CN103044850A - Black highlight acrylonitrile butadiene styrene (ABS) alloy and preparation method thereof - Google Patents
Black highlight acrylonitrile butadiene styrene (ABS) alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to black highlight acrylonitrile butadiene styrene (ABS) alloy and a preparation method thereof. The ABS alloy are prepared from the following components in parts by weight: 60-90 parts of high-property ABS resin, 10-40 parts of permeable acrylonitrile (SAN), 0-5 parts of polymethyl methacrylate (PMMA), 0-10 parts of a flexibilizer, 1-10 parts of black masterbatch, 0.2-2 parts of a light stabilizer, and 0.2-5 parts of a processing agent. The preparation method comprises the following steps of: respectively drying the components, evenly stirring the components in a high-speed mixer to fully mix the components, and feeding the mixture to a double-screw extruder; and mixing, extruding, stretching, cooling, pelletizing and drying the mixture to obtain the product. The black highlight ABS alloy is good in glossiness and permeability, has a good black effect, is high in mobility, impact strength and hardness at the same time, can be applied to various injection products, and is especially suitable for products, such as a front shell of a television, with high demands on an ornamental value in industries of household appliances.
Description
Technical field
The present invention relates to a kind of high-performance, dazzle high-light ABS resin of black effect and preparation method thereof, it is mainly used in the exigent large-scale Thin-shell outward appearance moulding of product appearance (comprising glossiness, weld mark, current mark, color and luster etc.) (such as front shell of television etc.), low, the high comprehensive performance of production cost has wide market outlook.
Background technology
ABS(Acrylonitrile butadiene Styrene) the splendid terpolymer of over-all properties that formed by vinyl cyanide, divinyl and vinylbenzene of resin.ABS resin is because showing the synergisticing performance of three kinds of components, so have good fluidity, tough and tensile, the excellent properties such as low-temperature impact resistance good, creep resistant good, good stability of the dimension, molding shrinkage is little, glossiness is good, formability is good, be widely used in the vast fields such as household electrical appliance, mechanical fitting, office appliance, electron device, automotive industry, become the main flow plastic raw materials that enjoys each large enterprises and research institution's favor.
Along with the pursuit of people to high-quality life, the outward appearance of elegant, steady atmosphere more and more becomes one of important means that attracts the human consumer, simultaneously in large-scale shell product industry, especially the green Shooting Technique in the household electric appliances constantly brings forth new ideas, hardness, thermotolerance, scratch resistance, glossiness, permeability and color and luster etc. to product are had higher requirement, a large amount of work has also been done by enterprise and research institution, constantly original ABS is carried out modification, caters to the demand in market.
The PMMA(polymethylmethacrylate) as the desirable modified blends of a kind of damage resistant, high-light ABS alloy, receives much concern always.2012, Long Jia (Shanghai) Industrial Co., Ltd. utilized height ratio PMMA and MBS proportioning to develop high scratch resistance and injures the high-ductility alloy material, and applied for a patent 201210288752.3 " a kind of ABS material of spraying high transparent high gloss and preparation method thereof of exempting from "; Golden hair science and technology applies for a patent 201210037436 " a kind of have weathering resistance, scratch resistance, high gloss and high heat-resisting thermoplastic resin composition and preparation method thereof ", and PMMA content is up to 33-80%.2011, Sichuan Changhong Electric Appliance Co., Ltd's develop went out high rigidity (H level, even 3H level) ABS alloy material, and applies for a patent 201110398087.9 " ABS/PMMA matrix materials and preparation method thereof ".2010, silver-colored auspiciousness engineering plastics (Dongguan) company limited applies for a patent 201010213189.4 " electronic apparatus highlight high-hardness dustproof ABS alloy materials and preparation method thereof ", and PMMA content is 23-60%; Shanghai Pulite Composite Material Co., Ltd applies for a patent 201010611626.8 " a kind of transparent, high rigidity, shock resistance ABS plastic alloy composite ", poly-novel material company limited of Shenzhen section applies for a patent 201010296190.8 " a kind of flame-retarding high-lustre ABS Alloy And Preparation Methods ", Foshan City Shunde District Weilin Engineering Plastics Co., Ltd " a kind of have dazzle black, as to dazzle color effect PMMA/ABS Alloy And Preparation Method ", all pass through to add large ratio PMMA and cooperate with AS, reach the purpose of Gao Guang, damage resistant.In addition, patent 200910196729.X, 200810241237.3,200810241325.3,200810203577.7 also adopts the high-light ABS alloy raw material of height ratio PMMA exploitation high-ductility, high hard, damage resistant, high comprehensive performance.Although the adding of PMMA can significantly improve the multinomial performance (high glossiness, high hard, high-strength, scratch resistance etc.) of ABS alloy and enlarge the Application Areas of ABS resin, but because of PMMA expensive, obviously increase the raw materials cost of high-light ABS alloy, affected its market competitiveness.
