CN101987897A - Permanent antistatic molding composition and preparation method thereof - Google Patents
Permanent antistatic molding composition and preparation method thereof Download PDFInfo
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- CN101987897A CN101987897A CN2010105105834A CN201010510583A CN101987897A CN 101987897 A CN101987897 A CN 101987897A CN 2010105105834 A CN2010105105834 A CN 2010105105834A CN 201010510583 A CN201010510583 A CN 201010510583A CN 101987897 A CN101987897 A CN 101987897A
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Abstract
The invention relates to a permanent antistatic molding composition with low antistatic agent content and excellent comprehensive performance and a preparation method thereof. The permanent antistatic molding composition is characterized by consisting of the following raw materials in part by weight: 50 to 95 parts of thermoplastic resin, 5 to 30 parts of polymer type permanent antistatic agent, 5 to 40 parts of mineral filler and 0 to 15 parts of interface binder. The preparation method comprises a step of producing the composition on conventional extruders, such as single-screw extruders, double-screw extruders and the like. The invention has the advantage that the excellent surface antistatic performance of the final material can be realized by only adding a little polymer type permanent antistatic agent into the whole composite material.
Description
Technical field
The present invention relates to the thermoplastics technical field, specifically, disclose permanent anti-static moulding compound of a kind of low static inhibitor content and high comprehensive performance and preparation method thereof.
Background technology
In daily life and producing, many materials in use are easy to generate accumulation of static electricity, cause dust suction, electric shock, even produce serious accidents such as causing blast behind the spark.Production and processing as synthon in textile industry; The production of various electrostatic susceptibility elements, transportation, seasoning in the electronic industry are because the accumulation of static charge tends to cause heavy losses; In chemical industry, oil refining industry, mining industry and the war industry, the harm that accumulation of static electricity caused that is caused by the application of various non-metallic material is also of common occurrence, so electrostatic control having caused people's attention.The most frequently used and efficient ways is to use static inhibitor to reduce the surface resistivity of material at present.
Static inhibitor is according to the ageing of short duration type static inhibitor of small molecules and the long-acting type static inhibitor of polymkeric substance of being divided into of performance antistatic property.The former is along with the time is diffused into polymer surfaces formation skim gradually, thereby this layer static inhibitor thin layer forms the gathering that a conductive path stops static charge by the water molecules that absorbs in the external environment.Such static inhibitor can allow the surface resistivity of polymkeric substance drop to 10
10～10
12Ohms/sq makes polymkeric substance have slower electrostatic dissipation speed and stops electric charge accumulative total.Its shortcoming is conspicuous, the first, economic electrostatic protection can only be provided in some short application use fields, and the surface resistivity of polymkeric substance can drop to 10
10～10
12Ohms/sq; The second, the performance of its antistatic effect depends critically upon ambient moisture, competence exertion effect under general relative humidity RH＞50% condition; The 3rd, because the transport property of such static inhibitor makes it can not use at some using the very clean occasion (as electronics pallet and electronic packaging) of environmental requirement.Comparatively speaking, the polymkeric substance permanent antistatic agent has incomparable advantage, according to the content of static inhibitor in the polymkeric substance with distribute and surface resistivity can be dropped to 10
8～10
12Ohms/sq, this makes it to be applied in and need lower resistivity be avoided spark and prevent the field that electronic product generation static discharges.Different with the transport property static inhibitor is that although in very low humidity lower surface resistivity rising may be arranged slightly, most of such static inhibitor relies on relative humidity hardly and plays a role.This makes it can bring into play effect equally in some harsh dry environments.In addition, because it does not have transport property, can not cause any pollution, this makes it yield unusually brilliant results in some high-end antistatic Application Areass.
Yet, aspect the polymkeric substance permanent antistatic agent, it is all more welcome all the time polyether-type static inhibitor, or the metal-salt ionomer type static inhibitor that just emerged in nearly 2 years, reach reasonable antistatic effect as need, their additions in resin matrix all than higher (be generally 10wt%～20wt%), for some antistatic Application Areass of having relatively high expectations or adopting non-injection moldings such as blow molding, addition even will surpass 25wt%.Higher addition has brought many problems, and at first, material cost significantly rises, and the market competitiveness descends; Secondly, the polymkeric substance permanent antistatic agent belongs to the elastomerics category mostly, and behind a large amount of such static inhibitor of adding, the intensity and the rigidity of material obviously descend in the resin matrix.Therefore how under less static inhibitor addition, make matrix material can reach same good antistatic surface effect, become the research focus in current anti-static plastic field, have important theoretical and realistic meaning.
Summary of the invention
The antistatic moulding compound that the purpose of this invention is to provide a kind of low static inhibitor content and high comprehensive performance.
