CN106317757A - Antistatic and easy-to-clean material and preparation method thereof - Google Patents
Antistatic and easy-to-clean material and preparation method thereof Download PDFInfo
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- CN106317757A CN106317757A CN201610876555.1A CN201610876555A CN106317757A CN 106317757 A CN106317757 A CN 106317757A CN 201610876555 A CN201610876555 A CN 201610876555A CN 106317757 A CN106317757 A CN 106317757A
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract
The invention relates to an antistatic and easy-to-clean material and a preparation method thereof. The antistatic and easy-to-clean material is prepared from a thermoplastic plastic master batch and the following components in percentage by mass of the thermoplastic plastic master batch: an antistatic agent accounts for 8 percent to 39.4 percent of the thermoplastic plastic master batch, montmorillonoid accounts for 0.5 percent to 8 percent of the thermoplastic plastic master batch, zirconium aluminate accounts for 0.5 percent to 6.1 percent of the thermoplastic plastic master batch, calcium carbonate accounts for 0.5 percent to 1.2 percent of the thermoplastic plastic master batch, sodium dodecyl sulfonate accounts for 1.2 percent to 18.3 percent of the thermoplastic plastic master batch, ethylene glycol ester accounts for 0.2 percent to 11.9 percent of the thermoplastic plastic master batch, stearate accounts for 0.1 percent to 3.4 percent of the thermoplastic plastic master batch and acetone accounts for 0.5 percent to 7.7 percent of the thermoplastic plastic master batch; all the components are compounded together according to the ratio, are uniformly mixed and are subjected to injection molding. The antistatic and easy-to-clean material and the preparation method thereof, provided by the invention, have the advantages of antistatic property, easiness of being cleaned and the like.
Description
Technical field
The invention belongs to field of material technology, particularly relate to a kind of antistatic material easy to clean and preparation method thereof.
Background technology
Often there is the phenomenon of dust stratification in some plastics during using, such as: the dust in air can be with
Float, antibacterial is floating, can surface deposit, also can dynamic friction air, cause Electrostatic Absorption dust.Not only need the most clear
Reason operation is cumbersome, and can affect the service life of equipment.It is specifically introduced as a example by flabellum or impeller below.
As a example by outdoor machine of air-conditioner impeller, the impeller of long-term dust stratification can make air conditioner refrigerating efficiency decay more than 30%, air-conditioning
In use, dust, easily in its surface attachment and then deposition, affects air quantity, efficiency, and easily shape to interior machine ducting part
Become secondary pollution, a lot of antibacterial health risk can be grown, therefore, improve material surface character so that surface is difficult to be stained with ash and becomes
Highly significant.
Electric fan and impeller are during running up, and flabellum (impeller leaf) and air interact and produce dynamic static friction,
Dust adsorption charged ion can be made.Positively or negatively, same sex electric charge repels enhancing to the suspension of about 90%-95% mutually
The degree of stability of dust in air, the charges of different polarity attract to promote dust accumulation to settle flabellum and the windage band of rotation mutually
Upper electric charge, and electrical body has the character attracting slight small item body, so dust can be attracted on flabellum.According to the literature in air
Particle diameter is less than the solid suspension of 75 μm, and the especially many dispersion at the dust of 0.1-10 μ m of particle diameter are the highest, dust
Grain is the most tiny, and the time floated in atmosphere is the longest, and dust also has an antibacterial corpse in atmosphere, oil stain, moisture, some
The fiber of batting shape so that the aerial dust pattern that suspends is extremely complex, it is viscous that the most multi-component dust is easier to enrichment
On impeller or flabellum, long-term flabellum or impeller the most gradually become the dirtiest, and at air-conditioning, the inside leaf of the electrical equipment such as vacuum cleaner
Wheel, if radiator fan impeller is stained with ash for a long time, can affect its normal operating efficiency, a kind of imperial ash flabellum easy to clean and
Impeller can become extremely important.