In recent years, on the basis of PMMA modification high-light ABS alloy, emerge gradually a collection of high-light ABS alloy modifying material new, low PMMA content (even not containing PMMA), and occuping market share progressively.It is " high heat-resisting that Shenzhen Keju New Material Co., Ltd. applies for a patent 201010296190.8 " a kind of flame-retarding high-lustre ABS Alloy And Preparation Methods " and 200910110381.8, high gloss, fire-retardant ABS is material modified and preparation method thereof ", golden hair science and technology applies for a patent 200910199794.8 " a kind of superelevation flow fire retardant modified ABS resin ", peak difficult to understand, Fujian Science and Technology Ltd. applies for a patent 201010568964.8 " high photoresistance combustion heat-proof ABS Alloy And Preparation Methods ", and China National Petroleum company limited applies for a patent 200910243758.7 " a kind of ABS resin compositions with excellent fluidity energy ".Foregoing invention is all reducing the PMMA consumption in varying degrees, or even abandon the modification mode of PMMA fully, realize high scratch resistance, high glossiness and the good comprehensive mechanical property thereof of high-light ABS alloy by the synergy of the modified additives such as height ratio SAN, fire retardant, toughner, heat-resistant agent.Although foregoing invention has changed the high-light ABS alloy preparation method of traditional height ratio PMMA blend, it is mainly used in the field that thermotolerance, flame retardant resistance are had relatively high expectations, and the cost of the auxiliary agents such as the fire retardant of introducing, thermo-stabilizer is far above PMMA.
The injectable plastic material of the high light plastic of China's electrical equipment outward appearance mostly is ABS/PMMA alloy (being also referred to as high-light ABS alloy) at present, but face the higher problem of high-content PMMA cost, and along with the plastic thin and thick is more and more less, existing ABS/PMMA alloy is when moulding Thin-shell plastic, plastic blackness successful descends, and affects the overall appearance quality of plastic.The CN102311590A patent disclosure a kind of flame-retarding high-lustre ABS Alloy And Preparation Method, flame-retarding high-lustre ABS alloy, composed of the following components by weight percentage: SAN30-40%; PMMA10-14%; ABS12-34%; Toughner 8-12%; Liquid flame-proof 1-2.5%; Solid flame retardant 16-18%; Lubricant 1-2%.Although this invention has adopted SAN to replace the method for modifying of part PMMA, but its PMMA content still surpasses 10%, price is expensive simultaneously toughner and fire retardant ratio are too high, and this has not only increased the alloy system cost, and also control has proposed stricter requirement to the blending technology temperature.Therefore, for the most general high-light ABSs that adopt of the current electrical equipment appearance component of China, in the urgent need to seeking a kind of modified method that reduces cost and satisfy again the high-light ABS alloy of dazzling black effect of injection molded electrical equipment Thin-shell appearance component strong mechanical performance and appearance requirement.For the problems referred to above, this patent adopts the SAN vast scale of the low high-permeability of cost, high rigidity to replace the higher PMMA of cost, and the proportioning of regulating other auxiliary agent, by rational physical modification method and technique, prepare a kind of high-performance, dazzled the high-light ABS alloy of deceiving effect, and reached mechanical property and the visual appearance of original ABS/PMMA alloy, significantly reduced the cost of PMMA modification high-light ABS alloy.
Summary of the invention
The purpose of this invention is to provide a kind of black high-light ABS alloy and preparation method thereof of dazzling, take high-performance ABS as main body, by regulating other batching proportioning and technique, reduce the higher PMMA content of cost, and guarantee scratch resistance and the glossiness requirement of product.