Another object of the present invention provides the preparation method of above-mentioned antistatic moulding compound.
For realizing above purpose, the present invention adopts following technical scheme:
A kind of antistatic moulding compound, form by the component of following weight part:
Thermoplastic resin 50-95 part
Polymer type antistatic agent 5-30 part
Mineral filler 5-40 part
Interfacial adhesion agent 0-15 part.
In above-mentioned moulding compound, described thermoplastic resin is polyacetal, polyolefine, polyvinyl chloride, polyacrylic, polystyrene, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polycarbonate, polymeric amide, polyamidoimide, polyphenylene oxide, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate or its mixture.
In above-mentioned moulding compound, described polymer type antistatic agent is segmented copolymer, metal-salt ionomer, quaternary, sulfonic acid type, betaine type or its mixture that contains polyethers.
In above-mentioned moulding compound, described mineral filler is glass fibre, kaolin, talcum powder, mica, wollastonite or its mixture.
In above-mentioned moulding compound, described glass fibre is one or more the mixture in E-glass fibre, S-glass fibre, A-glass fibre, C-glass fibre, D-glass fibre, M-glass fibre, the R-glass fibre; Described glass fibre is that length is the short glass fiber of 2～50mm or the long glass fibres of cutting without weak point; The diameter of described glass fibre is 5 μ m～20 μ m.
In above-mentioned moulding compound, described kaolin be natural hydration kaolin, do not have hydrokaolinite or its mixture through incinerating; Described kaolinic mean particle size (equivalent diameter) is 0.2 μ m～10 μ m.
In above-mentioned moulding compound, described talcous median size can be 2 μ m～50 μ m.
In above-mentioned moulding compound, described mica is white mica, phlogopite, biotite, lithionite, zinnwaldite, receive mica, fluorophlogopite or its mixture; Described micaceous radius-thickness ratio is 10～200; The length-to-diameter ratio of described wollastonite is 10: 1～30: 1.
In above-mentioned moulding compound, described interfacial adhesion agent is styrene-maleic anhydride copolymer, silane coupling agent, titanate coupling agent, aluminate coupling agent or its mixture.
The preparation method of above-mentioned static inhibitor moulding compound, comprise the steps: to adopt forcing machine production, thermoplastic resin adds from the main spout of forcing machine rearmost end, and polymer type antistatic agent, mineral filler and interfacial adhesion agent add at the main spout of forcing machine or other optional positions of extruding zone; If other additive is arranged, select after thermoplastic resin mixes, to add or add from the barrel position separately.
Compared with prior art, the present invention has following beneficial effect:
The polymer type antistatic agent that the present invention adopts belongs to hydrophilic polymer.After itself and macromolecule matrix blend, because the motor capacity of its molecular chain is stronger, and the intermolecular proton of being convenient to moves, conduct and discharge the static charge of generation by ionic conduction on the one hand; On the other hand, antistatic effect is to embody by its special dispersing morphology.Studies show that polymer type antistatic agent mainly is that the stratiform or the muscle shape that are fine on the goods top layer distribute, and constitutes the electroconductibility top layer, and almost is spherical distribution at centre portions, forms so-called " core shell structure ", and reveals static charge as path.
After polymer type antistatic agent being added in the single resin matrix, described as above-mentioned mechanism, it is fine stratiform or muscle shape and distributes on the goods top layer, especially be noted that, the inside of these stratiforms or muscle shape structure is solid, its inside has been full of static inhibitor, and these inner static inhibitor do not form extra conductive path, and they and outer field static inhibitor top layer play a role as a single conductive path integral body.
And another characteristics of the present invention are exactly to have added the specific mineral filler with certain structure level or length-to-diameter ratio on the basis of above-mentioned regular convention formula system, because interfacial tension and physics chemical action power is different between polymer type antistatic agent and resin matrix and the mineral filler surface, make polymer type antistatic agent preferentially depend on the surface arrangement of these mineral fillers, thereby form the very thin antistatic coating of one deck at the filler outermost layer, this antistatic coating has duplicated the surface structure of filler thereby has also had the structure level of filler, and this extremely helps the formation of conductive network.And, this very thin antistatic coating inside is mineral filler, compare with solid stratiform or muscle shape structure that polymer type antistatic agent is filled under the single resin system situation, under identical polymer type antistatic agent addition, the former can form more more efficient and complete surface charges and dredge network.In other words, in order to reach identical antistatic surface effect, the addition of the polymeric antistatic agent that the former is required is well below the latter.In addition, the polymeric antistatic agent content that belongs to the elastomerics category in the former system is seldom added the strengthening action of the mineral filler with certain structure level, and the physical and mechanical properties of the former material will obviously be better than the latter.
Therefore, the low and high comprehensive performance of static inhibitor content of antistatic moulding compound of the present invention.
