CN104448673A - Spraying-free high-weather-resistant scratch-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) preparation and process - Google Patents
Spraying-free high-weather-resistant scratch-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) preparation and process Download PDFInfo
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Abstract
The invention provides a spraying-free high-weather-resistant scratch-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) preparation and process. The ABS comprises the following components in part by weight: 60 ~ 80 parts of ABS; 10- 20 parts of a flame retardant agent; 10-20 parts of a toughening agent; 1 ~ 10 parts of a spraying-free compatibility agent; 1 ~ 5 parts of an anti scratch agent; 0.5 ~ 1 part of an antioxidant; 1 ~ 5 parts of a light stabilizer; 0.1 - 1 part of a dispersant; and 1- 5 parts of other processing aids. The material innovation is introduction of the flame retardant, the toughening agent, the spraying-free compatibility agent, the anti scratch agent, the antioxidant, the light stabilizer, the dispersant and the processing aids, good flame retardant effect is achieved, good mechanical properties weatherability and scratch resistance can be ensured, and the spraying-free high-weather-resistant scratch-resistant halogen-free flame-retardant ABS has the advantages of aging resistance, free spraying, scratch resistance, low cost, high mechanical properties and stabile flame retardance, and can be widely applied to the field of automobiles, electronics, communications, film and television multimedia, and the like.
Description
Technical field
The present invention relates to ABS alloy material technical field, particularly a kind ofly can obtain by twin screw extruder extrusion way the preparation method exempting from spraying, high durable, scrape resistant, halogen-free flame retardant ABS material.
Background technology
The terpolymer that ABS resin is made up of vinylbenzene, divinyl, vinyl cyanide.Because ABS resin has excellent processing characteristics, comprehensive mechanical property, and the advantage such as high gloss, excellent plating performance and moderate cost, be widely used in the fields such as automotive industry, mechanical industry, electronic apparatus.But before ABS material scratch resistance is poor, therefore ABS material is applied in field of terminal, most ABS material needs spraying to obtain enough scratch resistances, and ABS plastic coat-thickness is generally 15 ~ 20 μm, usually needs spraying just can complete for twice.Once need to dry after spraying, then carry out second time spraying.These complete processings not only increase the tooling cost of ABS material, and spraying coating process also can produce harm to workers ' health and environment protection.
Meanwhile, the existence of polyhutadiene unsaturated double-bond in ABS component, make alloy be exterior trimming parts for automobile, particularly during exterior trimming parts, ratio is easier to thermo-oxidative ageing, causes the deterioration of material property.The limiting oxygen index(LOI) (LOI) of ABS resin only has 18.3 ~ 20, easy firing.Be difficult to the service requirements meeting fire safety.The synergistic system that anti-flaming ABS material common at present mainly adopts halogenated flame retardant (as tetrabromo-bisphenol, brominated epoxy oligopolymer, decabromodiphenyl oxide etc.) and weisspiessglanz to form, give the flame retardant resistance that ABS is very high, but its exist raw smoke which greatly, not environmentally, the problem such as obnoxious flavour volatilization is more, therefore research and develop a kind of exempt from spraying, high durable, scrape resistant, halogen-free flame retardant ABS matrix material become the inexorable trend of future development.
Summary of the invention
Spraying that prepared by the present invention exempt from, high durable, scrape resistant, halogen-free flame retardant ABS be improve the scratch resistance of ABS resin poor, easily aging and flammable deficiency and adding due to processing aid cause the mechanical property of material own reduces, difficulty processes.Make the application that it is more suitable at household electrical appliances, decoration, office, machinery, electronic applications, mark meter formula of the present invention is by weight:
ABS 60 ~ 80 parts
Fire retardant 10 ~ 20 parts
Toughner 10 ~ 20 parts
Exempt to spray compatilizer 1 ~ 10 part
Anti-scratch liniment 1 ~ 5 part
0.5 ~ 1 part, oxidation inhibitor
Photostabilizer 1 ~ 5 part
Dispersion agent 0.1 ~ 0.5 part
Other processing aids 1 ~ 5 part
ABS resin is acrylonitrile-butadiene-phenylethene grafted copolymer, acrylonitrile-styrene-acrylic terpolymer (ASA) or MBS graft copolymer (MBS).
Fire retardant is the compound system of one or more in benzoxazine, phosphoric acid ester, resol, Ammonium sulfamate, zinc borate.
Toughner is one or more in styrene-butadiene-styrene block copolymer, styrene-maleic anhydride copolymer, high glue powder.
Exempting to spray compatilizer is the vinylbenzene of oxy radical and alkyl acrylate bi-functional monomer, vinyl cyanide tetrapolymer or the styrene copolymer containing methacrylic acid and maleic anhydride bi-functional monomer.
Anti-scratch liniment is one or more in silicone, PTFE micro mist.
Photostabilizer is nano-TiO
2, benzotriazole cresols class, Oxamides, one or more in hindered amines.
Oxidation inhibitor is hindered amines primary antioxidant and eye phosphoric acid ester auxiliary antioxidant composition.