The technical scheme that the present invention takes is:
A kind ofly dazzle black high-light ABS alloy, its weight part ratio consists of:
Describedly dazzle black high-light ABS alloy, its weight part ratio forms preferred:
Describedly dazzle black high-light ABS alloy, its weight part ratio forms further preferred:
Above-mentioned ABS resinoid is a kind of in acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), vinyl cyanide-ethylene, propylene elastomerics-phenylethene grafted copolymer (ABS), the acrylonitrile-styrene-acrylic terpolymer (ASA) or blend that they are several, as the emerging 121H in 757K, the LG river in Zhejiang Province of strange U.S., Korea S Jin Hu 750, Shanghai Gaoqiao 8391, the 0215A of Jilin Petrochemical, the AG15A1 of Taiwan, the GP22 of BASF etc.The vinyl cyanide mass content is between 20%-30% in the ABS resinoid, and the mass content of divinyl is between 13-20%, between the vinylbenzene mass content 40-60%.
Described permeability SAN melt flow coefficient should be at 20-40g/10min(220 ℃, 10kg) between, logical light rate should have high rigidity greater than 85%, high comprehensive performance.
Described PMMA is high rigidity, high-clarity polymethylmethacrylate, and its molecular-weight average is 8-30 ten thousand, and wherein the vinylformic acid mass content is 98-100%.The content of the PMMA that adds is decided with product requirement, and content and the technique because having regulated other batching in the present invention reduces the consumption of PMMA as far as possible, and addition can be kept to zero in case of necessity.
Selected toughner is one or more the mixture in MBS graft copolymer (MBS), chlorinatedpolyethylene, vinylformic acid-butadiene-styrene copolymer, methyl or ethyl propylene acid ester copolymer and the derivative thereof, take MBS as preferred toughner, rubber content should be between 50-60%.
Selected black masterbatch should be high-precision bright level, though the requirement of having satisfied blackness of general look female, but can certain influence be arranged to glossiness and flowability, and then affect processing characteristics.Black masterbatch can be private-use class, also can be general purpose grade, can be PE base, EVA is basic, ABS is basic, any or several mixture of AS in basic, but the special-purpose black masterbatch take ABS as base is for preferably.
The addition of black masterbatch adds according to the outward appearance needs of production product in theory, but for the higher large-scale shell part of appearance requirement (such as front shell of television etc.), its addition should be not less than the 3%(content of carbon black should be greater than 40%, the saturation ratio that black masterbatch allows also should be not less than 3%), especially when the saturating degree of the color of selected ABS base-material is not bery excellent.
Described photostabilizer is one or more the mixture in the single phenol of alkylation, alkylation polyphenol, diphenyl phosphite, triphenyl phosphite, sterically hindered phenol or the hydroxybenzotriazole.
Described processing aid comprises one or more mixture of lubricant, brightening agent, dispersion agent, white mineral oil, glycerine and coupling agent etc.Described processing aid preferred emollient, brightening agent, dispersion agent composite guarantees look mother's abundant dispersion, reaches light, dazzles black appearance requirement.
The above-mentioned preparation method who dazzles black high-light ABS alloy comprises the steps:
With high-performance ABS resinoid, permeability AS(SAN), PMMA, black masterbatch, photostabilizer and processing aid is prepared burden in proportion and respectively dry, in high-speed mixer, stir, fully mix, send in the twin screw extruder, mixing, extrude, tie rod, cooling, pelletizing, drying, acquisition raw material finished product.
Twin screw extrusion process Zhong Ge district temperature is controlled between 180-240 ℃, and the main frame frequency is between 30-45Hz.
The present invention by regulating other batching proportioning and technique, reduces the higher PMMA content of cost take high-performance ABS as main body, the content of the two can be reduced to zero under specific end use, and guarantees scratch resistance and the glossiness requirement of product.Gradually attenuation and affect the problem of blackness effect of the Shell-Class moulding of for industry outward appearance being had relatively high expectations simultaneously (such as front shell of television etc.) is controlled selection and the proportioning of black masterbatch, has obtained a kind of high-performance, has dazzled the high-light ABS alloy material of black effect.
The present invention dazzles black high-light ABS alloy to have good glossiness, permeability and dazzles black effect, simultaneously, also has high flowability, preferably shock strength, higher hardness, can be used in the multiple injecting products, especially in the product that the household electrical appliance industry has high requirements to sight, such as front shell of television etc.Easy dosing of the present invention adopts the twin screw extrusion process preparation, have flow process simple, continuously, the advantage of high, the constant product quality of production efficiency.
The present invention has following beneficial effect:
1. the present invention's high-light ABS of adopting ABS, PMMA, AS, the female and relevant processing aid of high-precision bright black to make has high glossiness.