Embodiment
Table 1-1 is the concrete formula table of embodiment 1～3 and comparative example 1～3
Static inhibitor-1 is a sylvite ionomer type static inhibitor.Mineral filler MICA is that white mica, radius-thickness ratio are 50: 1; Tackiness agent-1 is a silane coupling agent.
The preparation method: with thermoplastic resin, mineral filler and interfacial adhesion agent are carried out dry type and are mixed, and are that the main feeder of 40/1 parallel dual-screw extruding machine adds by length-to-diameter ratio then.Polymer type antistatic agent is added by the side spout the 5th section of extruding zone.Extrusion temperature is set in 160 ℃～200 ℃.To extrude particle in 80 ℃ dehumidifying heat pump dry 4 hours, in conventional injection moulding machine, test required sample then and test according to standard according to the testing standard moulding in the table.
Table 1-2 is a test result.While comparative example 1 and comparative example 1, embodiment 2 and comparative example 2, embodiment 3 and comparative example 3 all can find, the surface resistivity that is added with the system of white mica in the prescription is starkly lower than the system that do not add white mica, and the former physical strength is compared also with the latter with rigidity and is significantly improved.
Table 1-1
Table 1-2
Table 2-1 is the concrete formula table of embodiment 4～6 and comparative example 4～6
Static inhibitor-2 is the segmented copolymer type static inhibitor of polyethers.Mineral filler GF is that length is that the weak point of 6mm is cut the E glass fibre, and tackiness agent-1 is the multipolymer of vinylbenzene and maleic anhydride.
Dry type being carried out in acrylonitrile-butadiene-styrene copolymer and interfacial adhesion agent mix, is that the main feeder of 40/1 parallel dual-screw extruding machine adds by length-to-diameter ratio then.Glass fibre the 4th section of extruding zone by the feeding of side spout, polymer type antistatic agent is added by the side spout the 6th section of extruding zone.Extrusion temperature is set in 180 ℃～220 ℃.To extrude particle in 80 ℃ dehumidifying heat pump dry 4 hours, in conventional injection moulding machine, test required sample then and test according to standard according to the testing standard moulding in the table.
Table 2-2 is a test result.While comparative example 4 and comparative example 4, embodiment 5 and comparative example 5, embodiment 6 and comparative example 6 all can be found, the surface resistivity that is added with the system of glass fibre in the prescription is starkly lower than the system that do not add mineral filler, and the former physical strength is compared also with the latter with rigidity and is significantly improved.
Table 2-1
Table 2-2
Claims (10)
1. an antistatic moulding compound is characterized in that, is made up of the component of following weight part:
Thermoplastic resin 50-95 part
Polymer type antistatic agent 5-30 part
Mineral filler 5-40 part
Interfacial adhesion agent 0-15 part.
2. moulding compound as claimed in claim 1 is characterized in that described thermoplastic resin is polyacetal, polyolefine, polyvinyl chloride, polyacrylic, polystyrene, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polycarbonate, polymeric amide, polyamidoimide, polyphenylene oxide, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate or its mixture.
3. moulding compound as claimed in claim 1 is characterized in that described polymer type antistatic agent is segmented copolymer static inhibitor, metal-salt ionomer static inhibitor, quaternary static inhibitor, sulfonic acid type static inhibitor, betaine type static inhibitor or its mixture that contains polyethers.
4. moulding compound as claimed in claim 1 is characterized in that described mineral filler is glass fibre, kaolin, talcum powder, mica, wollastonite or its mixture.
5. moulding compound as claimed in claim 4 is characterized in that described glass fibre is one or more the mixture in E-glass fibre, S-glass fibre, A-glass fibre, C-glass fibre, D-glass fibre, M-glass fibre, the R-glass fibre; Described glass fibre is that length is the short glass fiber of 2～50mm or the long glass fibres that cut through weak point at the end; The diameter of described glass fibre is 5 μ m～20 μ m.
6. moulding compound as claimed in claim 4, it is characterized in that described kaolin be natural hydration kaolin, do not have hydrokaolinite or its mixture through incinerating; Described kaolinic mean particle size (equivalent diameter) is 0.2 μ m～10 μ m.
7. moulding compound as claimed in claim 4 is characterized in that described talcous median size can be 2 μ m～50 μ m.
8. moulding compound as claimed in claim 4 is characterized in that described mica is white mica, phlogopite, biotite, lithionite, zinnwaldite, receives mica, fluorophlogopite or its mixture; Described micaceous radius-thickness ratio is 10～200; The length-to-diameter ratio of described wollastonite is 10: 1～30: 1.
9. moulding compound as claimed in claim 1 is characterized in that described interfacial adhesion agent is styrene-maleic anhydride copolymer, silane coupling agent, titanate coupling agent, aluminate coupling agent or its mixture.
