CN101649102B - High-gloss composite material and preparation method thereof - Google Patents
High-gloss composite material and preparation method thereof Download PDFInfo
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- CN101649102B CN101649102B CN2009103080312A CN200910308031A CN101649102B CN 101649102 B CN101649102 B CN 101649102B CN 2009103080312 A CN2009103080312 A CN 2009103080312A CN 200910308031 A CN200910308031 A CN 200910308031A CN 101649102 B CN101649102 B CN 101649102B
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Abstract
The invention belongs to the technical field of high polymer engineering plastic, in particular a high-gloss composite material and a preparation method thereof. A technical problem to be solved by the invention is to provide the high-gloss composite material with low cost and high hardness. The high-gloss composite material is prepared from the following raw materials by weight part: 85-95 parts of ABS resin, 5-15 parts of PMMA resin, 5-15 parts of AS resin, 2.5-10 parts of compatilizer MBS and 0.15-0.35 part of antioxidant. The high-gloss composite material of the invention uses little amount of PMMA resin and has low cost and high hardness which can reach 2H maximally and 1H minimally; and the glossiness of the composite material reaches above 96% (60 DEG C). The composite material can be applied to industrial spare and accessory parts, shells of electronics/electric products, driving mediums, office equipment, instruments as well as meters and other fields.
Description
Technical field
The invention belongs to macromolecule engineering plastics technology field, particularly a kind of high-gloss composite material and preparation method thereof.
Background technology
ABS resin is the thermoplastic engineering plastic of a kind of novel universal of the exploitation forties in 20th century, and it is to grow up gradually on the basis of polystyrene resin modification.ABS resin is a kind of engineering plastics of excellent property, because its good electrical property, surface gloss, winter hardiness, oil-proofness, chemical stability, impact, low temperature tolerance characteristics, tinctorial property, processing fluidity and dimensional stability, be easy to molded, goods are rich in gloss, and have toughness and flexibility concurrently.Therefore at present ABS has become one of main plastics variety that household electrical appliances, instrument use, is widely used in industrial spare and accessory parts, shells of electronics and driving member, office equipment, instrument and other field.
But common ABS surface hardness is low, and rub resistance can be poor, and its glossiness can only reach 75, has limited its use range greatly.And improve ABS surface hardness and glossy method at present, all adopt methods such as spraying, Lacquer finish.There is the cost height in these methods, and qualification rate is low estimates contaminate environment, be difficult to problem such as recovery.
Studies show that in ABS, to add hardness and the surface gloss that PMMA can improve ABS, cooperate the terpolymer of still forming by acrylonitrile-butadiene-styrene (ABS), along with the variation acquisition ABS/PMMA alloy property of each component concentration is widely different owing to ABS.Because PMMA content in ABS is high more, material flowability is poor more simultaneously.The present invention is by each components contents among the control ABS and select suitable PMMA, and cooperate the cold and hot die injection technology of high light to improve the over-all properties of material greatly, the alloy material goods that make at last not only possess surface of good glossiness and hardness, possess mechanical property and processability preferably simultaneously, be used for the production of flat panel TV face frame.
Chinese patent 200810241237.3 and 200810203577.7 has been announced a kind of formation method of ABS/PMMA high-gloss composite material respectively, but it is well-known, the price of PMMA is than the high 40-50% of ABS, and in these two parts of patents the content of PMMA up to 30～70% (patents 200810241237.3), 30～60% (patents 200810203577.7), increased material cost greatly, and the content of material PMMA of the present invention is only 5～15%.
Summary of the invention
First technical problem to be solved by this invention provides the high-gloss composite material of a kind of low cost, high rigidity, and this high-gloss composite material is that the following raw materials in parts by weight ratio makes:
85～95 parts of ABS resin;
5～15 parts of PMMA resins;
5～15 parts of AS resins;
2.5～10 parts of compatilizer MBS;
0.15～0.35 part of antioxidant.
Preferably, this high-gloss composite material is that the following raw materials in parts by weight ratio makes:
88～94 parts of ABS resin;
6～12 parts of PMMA resins;
6～12 parts of AS resins;
3～6 parts of compatilizer MBS;
0.25 part of antioxidant.
Preferably, PMMA portions of resin AS portions of resin compatilizer MBS=1 by weight in the raw material: 1: 0.5.