The high-light ABS alloy that makes of the present invention solved owing to large-scale shell part thickness gradually attenuate affect the problem of plastic blackness effect, the black effect of dazzling that selection and the consumption control by the look mother has reached the shell plastic.
3. the high-light ABS alloy that makes of the present invention is when guaranteeing that institute's moulding plastic has excellent appearance, combine all other excellent physical mechanical properties of material, for example than high impact, fabulous scratch resistance, high flowability etc. is by regulating respectively prepare burden proportioning and technique, reduce the umber of expensive material, under the prerequisite that keeps excellent properties, reduce cost, accord with the demands of the market.
4, the preparation technology of a kind of high-light ABS alloy of mentioning of the present invention is simple, with low cost.
Embodiment
For ease of the present invention is further understood, now describe the present invention in conjunction with specific embodiments,
The ABS that matrix material selective flow speed is higher, properties is good adopts preferably AS(SAN of hardness, permeability) and PMMA, selected toughner is MBS graft copolymer (MBS).
Raw material of the present invention is the commercial goods, is convenient to promote.
Embodiment 1
Dazzle black high-light ABS alloy, its weight part ratio composition sees Table 1.
The ABS resinoid is selected acrylonitrile-styrene-butadiene graft copolymers, and melt flow rate (MFR) is greater than 18g/10min, and high comprehensive performance is such as BASF GP22, Jilin Petrochemical 0215A etc.;
Selected PMMA has high transparent, high scratch resistance, such as the strange beautiful CM207 in Taiwan, CM205 etc.;
Selected AS has high transparent and high melt flow rate (MFR), should be greater than 25g/10min, such as BASF 310TR;
Selected toughner is nucleocapsid structure toughner MBS, and rubber size should be not more than 400nm, such as EM500, the EM500A etc. of Korea S LG;
Selected look female is for the general look mother of import, such as Cabot UN2014, and the high Lay UN606 of Britain etc.;
ABS resinoid, PMMA, SAN, toughner, black masterbatch, photostabilizer and processing aid is dry respectively, mix through high-speed stirring, then said mixture is sent in the forcing machine through the feeder of delicate metering, under screw rod transmission and shearing action, fully fusing, compound, again through head extrude, tie rod, cooling, pelletizing, drying is packed at last.
Twin screw extruder is respectively distinguished temperature and is controlled between 180-240 ℃, and pressure 16MPa, rotating speed are 250-300 rev/min, stops 2-3 minute.
Injection moulding machine is to be injection molded into the standard testing batten under 110 ℃ of conditions at 210-230 ℃, die temperature, and tests after test bars at room temperature placed 24h.
Embodiment 2
Dazzle black high-light ABS alloy, its weight part ratio composition sees Table 1.
Embodiment 2 and embodiment 1 adopt the general look of import female, and its difference is that PMMA content is different.
Embodiment 3
Dazzle black high-light ABS alloy, its weight part ratio composition sees Table 1.
Embodiment 3 compares with 2 with embodiment 1, and its base material A BS and the AS trade mark are different, application be the high-precision light tone mother of domestic ABS base.The AG15A1 of ABS matrix adopting Taiwan, AS are Taiwan NF2200, and black masterbatch is smart brilliant pigment look mother's 2016C.
Embodiment 4
Dazzle black high-light ABS alloy, its weight part ratio composition sees Table 1.
The difference of embodiment 4 and embodiment 3 is that PMMA and toughner content all are that the contamination of black masterbatch changes in zero the situation.
Table 1 material mixture ratio
Black high-light ABS alloy testing standard and the performance test results of dazzling of the present invention is shown in table 2,3.
Table 2 testing standard
According to the proportioning of table 1, select different ABS base-materials, properties has certain difference, and test result is as shown in table 3.
Table 3 the performance test results
According to embodiment in the table 31 test result with embodiment 2, can find out, if select suitable AS(SAN), under certain technique, can reduce expensive PMMA content, even when reducing to zero, still little to the plastic performance impact; Can find out also that by the observation to the plastic outward appearance content of PMMA is also little on the impact of plastic surface sight (weld mark, current mark, permeability etc.).So under certain range of application and specific technique, can reduce or cancel the addition of PMMA fully, and then reach the purpose that reduces cost.
Can find out with the test result of embodiment 4 according to embodiment in the table 33, the base material A BS that selectivity is good and AS(SAN), in the less demanding occasion of shock strength, when fully phasing out PMMA and toughner, the flowability of material and the stretching of plastic, bending property also improve on the contrary to some extent.In addition, from the contrast of embodiment also as can be known, adopt different based blacks female and adjust its content, larger on the impact of outward appearance blackness.