10. the preparation method of the described static inhibitor moulding compound of claim 1, it is characterized in that comprising the steps: to adopt forcing machine production, thermoplastic resin adds from the main spout of forcing machine rearmost end, and polymer type antistatic agent, mineral filler and interfacial adhesion agent add at the main spout of forcing machine or other optional positions of extruding zone; If other additive is arranged, select after thermoplastic resin mixes, to add or add from the barrel position separately.
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| CN102146206A (en) * | 2011-03-31 | 2011-08-10 | 金发科技股份有限公司 | Mineral filled polyamide composite material and preparation method thereof |
| CN102304256A (en) * | 2011-06-13 | 2012-01-04 | 宜兴市光辉包装材料有限公司 | PVC (Poly Vinyl Chloride) thermal contraction printing film |
| CN102516681A (en) * | 2011-11-23 | 2012-06-27 | 四川朗迪塑胶电器有限公司 | Glass-fiber-reinforced AS (acrylonitrile-styrene) resin antistatic material and preparation method |
| CN102634191A (en) * | 2012-05-15 | 2012-08-15 | 金发科技股份有限公司 | Permanent antistatic nylon elastomer material and preparation method thereof |
| CN103131069A (en) * | 2011-11-28 | 2013-06-05 | 上海日之升新技术发展有限公司 | Permanent anti-static electricity high-density polyethylene (HDPE) composite material and preparation method thereof |
| CN103467881A (en) * | 2013-08-26 | 2013-12-25 | 晶锋集团股份有限公司 | High-toughness and high-shock-resistance polyvinyl chloride cable material and preparation method thereof |
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| CN106832865A (en) * | 2017-03-03 | 2017-06-13 | 深圳市景创科技电子有限公司 | A kind of antistatic material for handle casing and preparation method thereof |
| CN108699299A (en) * | 2016-02-16 | 2018-10-23 | 住友精化株式会社 | Polyolefin resin composite and polyolefin-based resins film |
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| CN102146206A (en) * | 2011-03-31 | 2011-08-10 | 金发科技股份有限公司 | Mineral filled polyamide composite material and preparation method thereof |
| CN102304256A (en) * | 2011-06-13 | 2012-01-04 | 宜兴市光辉包装材料有限公司 | PVC (Poly Vinyl Chloride) thermal contraction printing film |
| CN102304256B (en) * | 2011-06-13 | 2013-03-13 | 宜兴市光辉包装材料有限公司 | PVC (Poly Vinyl Chloride) thermal contraction printing film |
| CN102516681A (en) * | 2011-11-23 | 2012-06-27 | 四川朗迪塑胶电器有限公司 | Glass-fiber-reinforced AS (acrylonitrile-styrene) resin antistatic material and preparation method |
| CN102516681B (en) * | 2011-11-23 | 2013-07-24 | 四川朗迪塑胶电器有限公司 | Glass-fiber-reinforced AS (acrylonitrile-styrene) resin antistatic material and preparation method |
| CN103131069B (en) * | 2011-11-28 | 2015-07-15 | 上海日之升新技术发展有限公司 | Permanent anti-static electricity high-density polyethylene (HDPE) composite material and preparation method thereof |
| CN103131069A (en) * | 2011-11-28 | 2013-06-05 | 上海日之升新技术发展有限公司 | Permanent anti-static electricity high-density polyethylene (HDPE) composite material and preparation method thereof |
| CN102634191A (en) * | 2012-05-15 | 2012-08-15 | 金发科技股份有限公司 | Permanent antistatic nylon elastomer material and preparation method thereof |
| CN103525069B (en) * | 2012-07-07 | 2016-09-14 | 广东广信科技有限公司 | A kind of Merlon-polyphenylene oxide-ABS composite material being applicable to counter box insulation crust |
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| CN106750918B (en) * | 2016-12-08 | 2021-02-26 | 广东美的环境电器制造有限公司 | Dustproof and anti-fouling plastic, preparation method and application thereof, dustproof electric fan blade and dustproof electric fan |
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| CN114437438A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Permanent antistatic polyethylene composition and preparation method and application thereof |
| CN114437438B (en) * | 2020-10-30 | 2023-09-08 | 中国石油化工股份有限公司 | Permanent antistatic polyethylene composition and preparation method and application thereof |
| CN114196151A (en) * | 2021-11-30 | 2022-03-18 | 上海金发科技发展有限公司 | Polyacrylate resin composition and preparation method and application thereof |
| CN114196151B (en) * | 2021-11-30 | 2023-08-15 | 上海金发科技发展有限公司 | Polyacrylate resin composition and preparation method and application thereof |
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Application publication date: 20110323 |