Wherein, the terpolymer that described ABS resin is made up of acrylonitrile-butadiene-styrene (ABS), under the condition of 220 ℃/10Kg, its melting index is 18～25g/min.Average small particle size 0.1～0.5nm of the rubber of ABS resin and big particle diameter 1～4.5 possess bimodal or multi-peaks structure, and the weight percent content of vinyl cyanide is 23.5～29.5%.
Described PMMA resin is polymethylmethacrylate (the heat-resisting level of injection moulding), and its Vicat softening point is greater than 110 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min.
Described AS resin is a styrene-acrylonitrile copolymer, and the weight percent content of vinyl cyanide is not less than 24% in the multipolymer.
Described MBS compatilizer is methyl acrylate-butadiene-styrene copolymer, is transparent material.
Described antioxidant can adopt hindered phenol antioxidant, the preferred model that adopts is that 1010 hindered phenol antioxidant is as main anti-oxidant, model is 168 the auxilliary antioxidant of hindered phenol antioxidant conduct, master anti-1010 and auxilliary anti-168 presses 3: 1 weight ratio preparation, wherein 1010 content is high more, the stability of PMMA resin in ABS resin is good more, is not easy to occur the phenomenon of phase-splitting more.
Further, can add color concentrate in the high-gloss composite material of the present invention, can material be dyed distinct colors according to different demands.Described color concentrate is the staining reagent that the present technique field is commonly used, its consumption be high-gloss composite material the raw material gross weight 3～5%, be preferably 4%.
Second technical problem solved by the invention provides the preparation method of above-mentioned high-gloss composite material, and this method is specially following raw material mixing back fusing and pelleting and gets;
85～95 parts of ABS resin;
5～15 parts of PMMA resins;
5～15 parts of AS resins;
2.5～10 parts of compatilizer MBS;
0.15～0.35 part of antioxidant.
Need dry in the raw material before ABS resin, PMMA resin and the AS mixed with resin.Preferably, drying temperature is 70～90 ℃, 3～6 hours time of drying.
High-speed mixing is adopted in described mixing, and mixing time is 6～10 minutes.
The Heating temperature of described melt pelletization is 170～210 ℃, and head temperature is 215 ℃.
The invention has the beneficial effects as follows:
High-gloss composite material PMMA resin demand of the present invention is few, and cost is low; The high maximum of hardness can reach 2H, the minimum 1H that reaches; Glossiness (60 °) reaches more than 96%.Can be widely used in industrial spare and accessory parts, shells of electronics and driving member, office equipment, instrument and other field.
Embodiment
The invention will be further elaborated below in conjunction with embodiment.Embodiment only is used to illustrate the present invention, rather than limits the present invention by any way.
Below the raw material consumption of each embodiment see Table 1:
Table 1 raw material consumption (unit: kilogram)
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| ABS resin | 88 | 90 | 94 | 99 |
| The PMMA resin | 12 | 10 | 6 | 1 |
| The AS resin | 12 | 10 | 6 | 1 |
| MBS | 6 | 5 | 3 | 0.5 |
| Antioxidant 1010/168 | 0.25 | 0.25 | 0.25 | 0.25 |
| Color concentrate | 0 | 4.61 | 4.37 | 0 |
Wherein, the compound proportion of antioxidant is 1010 by weight: 168=3: 1.
Embodiment 1
Take by weighing various raw materials according to table 1 composition of raw materials, wherein ABS resin, PMMA resin, AS resin are 75 ℃ of dryings 3 hours before use respectively, each raw material is added high-speed mixer (SHR-200A) high speed mixed low speed discharging again 6～10 minutes.Material fusing and pelleting behind the mixing gets high-gloss composite material, and product property detects data and sees Table 2.The melt pelletization condition is: main-machine screw rotating speed 500r/min, reinforced rotating speed 28r/min, 1: 170 ℃ of Heating temperature section design temperature, 2:180 ℃, 3:195 ℃, 4:210 ℃, 5:210 ℃, 6:215 ℃, 7:215 ℃, 8:210 ℃, 9:210 ℃, head temperature: 215 ℃.