Scope of the present invention is not subjected to the restriction of described specific embodiments, and described embodiment is only wanted also to comprise method and the component of functional equivalent in the scope of the invention as the single example of specifically illustrating the inventive concept all respects.Except content described herein, those skilled in the art can grasp relatively easily multiple modification of the present invention with reference to above describing, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. dazzle black high-light ABS alloy for one kind, it is characterized in that, its weight part ratio consists of:
2. according to claim 1ly dazzle black high-light ABS alloy, it is characterized in that its weight part ratio consists of:
3. according to claim 2ly dazzle black high-light ABS alloy, it is characterized in that its weight part ratio consists of:
4. according to claim 1,2 or 3 describedly dazzle black high-light ABS alloy, it is characterized in that the vinyl cyanide mass content is between 20%-30% in the described ABS resinoid, the mass content of divinyl is between 13-20%, between the vinylbenzene mass content 40-60%.
5. according to claim 1,2 or 3 describedly dazzle black high-light ABS alloy, it is characterized in that described permeability SAN melt flow coefficient should be between 20-40g/10min under 220 ℃/10kg condition, the logical light rate of SAN should be greater than 85%.
6. according to claim 1,2 or 3 describedly dazzle black high-light ABS alloy, it is characterized in that described PMMA is high rigidity, high-clarity polymethylmethacrylate, molecular-weight average is 8-30 ten thousand, wherein the vinylformic acid mass content is 98-100%.
7. according to claim 1,2 or 3 describedly dazzle black high-light ABS alloy, it is characterized in that described processing aid is one or more the mixture in lubricant, brightening agent, white mineral oil, glycerine and the coupling agent.
8. according to claim 1,2 or 3 describedly dazzle black high-light ABS alloy, it is characterized in that selected black masterbatch is high-precision bright level, be the PE base, EVA is basic, ABS is basic, any or several mixture of AS in basic.
9. the preparation method who dazzles black high-light ABS alloy claimed in claim 1, it is characterized in that, high-performance ABS resinoid, permeability SAN, PMMA, black masterbatch, photostabilizer and processing aid are prepared burden and the difference drying in proportion, in high-speed mixer, stir, fully mix, send in the twin screw extruder, mixing, extrude, tie rod, cooling, pelletizing, drying, acquisition raw material finished product.
10. the preparation method who dazzles black high-light ABS alloy according to claim 9 is characterized in that twin screw extrusion process Zhong Ge district temperature is controlled between 180-240 ℃.
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| CN104559108A (en) * | 2014-12-22 | 2015-04-29 | 上海普利特复合材料股份有限公司 | Spray-free PC/ABS composite material with high gloss and high impact resistance and preparation method of spray-free PC/ABS composite material |
| CN105733171A (en) * | 2016-05-05 | 2016-07-06 | 合肥华凌股份有限公司 | Spray-free ABS (acrylonitrile butadiene styrene copolymers) material, spray-free ABS and ABS co-extruded decoration strip and refrigerator using decoration strip |
| CN106189047A (en) * | 2016-07-27 | 2016-12-07 | 金田集团（桐城）塑业有限公司 | A kind of high surface finish ABS material |
| CN107353573A (en) * | 2017-08-15 | 2017-11-17 | 丹阳新华美塑料有限公司 | A kind of chemically-resistant detergent ABS is material modified |
| CN109467833A (en) * | 2018-09-25 | 2019-03-15 | 上海金山锦湖日丽塑料有限公司 | A kind of dust-proof heat-resisting ABS resin and preparation method thereof |
| CN114573944A (en) * | 2022-03-31 | 2022-06-03 | 金发科技股份有限公司 | High-gloss high-surface-hardness ABS (acrylonitrile-butadiene-styrene) composite material as well as preparation method and application thereof |
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| CN104559108A (en) * | 2014-12-22 | 2015-04-29 | 上海普利特复合材料股份有限公司 | Spray-free PC/ABS composite material with high gloss and high impact resistance and preparation method of spray-free PC/ABS composite material |
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| CN114573944A (en) * | 2022-03-31 | 2022-06-03 | 金发科技股份有限公司 | High-gloss high-surface-hardness ABS (acrylonitrile-butadiene-styrene) composite material as well as preparation method and application thereof |
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Application publication date: 20130417 |