiger skin. However, by adding the ethylene-propylene block copolymer, the dispersion of the elastomer in the polypropylene and the phase interface strength of the elastomer and the polypropylene substrate are improved, so the appearance of the part is enhanced.
Description
Technical field
The present invention relates to polypropene composition, be specifically related to a kind of polypropene composition that injection moulding has the good appearance automotive part that is used for.
Background technology
Vestolen PP 7052 has advantages such as light weight, anti-solvent, easy processing, excellent mechanical property, easy recovery because of it, obtained widespread use, and particularly the application at automotive industry, household electrical appliances and mechanical field improves constantly.Automotive industry will develop to directions such as energy-saving and environmental protection, safety future.This just requires, and used quality of materials is light, processing is simple, be prone to recovery etc., and Vestolen PP 7052 has satisfied these requirements.But the polypropylene material resistance to low temperature is poor, and rigidity is low, can not satisfy to be used for the automotive part requirement, must improve its low temperature impact properties and rigidity through modification, satisfies automotive part requirement and standard.Automotive part is meant automotive upholstery and exterior trimming parts.Inside gadget comprises test board, auxiliary fasia console, A, B and C column, glove box, door-plate, trunk plate, threshold etc.; Exterior trimming parts comprises collision bumper, rubbing strip, beater or beat-up and splash pan etc.These products all are according to certain Shooting Technique the mould cavity cooling to be injected in the polypropene composition fusion through injection moulding machine to form.
Be used for requirement and the standard of polypropene composition in order to satisfy automotive applications of automotive part, particularly will have good low temperature impact property and rigidity.Improve low temperature impact properties through adding elastomerics (like alpha-olefin copolymers such as ethylene-propylene diene copolymer, ethylene-octene copolymers).Through adding the rigidity of talcum powder raising material.But,, often add a large amount of elastomericss in order to improve low temperature impact properties.Elastomericly add the defective of outward appearance that affiliation causes automotive part, influence the visual appearance of product.Particularly can produce the phenomenon of tiger fur line on the surface of product.The tiger fur line is meant the periodicity striped at vertical and material fused flow direction generation rule shade.In order to eliminate these defectives, people adopt to spray paint, improve Shooting Technique or improve material flowability and solve.Employing is sprayed paint and can be caused production efficiency to reduce, and produces wild effect.Employing improves Shooting Technique and can cause production efficiency to reduce, and causes other problemses such as product distortion.Adopt and improve flowability, can cause the low temperature impact properties of material and intensity to reduce.
Along with automobile industry to the more and more stricter requirement of product visual appearance, people have proposed the method for a lot of solution tiger fur line phenomenons.
At present, many patents solve automotive part visual appearance defective through number of ways.CN1458958A improves polyacrylic composition through dystectic alfon of special metallocene catalysts or propylene-based block copolymer and solves macroscopic irregularity.CN1803909A discloses and has a kind ofly solved through improving polyacrylic composition.It improves the Vestolen PP 7052 structure through synthetic special ethylene-propylene copolymer and solves macroscopic irregularity.CN1803910A is similar with CN1803909A, also is that the composition of the ethylene-propylene copolymer of adjustment acrylic resin solves macroscopic irregularity.CN101103054A adds to through the wide propylene copolymer of MWD and solves macroscopic irregularity in the acrylic resin.CN101550252A discloses a kind of polypropene composition of being made up of Vestolen PP 7052, Vilaterm, ethylenic copolymer rubber, talcum powder and oxidation inhibitor with good low temperature properties and good appearance.CN101495563A discloses a kind of compsn of being made up of Vestolen PP 7052, ethylene-propylene copolymer, talcum powder etc. and has had good performance and outward appearance.CN1241196A discloses a kind of Vestolen PP 7052 of special construction, has good surface appearance.
These patents have solved the problem of appearance of polypropene composition product to a certain extent.But these patents all are to improve polyacrylic low temperature impact properties with ethylene-propylene copolymer, improve low-temperature performance through its special construction.Low temperature impact properties and rigidity do not had good balance.The tiger fur line that in addition polypropene composition that improves low temperature impact properties owing to interpolation ethylene-octene copolymer, ethylene-butene copolymer or ethene-hexene copolymer elastomerics is produced does not relate to or does not offer some clarification on.
Summary of the invention
The objective of the invention is to deficiency, a kind of polypropene composition that injection moulding has the good appearance automotive part that is used for is provided to the prior art existence.