Existing unmodified flabellum or impeller operate for a long time or stand a period of time, will deposit on impeller or flabellum
A lot of dusts, flabellum impeller the most gradually becomes the dirtiest, has a strong impact on the outward appearance of flabellum impeller.And as air-conditioning, vacuum cleaner
Deng the internal impeller of electrical equipment, if radiator fan impeller is stained with ash for a long time, can affect inside its normal operating efficiency, such as air-conditioning
Impeller, being stained with ash can seriously make windage increase, and affects the refrigeration of complete machine, and additionally dust is enriched with at flabellum fluorine, can affect
The dynamic balancing that flabellum rotates, has a strong impact on flabellum and impeller place air output and the impact of other side.Existing technical scheme
Being exactly periodically to take cleaning dust apart, operate inconvenience and time-consuming, especially cleaning can be pretty troublesome, and cleaning meeting airborne dust is harmful.
Therefore, by antistatic additive modified plastics surface characteristic, reduce dust significant with the adhesion of plastic interface.
Summary of the invention
In view of the problem existing for prior art, the present invention provides antistatic material easy to clean and preparation method thereof, has
Antistatic, imperial advantage such as grey and easy to clean.
The technical scheme is that
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite, zirconium aluminate, carbonic acid
Calcium, dodecyl sodium sulfate, glycol ester, stearate and acetone；All with the mass percent of thermoplastic plastic parent particles, anti-
Electrostatic agent is the 8%-39.4% of thermoplastic plastic parent particles, and montmorillonite is the 0.5%-8% of thermoplastic plastic parent particles, and zirconium aluminate is
The 0.5%-6.1% of thermoplastic plastic parent particles, calcium carbonate is the 0.5%-1.2% of thermoplastic plastic parent particles, dodecyl sodium sulfonate
Sodium is the 1.2%-18.3% of thermoplastic plastic parent particles, and glycol ester is the 0.2%-11.9% of thermoplastic plastic parent particles, stearic
Acid esters is the 0.1%-3.4% of thermoplastic plastic parent particles, and acetone is the 0.5%-7.7% of thermoplastic plastic parent particles.
The invention has the beneficial effects as follows:
Inventor is under study for action it was unexpectedly observed that add the antistatic additive of proper ratio, illiteracy in thermoplastic plastic parent particles
De-soil, zirconium aluminate, calcium carbonate, dodecyl sodium sulfate, glycol ester, stearate and acetone, ensureing the original property of material
On the premise of energy is unaffected, the antistatic property of prepared material can be improved simultaneously, make the material prepared have the effect of imperial ash
Really.Especially, be montmorillonite, zirconium aluminate, calcium carbonate, dodecyl sodium sulfate, glycol ester, stearate and acetone with properly than
The addition of example, with antistatic additive with the use of, can further enhance anlistatig effect, improve the performance of integral material.
Montmorillonite (English name montmorillonite) has another name called montmorillonite, montmorillonite, a kind of silicate natural
Mineral, for the essential mineral component of bentonite ore.Containing Al2O316.54%；MgO4.65%；SiO250.95%.Structural formula is
(Al, Mg)2〔SiO10〕(OH)2·n H2O。
Addition one side of montmorillonite, zirconium aluminate, calcium carbonate, dodecyl sodium sulfate, glycol ester, stearate and acetone
Face can reduce the viscosity of molten synthetic resin, improves the dispersion of filler, improves processing characteristics, it is also possible to by contain
Reaction complicated between Al, Si, Ca etc. and antistatic additive significantly improves antistatic property and imperial ash performance.Such as: silicon atom
" Si-O-Si " key formed with oxygen atom, has good hydrophobic waterproof, reduces the surface energy of material, thus improves imperial ash
Performance.
The material of the present invention can be able to be by the thermoplastic of any kind as thermoplastic plastic parent particles but not limit
In following title: described thermoplastic plastic parent particles selected from acrylonitritrile-styrene resin, PA plastics, polyethylene, polypropylene,
Answering of one or more in polrvinyl chloride, polystyrene, acronitrile-butadiene-styrene co-polymer and Merlon
Join.
Further, the particle diameter of described montmorillonite is: 50-100nm；The particle diameter of described calcium carbonate is: 50-100nm.
Such scheme is used to provide the benefit that: to use montmorillonite and the calcium carbonate of appropriate particle size, improve material further
The processing characteristics of formula, can improve antistatic additive has slippage effect, a small amount of montmorillonite and calcium carbonate to play with base material
Increase rubbing action, improve processing characteristics.
Further, the particle diameter of described montmorillonite is 50-70nm, and the particle diameter of described calcium carbonate is 50-70nm.