Dispersion agent is TAF(ethylene bis-fatty acid amides), EBS(vinyl bis-stearamides) or montanin wax in one or more.
Other processing aids be silicone oil, white mineral oil one or more.
The concrete technology route that the present invention adopts is as follows:
Step one, take each component by the mass fraction of proportioning;
Step 2, by ABS, fire retardant, the toughner after weighing, exempt from spraying agent, anti-scratch liniment, oxidation inhibitor, photostabilizer, dispersion agent and other processing aid and put into high-speed mixer, stir 10 ~ 20min at normal temperatures;
Step 3, mixed for step 2 material is joined in the hopper of twin screw extruder, extrudes through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing; Wherein, barrel temperature is set to: back segment 200 ~ 230 DEG C, 200 ~ 230 DEG C, stage casing, leading portion 200 ~ 220 DEG C, screw slenderness ratio 35 ~ 40, screw speed 350 ~ 500r/min.
Prepare the injecting condition of exemplar: injection temperature 210 ~ 260 DEG C, injection pressure 30 ~ 50Mpa, injection moulding speed 30 ~ 60mm/s.
Each embodiment performance is all tested by following standard, and specific standards is as follows:
Shock strength DIN 53453
Tensile strength DIN 53455
Flexural strength DIN 53452
Modulus in flexure DIN 53452
Horizontal vertical combustion instrument ANSI/UL94
Anti-scratch performance PV 3952
Weathering resistance (aberration) thermal ageing 6000h.
Embodiment
Embodiment one
Take ABS:70%, it is mixed 20min in high-speed mixer, the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment two
Take ABS:70%, toughner: 10%, exempt to spray compatilizer: 3%, anti-scratch liniment a:3%, oxidation inhibitor 0.5%, photostabilizer: 1%, dispersion agent: 0.5%, other processing aids: 2%, mix 20min by it in high-speed mixer, the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment three
Take ABS:70%, fire retardant 1:10%, toughner: 10%, exempts to spray compatilizer: 3%, anti-scratch liniment a:3%, oxidation inhibitor 0.5%, photostabilizer: 1%, dispersion agent: 0.5%, other processing aids: 2%, it is mixed 20min in high-speed mixer, and the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment four
Take ABS:70%, fire retardant 2:10%, toughner: 10%, exempts to spray compatilizer: 3%, anti-scratch liniment a:3%, oxidation inhibitor 0.5%, photostabilizer: 1%, dispersion agent: 0.5%, other processing aids: 2%, it is mixed 20min in high-speed mixer, and the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment five
Take ABS:70%, fire retardant 3:10%, toughner: 10%, exempts to spray compatilizer: 3%, anti-scratch liniment a:3%, oxidation inhibitor 0.5%, photostabilizer: 1%, dispersion agent: 0.5%, other processing aids: 2%, it is mixed 20min in high-speed mixer, and the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment six
Take ABS:70%, fire retardant 1:10%, toughner: 10%, exempts to spray compatilizer: 3%, oxidation inhibitor 0.5%, photostabilizer: 1%, dispersion agent: 0.5%, other processing aids: 2%, mix 20min by it in high-speed mixer, the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment seven
Take ABS:70%, fire retardant 1:10%, toughner: 10%, exempts to spray compatilizer: 3%, anti-scratch liniment b:3%, oxidation inhibitor 0.5%, photostabilizer: 1%, dispersion agent: 0.5%, other processing aids: 2%, it is mixed 20min in high-speed mixer, and the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment eight
Take ABS:70%, fire retardant 1:10%, toughner: 10%, exempts to spray compatilizer: 3%, anti-scratch liniment c:3%, oxidation inhibitor 0.5%, photostabilizer: 1%, dispersion agent: 0.5%, other processing aids: 2%, it is mixed 20min in high-speed mixer, and the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
Embodiment nine
Take ABS:70%, fire retardant 1:10%, toughner: 10%, anti-scratch liniment a:3%, dispersion agent: 0.5%, other processing aids: 2%, mix 20min by it in high-speed mixer, the material mixed joins in twin screw extruder by loading hopper, extrude through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing.Wherein, barrel temperature is set to: back segment 220 DEG C, 220 DEG C, stage casing, leading portion 200 DEG C, and screw slenderness ratio is 35, head 220 DEG C, screw speed 400r/min.
By the ABS sample of embodiment one to nine, be injection molded into standard test specimen, test its mechanical property; Its flame retardant properties is compared according to embodiment one to five; Its scraping performance is compared according to embodiment three, six to eight; Its weather resistance is compared according to embodiment three, ten.Utilize once painted thermal ageing 6000h to compare its chromatic aberration, thus reflect that it colour fastness.
table 1:example formulations table (%).