To achieve these goals, the present invention adopts following scheme:
A kind of polypropene composition, said composition are processed by following component by weight percentage:
Acrylic resin 50～78%;
Elastomerics 2～20%;
Ethylene-Propylene Block Copolymer 2～10%;
Surplus is an auxiliary agent.
Above-mentioned polypropene composition by weight percentage, preferred version is processed by following component:
Acrylic resin 50～78%;
Elastomerics 2～20%;
Ethylene-Propylene Block Copolymer 2～10%;
Mineral filler 15～30%.
In above-mentioned polypropene composition, said acrylic resin is the COPP resin.The melt flow rate(MFR) of COPP (MFR) is 5～35g/10min, and its socle girder notched Izod impact strength is at>=5KJ/m
2That (23 ℃), COPP can be selected is random, block or branch shape multipolymer.Can adopt cationic coordinate polymerization, Ziegler-Natta negative ion coordination polymerization perhaps with metallocene catalyst synthetic Vestolen PP 7052.
In above-mentioned polypropene composition, said elastomerics is an alpha-olefin copolymer, adds elastomerics and has guaranteed to be used for the requirement of automotive part low-temperature flexibility, plays a key effect to improving low-temperature impact.Can adopt in ethene-hexene copolymer, ethylene-butene copolymer, the ethylene-octene copolymer etc. one or more; Elastomerics of the present invention is when selecting, and selection density is 0.850～0.900g/cm
3, preferentially selecting density is 0.855～0.870g/cm
3Elastomerics.These elastomericss have the EXACT trade mark series of Exxon Exxon Mobil (Exxonmobil), the ENGAGE trade mark series of Tao Shi (DOW), the TFMER trade mark series of Mitsui Chemicals (Mitsuichemicals).
In above-mentioned polypropene composition, propylene content is 80～98% in the said Ethylene-Propylene Block Copolymer, and ethylene content is 20～2%.The MWD of Ethylene-Propylene Block Copolymer is 1.7～4.The number-average molecular weight of Ethylene-Propylene Block Copolymer is 60000～250000, and percent crystallinity is 10～20%.Can use gel permeation chromatography weight-average molecular weight and number-average molecular weight, calculate weight-average molecular weight and number-average molecular weight ratio then, promptly be MWD.
In above-mentioned polypropene composition, said mineral filler is a talcum powder, and its particle diameter is 0.1～5 μ m.The preferential talcum powder of selecting 0.1～1 μ m particle diameter.Its dioxide-containing silica>=61%, loss on ignition (1000 ℃)≤6%.Talcum powder is a kind of laminal filler, and its effect is the rigidity that improves polypropylene modified material, improves modulus in flexure and heat-drawn wire.
In above-mentioned polypropene composition, can also comprise pigment dyestuff and mineral dye.Because the present invention is used for the injection molded automobile product, in order to reach needs attractive in appearance, often makes different colours.So also include micro-pigment dyestuff and mineral dye in the present composition.Pigment dyestuff has permanent bordeaux, permanent yellow, phthalocyanine blue, phthalocyanine green etc., and inorganic have titanium oxide, carbon black, red iron oxide, iron oxide black, a ultramarine etc.These pigment can require to use separately according to the moulding color, also can compoundly use.
Another object of the present invention is to provide the preparation method of above-mentioned polypropene composition.
After the preparation method of above-mentioned polypropene composition comprises the steps: each component mixed, through twin screw extruder, melting mixing, the melting mixing temperature is 170～230 ℃, screw slenderness ratio is not less than 32, extruding pelletization, packing gets final product.
Further purpose of the present invention is to provide the application of above-mentioned polypropene composition in the preparation automotive part.Polypropene composition of the present invention can be used for preparing automobile and uses product, and automotive part is meant automotive upholstery and exterior trimming parts.Inside gadget comprises test board, auxiliary fasia console, A, B and C column, glove box, door-plate, trunk plate, threshold etc.; Exterior trimming parts comprises collision bumper, rubbing strip, beater or beat-up and splash pan etc.By the standard testing sample by CJ80C type injection moulding machine at 200～230 ℃ of temperature compacted unders.Condition of molding and specimen preparation meet the requirement of ISO294.1-96 and ISO1873.2-97.