Embodiment 2
Take by weighing various raw materials according to table 1 composition of raw materials, wherein ABS resin, PMMA resin, AS resin are 80 ℃ of dryings 5 hours before use respectively, each raw material is added high-speed mixer (SHR-200A) high speed mixed low speed discharging again 6～10 minutes.Material fusing and pelleting behind the mixing gets high-gloss composite material, and product property detects data and sees Table 2.The melt pelletization condition is: main-machine screw rotating speed 500r/min, reinforced rotating speed 28r/min, 1:170 ℃ of Heating temperature section design temperature, 2:180 ℃, 3:195 ℃, 4:210 ℃, 5:210 ℃, 6:215 ℃, 7:215 ℃, 8:210 ℃, 9:210 ℃, head temperature: 215 ℃.
Embodiment 3
Take by weighing various raw materials according to table 1 composition of raw materials, wherein ABS resin, PMMA resin, AS resin are 80 ℃ of dryings 4 hours before use respectively, each raw material is added high-speed mixer (SHR-200A) high speed mixed low speed discharging again 6～10 minutes.Material fusing and pelleting behind the mixing gets high-gloss composite material, and product property detects data and sees Table 2.The melt pelletization condition is: main-machine screw rotating speed 500r/min, reinforced rotating speed 28r/min, 1:170 ℃ of Heating temperature section design temperature, 2:180 ℃, 3:195 ℃, 4:210 ℃, 5:210 ℃, 6:215 ℃, 7:215 ℃, 8:210 ℃, 9:210 ℃, head temperature: 215 ℃.
Comparative Examples 1
Take by weighing various raw materials according to table 1 composition of raw materials, wherein ABS resin, PMMA resin, AS resin are 80 ℃ of dryings 3 hours before use respectively, each raw material is added high-speed mixer (SHR-200A) high speed mixed low speed discharging again 6～10 minutes.Material fusing and pelleting behind the mixing gets high-gloss composite material, and product property detects data and sees Table 2.The melt pelletization condition is: main-machine screw rotating speed 500r/min, reinforced rotating speed 28r/min, 1:170 ℃ of Heating temperature section design temperature, 2:180 ℃, 3:195 ℃, 4:210 ℃, 5:210 ℃, 6:215 ℃, 7:215 ℃, 8:210 ℃, 9:210 ℃, head temperature: 215 ℃.
Each embodiment product property of table 2 detects data
Tensile strength is tested according to GB GB/T1040.2-2006 in the table 2; Flexural strength, modulus in flexure are tested according to GB GB/T9341-2000; The socle girder notched Izod impact strength is tested according to GB GB/T1843.2-1996; Heat-drawn wire is tested according to GB GB/T1634.2-2004; Melt flow rate (MFR) is tested according to GB GB/T3682-2000; Surface gloss is according to GB GB/8807, and plastics mirror surface luster test method is tested; Surface hardness is according to GB GB/T6739, hardness of film pencil assay method.
As can be seen from Table 2, Comparative Examples 1 is because the add-on of PMMA is too little, though the good mechanical performance is arranged, its surface hardness is too poor, can not be applied to actual production.
The present invention is by rationally controlling the ratio and the composition of each component in the raw material, can be effectively surface hardness, the surface gloss of ABS/PMMA matrix material be significantly improved adding under the situation of less PMMA resin, realized the high performance of ABS matrix material and exempted from spraying with lower cost.
Claims (9)
1. high-gloss composite material is characterized in that: be that the following raw materials in parts by weight ratio makes:
85～95 parts of ABS resin;
5～15 parts of PMMA resins;
5～15 parts of AS resins;
2.5～10 parts of compatilizer MBS;
0.15～0.35 part of antioxidant;
The weight percent content of described ABS resin vinyl cyanide is 23.5～29.5%, and under the condition of 220 ℃/10Kg, its melting index is 18～25g/min; Average small particle size 0.1～0.5nm of the rubber of ABS resin and big particle diameter 1～4.5 possess bimodal or multi-peaks structure;
Described PMMA resin is a polymethylmethacrylate, and its Vicat softening point is greater than 110 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min.
2. high-gloss composite material according to claim 1 is characterized in that: PMMA portions of resin AS portions of resin compatilizer MBS=1 by weight: 1: 0.5.