Using such scheme to provide the benefit that: particle diameter is less, specific surface area is relatively big, and less addition just can be notable
Improve the performance of material.
Further, the particle diameter of described montmorillonite is 71-90nm, and the particle diameter of described calcium carbonate is 71-90nm.
Such scheme is used to provide the benefit that: to be conducive to surface to process and dispersed.
Further, the particle diameter of described montmorillonite is 91-100nm, and the particle diameter of described calcium carbonate is 91-100nm.
Such scheme is used to provide the benefit that: granule is bigger, easily disperses and is easy to industrialized production.
Further, described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated carbon
Acid calcium；The treating method comprises following steps: montmorillonite and calcium carbonate are mixed with ethanol solution, instill compounding coupling agent,
The montmorillonite of compounding coupling agent and interpolation and calcium carbonate quality and mass percent be 0.5-2%, described compounding coupling agent
Formed by silane coupler and titanate coupling agent are compounding, ultrasonic agitation, sucking filtration, dry, grind to form homopolymerization granule.
Such scheme is used to provide the benefit that: to be conducive to improving montmorillonite and the performance of calcium carbonate, use the water of ethanol
Solution is conducive to hydrolyzing coupling agent so that in resin matrix the most evenly, surface processes improves for montmorillonite and calcium carbonate
The compatibility of montmorillonite and calcium carbonate and resin matrix.
Further, described antistatic additive is selected from cationic antistatic agent, anionic antistatic agents, nonionic antistatic
Agent, the modified copolymer of CNT, Graphene, polyethers and polyamide, metal powder, electrically conductive graphite, dibutyl oleamide,
One or more in HMPA, oxirane epoxy the third Anhui addition product of ethylenediamine, N oxygen ethylization alkylamine
Compounding.
Such scheme is used to provide the benefit that:
Owing to the specific insulation of existing material is generally up to 1012-1020Ω/, easily puts aside electrostatic and causes danger
And easily it is stained with ash.Use mentioned kind antistatic additive so that isolated electric charge can be pulled away, the electricity on conductive material surface
Lotus, reduces the electric charge that material surface is carried, so that dust is not easy to stick in the surface of material.
Further, described cationic antistatic agent is selected from the quaternary ammonium alkyl of long-chain, phosphate and the polymerization of naphthenic acid salt high-molecular
In thing, one or more is compounding.
Such scheme is used to provide the benefit that: to use the cationic antistatic agent of mentioned kind to coordinate with other components and make
With, be conducive to improving antistatic effect further.
Further, described anionic antistatic agents is selected from alkyl sulfonic acid, alkyl sodium sulfate, carboxylate, phosphate and dithio
Compounding of one or more in carbamic alkali metal salt.
Such scheme is used to provide the benefit that: to use the anionic antistatic agents of mentioned kind to coordinate with other components and make
With, be conducive to improving antistatic effect further.
Further, described non-ionic antistatic agent is selected from ethoxylated fat race alkylamine, macrogol ester or ether, fat
Fat acid esters, glycollic amide, fatty alcohol-polyoxyethylene ether, polyol fatty acid ester, monoglyceride monostearate, oleic acid monoglyceride, Laurel
Compounding of one or more in acid monoglyceride, polyoxyethylene carboxylate.
Such scheme is used to provide the benefit that: to use the non-ionic antistatic agent of mentioned kind to coordinate with other components and make
With, be conducive to improving antistatic effect further.
The present invention also provides for the preparation method of a kind of antistatic material easy to clean, comprises the following steps: join according to above-mentioned
Each component is compounded together by ratio, mixing, injection mo(u)lding.
Use such scheme to provide the benefit that: it is simple that the present invention has preparation method, there is antistatic and imperial ash etc. excellent
Point.
The present invention also provides for a kind of antistatic product easy to clean, and the material of this product includes above-mentioned antistatic material easy to clean
Material.By the product using above-mentioned material to prepare, there is good antistatic property and imperial ash performance.Described product can be but
It is not limited to the products such as fan, impeller, the aerofoil fan of air-conditioning, steam cleaner dust stratification bucket, electric appliance casing or electric plastics device.