Compared with prior art, the present invention has following beneficial effect:
The present invention is through having discovered a kind of polypropene composition, and process is tested, the trolley part of this polypropylene material preparation, and its various performances all reach request for utilization, have overcome product and have produced tiger fur line macroscopic irregularity, and had good low-temperature performance and rigidity.Because elastomerics and polyacrylic melt viscosity difference are bigger, cause elastomerics can not well disperse at Vestolen PP 7052, make elastomerics dispersive particle diameter in polypropylene base bigger, have reduced rigidity, the product of injection moulding has produced the tiger fur line.Improve the dispersion of elastomerics in polypropylene base and the phase interface intensity of elastomerics and polypropylene base through adding Ethylene-Propylene Block Copolymer, thereby improve the outward appearance of product.Along with the automobile usage quantity increases year by year, the automobile production Absatzvolumen also increases year by year.This will use by driving automobile product polypropylene material.
Embodiment
Testing method:
(1) density: press the ISO1183 test;
(2) tensile strength: press the ISO527 test; Speed is 50mm/min;
(3) socle girder notched Izod impact strength: press the ISO180 test;
(4) melt flow rate(MFR) (MFR): press the ISO1133 test, 230 ℃ of conditions, 2.16Kg;
(5) modulus in flexure: press the ISO178 test, speed is 2mm/min;
(6) the tiger fur line is estimated: the smooth surface that is of a size of 225mmX35mmX2mm with the injection moulding machine injection moulding is dull and stereotyped.Observe its surperficial tiger fur line situation.
The performance perameter of Ethylene-Propylene Block Copolymer is seen table 1 in the embodiment of the invention.CA1 to CA6 is the Ethylene-Propylene Block Copolymer of different model.
Table 1 Ethylene-Propylene Block Copolymer performance perameter
Embodiment 1
The polypropene composition of present embodiment, its composition is as shown in table 2.
The raw material of table 2 polypropene composition and consumption
The polypropene composition of present embodiment, its preparation method is following:
Weigh up by its usage ratio by the said raw material of table 2, after mixing, add twin screw extruder, melting mixing under 190～210 ℃ temperature, extruding pelletization, water-cooled, air-dry, particle diameter is 3mm, packing gets final product.
The detected result of the polypropene composition of present embodiment, as shown in table 3.
Table 3 product performance test result
| Performance | Unit | Numerical value |
| Tensile strength | MPa | 16.6 |
| 23 ℃ of socle girder notched Izod impact strength | KJ/m 2 | 58 |
| Socle girder notched Izod impact strength-30 ℃ | KJ/m 2 | 8.6 |
| Melt flow rate(MFR) | g/10min | 7.1 |
| Modulus in flexure | MPa | 1232 |
| Ocular estimate | Good |
Present embodiment adds Ethylene-Propylene Block Copolymer, and its appearance property is better, and the product surface does not have the tiger fur line.
Embodiment 2
The polypropene composition of present embodiment, its composition is as shown in table 4.
The raw material of table 4 polypropene composition and consumption
The polypropene composition of present embodiment, its preparation method such as embodiment 1.
The detected result of the polypropene composition of present embodiment, as shown in table 5.
Table 5 product performance test result
| Performance | Unit | Numerical value |
| Tensile strength | MPa | 18.2 |
| 23 ℃ of socle girder notched Izod impact strength | KJ/m 2 | 57 |
| Socle girder notched Izod impact strength-30 ℃ | KJ/m 2 | 7.3 |
| Melt flow rate(MFR) | g/10min | 15.8 |
| Modulus in flexure | MPa | 1541 |
| Ocular estimate | Good |
Embodiment 3
The polypropene composition of present embodiment, its composition is as shown in table 6.
The raw material of table 6 polypropene composition and consumption
The polypropene composition of present embodiment, its preparation method such as embodiment 1.
The detected result of the polypropene composition of present embodiment, as shown in table 7.
Table 7 product performance test result
| Performance | Unit | Numerical value |
| Tensile strength | MPa | 18.1 |
| 23 ℃ of socle girder notched Izod impact strength | KJ/m 2 | 55 |
| Socle girder notched Izod impact strength-30 ℃ | KJ/m 2 | 7.8 |
| Melt flow rate(MFR) | g/10min | 23.2 |
| Modulus in flexure | MPa | 2104 |
| Ocular estimate | Good |
Embodiment 4
The polypropene composition of present embodiment, its composition is as shown in table 8.