| Project | Example one | Example two | Example three | Example four | Example five | Example six | Example seven | Example eight | Example nine |
| ABS | 100 | 70 | 70 | 70 | 70 | 70 | 70 | 70 | 70 |
| Fire retardant 1 | --- | --- | 10 | --- | --- | 10 | 10 | 10 | 10 |
| Fire retardant 2 | --- | --- | --- | 10 | --- | --- | --- | --- | --- |
| Fire retardant 3 | --- | --- | --- | --- | 10 | --- | --- | --- | --- |
| Toughner | --- | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Scrape liniment a | --- | 3 | 3 | 3 | 3 | --- | --- | --- | 3 |
| Scrape liniment b | --- | --- | --- | --- | --- | --- | 3 | --- | --- |
| Scrape liniment c | --- | --- | --- | --- | --- | --- | --- | 3 | --- |
| Exempt to spray compatilizer | --- | 3 | 3 | 3 | 3 | 3 | 3 | 3 | --- |
| Oxidation inhibitor | --- | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | --- |
| Photostabilizer | --- | 1 | 1 | 1 | 1 | 1 | 1 | 1 | --- |
| Dispersion agent | --- | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Other processing aids | --- | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
table 2:each embodiment performance test table.
Claims (10)
1. exempt from spraying, high durable, scrape resistant, a halogen-free flame retardant ABS, it is characterized in that with weight parts, be made up of the component of following parts by weight:
ABS 60 ~ 80 parts
Fire retardant 10 ~ 20 parts
Toughner 10 ~ 20 parts
Exempt to spray compatilizer 1 ~ 10 part
Anti-scratch liniment 1 ~ 5 part
0.5 ~ 1 part, oxidation inhibitor
Photostabilizer 1 ~ 5 part
Dispersion agent 0.1 ~ 0.5 part
Other processing aids 1 ~ 5 part.
2. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described ABS contains the graft copolymer of divinyl and acrylonitrile-styrene copolymerized mixture, wherein, vinyl cyanide accounts for 15 ~ 35%, divinyl accounts for 5 ~ 30%, and vinylbenzene accounts for 40 ~ 60%.
3. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described fire retardant is the compound system of one or more in benzoxazine, phosphoric acid ester, resol, Ammonium sulfamate, zinc borate.
4. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described toughner is styrene-butadiene-styrene block copolymer, one or more compound system of styrene-maleic anhydride copolymer.
5. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described oxidation inhibitor is made up of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary antioxidant.
6. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described anti-scratch liniment is the compound system of one or more in silicone, PTFE micro mist.
7. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described exempting to spray vinylbenzene that compatilizer is oxy radical and alkyl acrylate bi-functional monomer, vinyl cyanide tetrapolymer or the polystyrene ternary polymkeric substance containing methacrylic acid and maleic anhydride bi-functional monomer.
8. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described photostabilizer is nano-TiO
2, tinuvin class, Oxamides, the compound system of one or more in hindered amines.
9. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described dispersion agent is TAF(ethylene bis-fatty acid amides), EBS(vinyl bis-stearamides) or montanin wax in the compound system of one or more.
10. according to claim 1ly exempt from spraying, high durable, halogen-free flame retardant ABS, it is characterized in that described operational path is: (1) takes each component by the mass fraction of proportioning; (2) by ABS, fire retardant, the toughner after weighing, exempt from spraying agent, anti-scratch liniment, oxidation inhibitor, photostabilizer, dispersion agent and other processing aid and put into high-speed mixer, stir 10 ~ 20min at normal temperatures; (3) mixed for step 2 material is joined in the hopper of twin screw extruder, extrudes through melt blending, water-cooled, air knife cooling drying, granulation, homogenizing; Wherein, barrel temperature is set to: back segment 200 ~ 230 DEG C, 200 ~ 230 DEG C, stage casing, leading portion 200 ~ 220 DEG C, screw slenderness ratio 35 ~ 40, screw speed 350 ~ 500r/min, prepare the injecting condition of exemplar: injection temperature 210 ~ 260 DEG C, injection pressure 30 ~ 50Mpa, injection moulding speed 30 ~ 60mm/s.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310414024.7A CN104448673A (en) | 2013-09-12 | 2013-09-12 | Spraying-free high-weather-resistant scratch-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) preparation and process |
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| CN201310414024.7A CN104448673A (en) | 2013-09-12 | 2013-09-12 | Spraying-free high-weather-resistant scratch-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) preparation and process |
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| CN104890992A (en) * | 2015-05-26 | 2015-09-09 | 铜陵方正塑业科技有限公司 | Flame-retardant paper-plastic composite bag and preparing method thereof |
| CN104945836A (en) * | 2015-07-13 | 2015-09-30 | 苏州新区华士达工程塑胶有限公司 | Plastic for wear-resisting interior trim panel |
| CN105015904A (en) * | 2015-05-29 | 2015-11-04 | 铜陵方正塑业科技有限公司 | High-temperature-resistant paper-plastic composite bag and preparation method thereof |
| CN105462154A (en) * | 2015-12-21 | 2016-04-06 | 佛山市中科院环境与安全检测认证中心有限公司 | Fireproof plastic material |
| CN106810812A (en) * | 2016-12-20 | 2017-06-09 | 吴中区穹窿山福顺生物技术研究所 | A kind of anti-aging wear-resisting modified ABS plastics |
| CN113462115A (en) * | 2021-06-29 | 2021-10-01 | 上海艾镇新材料有限公司 | High-weather-resistance spraying-free ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
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Application publication date: 20150325 |