Accompanying drawing explanation
Fig. 1 is that dust is stained with, with base material, the microgram connect；
Fig. 2 is the schematic diagram being stained with ash situation of present invention material easy to clean；
Fig. 3 is the schematic diagram being stained with ash situation of general material (non-imperial putty material).
Fig. 4 is the testing result of optical microscope X50 times；Left side part A represent comparative example be stained with ash situation, right side B table
That shows embodiment 8 is stained with ash situation.
Fig. 5 is the testing result of general camera, left side part A represent comparative example be stained with ash situation, right side B represents embodiment
1 be stained with ash situation.
Detailed description of the invention
Principle and feature to the present invention are described below, and example is served only for explaining the present invention, is not intended to limit
Determine the scope of the present invention.
Component of the present invention the most all can be prepared by the conventional method of this area or commercial obtain
?.
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite, zirconium aluminate, carbonic acid
Calcium, dodecyl sodium sulfate, glycol ester, stearate and acetone；All with the mass percent of thermoplastic plastic parent particles, anti-
Electrostatic agent is the 8%-39.4% of thermoplastic plastic parent particles, and montmorillonite is the 0.5%-8% of thermoplastic plastic parent particles, and zirconium aluminate is
The 0.5%-6.1% of thermoplastic plastic parent particles, calcium carbonate is the 0.5%-1.2% of thermoplastic plastic parent particles, dodecyl sodium sulfonate
Sodium is the 1.2%-18.3% of thermoplastic plastic parent particles, and glycol ester is the 0.2%-11.9% of thermoplastic plastic parent particles, stearic
Acid esters is the 0.1%-3.4% of thermoplastic plastic parent particles, and acetone is the 0.5%-7.7% of thermoplastic plastic parent particles.
Described thermoplastic plastic parent particles selected from acrylonitritrile-styrene resin (AS plastics), PA plastics, polyethylene (PE),
Polypropylene (PP), polrvinyl chloride (PVC), polystyrene (PS), acronitrile-butadiene-styrene co-polymer (ABS) and poly-
Compounding of one or more in carbonic ester (PC).
In each embodiment, all using acronitrile-butadiene-styrene co-polymer (ABS) as thermoplastic plastic parent particles.
The particle diameter of described montmorillonite is: 50-100nm；The particle diameter of described calcium carbonate is: 50-100nm.Preferably, described illiteracy
The particle diameter of de-soil is 50-70nm, and the particle diameter of described calcium carbonate is 50-70nm；Or the particle diameter of described montmorillonite is 71-90nm, institute
The particle diameter stating calcium carbonate is 71-90nm；Or the particle diameter of described montmorillonite is 91-100nm, the particle diameter of described calcium carbonate is 91-
100nm。
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Institute
State processing method to comprise the following steps: montmorillonite and calcium carbonate are mixed with ethanol solution, instill compounding coupling agent, compounding coupling
The montmorillonite of agent and interpolation and calcium carbonate quality and mass percent be 0.5-2%, described compounding coupling agent is even by silane
Connection agent and titanate coupling agent compound and form, ultrasonic agitation, and sucking filtration is dried, ground to form homopolymerization granule.
Concrete, following operation can be used: first pass through drainage screen screening montmorillonite and the calcium carbonate of 50-100 mesh,
Montmorillonite after screening and calcium carbonate pour in the aqueous solution of ethanol that (volume fraction of ethanol is 98%, and the volume fraction of water is into
2%) (compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler selects, to instill a certain amount of compounding coupling agent
Compounding of one or more in KH550, KH560 and KH570), the quality of compounding coupling agent is the montmorillonite and carbon added
The 0.5-2% of quality sum of acid calcium, stirs 1.5-3h ultrasonic cleaning tank 80-95 DEG C is ultrasonic, and reduce pressure sucking filtration by scattered suspension,
Add at 50-65 DEG C and dry, grind to form homopolymerization granule standby.
Described antistatic additive is selected from cationic antistatic agent, anionic antistatic agents, non-ionic antistatic agent, modified
The copolymer of CNT, Graphene, polyethers and polyamide, metal powder, electrically conductive graphite, dibutyl oleamide, hempa
Compounding of one or more in acyl triamine, oxirane epoxy the third Anhui addition product of ethylenediamine, N oxygen ethylization alkylamine.