The raw material of table 8 polypropene composition and consumption
| Material name | Consumption % |
| (weight percent) | |
| COPP: SP179, Qilu Petrochemical branch office of SINOPEC | 60 |
| Talcum powder: He Prefecture, Guangxi talcum powder ltd | 20 |
| Toughner: POE, density 0.870g/cm 3, ExxonMobil Chemical | 10 |
| Ethylene-Propylene Block Copolymer (model C A4) | 10 |
The polypropene composition of present embodiment, its preparation method such as embodiment 1.
The detected result of the polypropene composition of present embodiment, as shown in table 9.
Table 9 product performance test result
| Performance | Unit | Numerical value |
| Tensile strength | MPa | 17.2 |
| 23 ℃ of socle girder notched Izod impact strength | KJ/m 2 | 54 |
| Socle girder notched Izod impact strength-30 ℃ | KJ/m 2 | 8.1 |
| Melt flow rate(MFR) | g/10min | 7.8 |
| Modulus in flexure | MPa | 1354 |
| Ocular estimate | Good |
Embodiment 5
The polypropene composition of present embodiment, its composition is as shown in table 10.
The raw material of table 10 polypropene composition and consumption
The polypropene composition of present embodiment, its preparation method such as embodiment 1.
The detected result of the polypropene composition of present embodiment, as shown in table 11.
Table 11 product performance test result
| Performance | Unit | Numerical value |
| Tensile strength | MPa | 17.8 |
| 23 ℃ of socle girder notched Izod impact strength | KJ/m 2 | 53 |
| Socle girder notched Izod impact strength-30 ℃ | KJ/m 2 | 7.5 |
| Melt flow rate(MFR) | g/10min | 7.9 |
| Modulus in flexure | MPa | 1405 |
| Ocular estimate | Good |
Embodiment 6
The polypropene composition of present embodiment, its composition is as shown in table 12.
The raw material of table 12 polypropene composition and consumption
The polypropene composition of present embodiment, its preparation method such as embodiment 1.
The detected result of the polypropene composition of present embodiment, as shown in table 13.
Table 13 product performance test result
| Performance | Unit | Numerical value |
| Tensile strength | MPa | 19.2 |
| 23 ℃ of socle girder notched Izod impact strength | KJ/m 2 | 53 |
| Socle girder notched Izod impact strength-30 ℃ | KJ/m 2 | 6.4 |
| Melt flow rate(MFR) | g/10min | 22.5 |
| Modulus in flexure | MPa | 1956 |
| Ocular estimate | Good |
Product test result by each embodiment can find out; The present invention has overcome problems such as preparing automotive part outward appearance tiger fur line defective in the prior art; Adopt Ethylene-Propylene Block Copolymer not only to improve the low-temperature performance of material; Make prepared automotive part have good appearance, guaranteed also that simultaneously material has favorable rigidity, reach each item standard that automotive material uses.
Comparative Examples 1
The polypropene composition of present embodiment, its composition is as shown in table 14.
The raw material of table 14 polypropene composition and consumption
The polypropene composition of present embodiment, its preparation method is following:
Weigh up by its usage ratio by the said raw material of table 14, after mixing, add twin screw extruder, melting mixing under 190～210 ℃ temperature, extruding pelletization, water-cooled, air-dry, particle diameter is 3mm, packing gets final product.
The detected result of the polypropene composition of present embodiment, as shown in Tble 15.
Table 15 product performance test result
| Performance | Unit | Numerical value |
| Tensile strength | MPa | 19 |
| 23 ℃ of socle girder notched Izod impact strength | KJ/m 2 | 58 |
| Socle girder notched Izod impact strength-30 ℃ | KJ/m 2 | 6.6 |
| Melt flow rate(MFR) | g/10min | 22 |
| Modulus in flexure | MPa | 1902 |
| Ocular estimate | Difference |
Present embodiment does not have Ethylene-Propylene Block Copolymer, and its appearance property is relatively poor, and there is a large amount of tiger fur lines on the product surface.
Claims (7)
1. a polypropene composition is characterized in that, said composition is processed by following component by weight percentage:
Acrylic resin 50～78%;
Elastomerics 2～20%;
Ethylene-Propylene Block Copolymer 2～10%;
Surplus is an auxiliary agent;
Propylene content is 80～98% in the said Ethylene-Propylene Block Copolymer, and ethylene content is 20～2%;
The MWD of said Ethylene-Propylene Block Copolymer is 1.7～4;
The number-average molecular weight of said Ethylene-Propylene Block Copolymer is 60000～250000, and percent crystallinity is 10～20%.