3. high-gloss composite material according to claim 1 is characterized in that: the raw material consumption is:
88～94 parts of ABS resin;
6～12 parts of PMMA resins;
6～12 parts of AS resins;
3～6 parts of compatilizer MBS;
0.25 part of antioxidant.
4. high-gloss composite material according to claim 3 is characterized in that: PMMA portions of resin AS portions of resin compatilizer MBS=1 by weight: 1: 0.5.
5. according to each described high-gloss composite material of claim 1～4, it is characterized in that: described antioxidant is to be prepared by 3: 1 weight ratio by 1010 hindered phenol antioxidant and 168 hindered phenol antioxidant.
6. the preparation method of high-gloss composite material is characterized in that: following raw material mixes the back fusing and pelleting and gets;
85～95 parts of ABS resin;
5～15 parts of PMMA resins;
5～15 parts of AS resins;
2.5～10 parts of compatilizer MBS;
0.15～0.35 part of antioxidant;
The weight percent content of described ABS resin vinyl cyanide is 23.5～29.5%, and under the condition of 220 ℃/10Kg, its melting index is 18～25g/min; Average small particle size 0.1～0.5nm of the rubber of ABS resin and big particle diameter 1～4.5 possess bimodal or multi-peaks structure;
Described PMMA resin is a polymethylmethacrylate, and its Vicat softening point is greater than 110 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min.
7. the preparation method of high-gloss composite material according to claim 6 is characterized in that: need dry in the raw material before ABS resin, PMMA resin and the AS mixed with resin.
8. the preparation method of high-gloss composite material according to claim 7 is characterized in that: high-speed mixing is adopted in described mixing, and mixing time is 6～10 minutes.
9. the preparation method of high-gloss composite material according to claim 8, it is characterized in that: the Heating temperature of described melt pelletization is 170～210 ℃, head temperature is 215 ℃.
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Cited By (1)
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| CN102766306A (en) * | 2012-08-14 | 2012-11-07 | 龙甲（上海）实业有限公司 | Spraying-free high-transparent high-glossy acrylonitrile butadiene styrene (ABS) material and preparation method thereof |
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| CN101786360B (en) * | 2010-03-04 | 2013-01-16 | 青岛海信电器股份有限公司 | Bicolor injection composite material and electric appliance casing made of the same |
| CN102101932B (en) * | 2010-12-01 | 2012-08-08 | 福建奥峰科技有限公司 | High-gloss, flame-retarding and heat-resistance ABS alloy and preparation method thereof |
| CN102532782A (en) * | 2010-12-08 | 2012-07-04 | 合肥杰事杰新材料股份有限公司 | High-glossiness spraying-free ABS (acrylonitrile butadiene styrene) resin and preparation method thereof |
| TWI478976B (en) * | 2010-12-31 | 2015-04-01 | Chi Mei Corp | Thermoplastic resin composition |
| CN102492255A (en) * | 2011-12-05 | 2012-06-13 | 四川长虹电器股份有限公司 | ABS/PMMA (Acrylonitrile Butadiene Styrene/Polymethyl Methacrylate) composite material and preparation method thereof |
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| 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 |
| CN107216598A (en) * | 2017-06-22 | 2017-09-29 | 合肥会通新材料有限公司 | A kind of high glaze, high convergency ABS alloy material and preparation method thereof |
| CN107266808A (en) * | 2017-08-20 | 2017-10-20 | 苏建 | A kind of high glaze toughness reinforcing AS composites and preparation method thereof |
| CN108641272A (en) * | 2018-05-03 | 2018-10-12 | 苏州优利金新材料有限公司 | A kind of metallic silver exempts to spray ABS material and preparation method thereof |
| CN114573944B (en) * | 2022-03-31 | 2023-11-03 | 金发科技股份有限公司 | High-gloss high-surface-hardness ABS composite material and preparation method and application thereof |
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Effective date of registration: 20160511 Address after: Hefei New Station District 230000 West Feihe River Road three yuan in Anhui Province Economic and Technological Development Zone No. 3 Patentee after: Hefei Yuda Plastic Industry Co., Ltd. Address before: 621000 Intellectual Property Office, Ministry of legal affairs, 35 Hing Tung Road, Mianyang hi tech Development Zone, Sichuan Patentee before: Sichuan Changhong Electrical Appliance Co., Ltd. |