2. polypropene composition according to claim 1 is characterized in that said composition by weight percentage, is processed by following component:
Acrylic resin 50～78%;
Elastomerics 2～20%;
Ethylene-Propylene Block Copolymer 2～10%;
Mineral filler 15～30%.
3. polypropene composition according to claim 1 is characterized in that: said acrylic resin is the COPP resin.
4. polypropene composition according to claim 1 is characterized in that: said elastomerics is one or more the mixture in ethene-hexene copolymer, ethylene-butene copolymer, the ethylene-octene copolymer, and its density is 0.850～0.900g/cm
3
5. polypropene composition according to claim 2 is characterized in that: said mineral filler is a talcum powder, and its particle diameter is 0.1～5 μ m.
6. the preparation method of said each polypropene composition of claim 1～5; After it is characterized in that this preparation method comprises the steps: each component mixed, through twin screw extruder, melting mixing; The melting mixing temperature is 170～230 ℃; Screw slenderness ratio is not less than 32, extruding pelletization, and packing gets final product.
7. said each polypropene composition of claim 1～5 is used in the preparation automotive part.
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| CN103131083A (en) * | 2011-11-23 | 2013-06-05 | 合肥杰事杰新材料股份有限公司 | Polypropylene composite material with high energy absorption and preparation method thereof |
| CN102875895B (en) * | 2012-09-29 | 2014-06-11 | 天津金发新材料有限公司 | Low-emission type polypropylene material and preparation method and application thereof |
| CN102964686B (en) * | 2012-12-04 | 2015-10-28 | 上海日之升新技术发展有限公司 | A kind of elimination tiger fur line polypropylene composite material and preparation method thereof |
| CN103030918A (en) * | 2013-01-05 | 2013-04-10 | 中国石油化工股份有限公司 | Impact-resistant polypropylene composition with medium flowability and preparation method thereof |
| CN104974416A (en) * | 2014-04-11 | 2015-10-14 | 中国石化扬子石油化工有限公司 | High-rigidity and -toughness polypropylene composite material and preparation method thereof |
| CN104109330A (en) * | 2014-07-04 | 2014-10-22 | 浙江俊尔新材料股份有限公司 | Polypropylene composite material as well as preparation method and application thereof |
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| CN111527141B (en) * | 2017-12-22 | 2024-03-15 | 博禄塑料（上海）有限公司 | Soft polyolefin composition |
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| CN110964249B (en) * | 2019-12-06 | 2022-08-05 | 万华化学（宁波）有限公司 | Injection molding polypropylene modified material capable of eliminating tiger stripes and preparation method thereof |
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| CN112662075B (en) * | 2020-12-11 | 2024-01-09 | 成都金发科技新材料有限公司 | Polypropylene composite material capable of eliminating ghosting and tiger skin line appearance defects |
| CN112708208B (en) * | 2020-12-23 | 2023-07-11 | 成都金发科技新材料有限公司 | Polypropylene composite material and preparation method thereof |
| CN114044977A (en) * | 2021-12-24 | 2022-02-15 | 广州仕天材料科技有限公司 | Anti-tiger stripe polypropylene composite material and preparation method and application thereof |
| CN114672092B (en) * | 2022-03-28 | 2023-06-06 | 成都金发科技新材料有限公司 | Polypropylene composite material, and preparation method and application thereof |
| CN114702754A (en) * | 2022-03-31 | 2022-07-05 | 金发科技股份有限公司 | Low-density high-rigidity high-toughness polypropylene material and preparation method and application thereof |
| CN116218087B (en) * | 2023-02-28 | 2024-08-06 | 天津金发新材料有限公司 | Polypropylene composite material and preparation method and application thereof |
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| CA2128920C (en) * | 1993-07-28 | 1999-06-01 | Akihiko Yamamoto | Propylene polymer compositions |
| CN101659768B (en) * | 2008-08-28 | 2012-07-11 | 金发科技股份有限公司 | Low-temperature impact-resistant polypropylene composition, and preparation method and application thereof as decoration in automobile |
| CN101747555B (en) * | 2008-12-16 | 2013-03-20 | 金发科技股份有限公司 | Scratch resisting polypropylene composition |
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