The principle of antistatic additive is: 1) the electrostatic partial electrostatic being gathered in impeller surface is led away so that electrostatic less concentration of local；
2) on plastic basis material surface, formation can repel same electric charge dust with counterions so that static electrification dust and base
Material surface combines more weak；3) antistatic additive can capture electronics and neutralize contrary Electrostatic Electron (such as: static electrification dust
Grain).
The copolymer of polyethers and polyamide can also write " polyether-polyamide block copolymer ", " polyamide-polyether is many
Block copolymer ", the form of presentation such as " polyamide-block and the copolymer of polyether block ".Polyethers of the present invention and the copolymerization of polyamide
Thing does the understanding of broad sense, can be grafted electrolyte side chain and can not also be grafted electrolyte side chain, such as, can be grafted band potassium ion
Electrolyte side chain etc..Such as can be grafted the electrolyte side chain etc. of band potassium ion.Such as: polyethers and polyamide form support and gather
Electrolyte side chain is mutually wound the network structure of band like charges, is i.e. similar to the charged microsphere of cage structure, can pull-in range
The electronics (on the dust of these electronics source) of opposite charges, can gradually bury in oblivion the electronics (charged dust) of described electric charge.
Described cationic antistatic agent is a kind of in the quaternary ammonium alkyl of long-chain, phosphate and naphthenic acid salt high-molecular polymer
Or several compounding.
Described anionic antistatic agents is selected from alkyl sulfonic acid, alkyl sodium sulfate, carboxylate, phosphate and aminodithioformic acid
Alkali metal salt in one or more compounding.
Described non-ionic antistatic agent selected from ethoxylated fat race alkylamine, macrogol ester or ether, fatty acid ester,
Glycollic amide, fatty alcohol-polyoxyethylene ether, polyol fatty acid ester, monoglyceride monostearate, oleic acid monoglyceride, lauric acid list are sweet
Compounding of one or more in ester, polyoxyethylene carboxylate.
The preparation method of a kind of antistatic material easy to clean, comprises the following steps: according to above-mentioned proportioning, each component is multiple
It is fitted on together, mixing, pelletize, injection mo(u)lding.The temperature of injection mo(u)lding is 180-200 DEG C.
Formula of the present invention may be used for the antistatic modified scheme of all of plastics.
A kind of antistatic product easy to clean, the material of this product includes above-mentioned antistatic material easy to clean.
Described product is fan, impeller, the aerofoil fan of air-conditioning, steam cleaner dust stratification bucket, electric appliance casing, plastic sheeting
Or electric plastics device.Plastic sheeting can be to need the plastic sheetings such as anlistatig PET, PI or PVC.
Compounding in the present invention is not being blended simply of single various formula, also further indicate that dispersed,
Various component proportionings, chemically and physically intermiscibility, order of addition, addition manner and technique.
Due to the effect of electrostatic, dust is easy to be stained with the surface being connected on plastic basis material, as it is shown in figure 1, the table of plastic basis material
Face is covered by dust, and impact is normal to be used.The present invention, by the setting of rational formula, has good antistatic and drives ash
Effect, as in figure 2 it is shown, be the ash situation of being stained with of the material meeting technical solution of the present invention, (non-imperial with the general material of Fig. 3 signal
Putty material) ash situation of being stained with compare, technical solution of the present invention has the effect substantially reducing material surface amount of dust, is using
Time, easily clear up dust, it is ensured that the normal work of this material.
It is introduced below by some specific embodiments.
Embodiment 1
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 50nm),
Zirconium aluminate, calcium carbonate (50nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All with thermoplastic plastic parent particles
Mass percent, antistatic additive is the 8% of thermoplastic plastic parent particles, and montmorillonite is the 0.5% of thermoplastic plastic parent particles, aluminum
Acid zirconium is the 0.5% of thermoplastic plastic parent particles, and calcium carbonate is the 0.5% of thermoplastic plastic parent particles, and dodecyl sodium sulfate is heat
The 1.2% of thermoplastic plastic master batch, glycol ester is the 0.2% of thermoplastic plastic parent particles, and stearate is thermoplastic plastic parent particles
0.1%, acetone is the 0.5% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 50 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
Connection agent (compounds coupling agent and includes the mass ratio of silane coupler and titanate coupling agent, silane coupler and titanate coupling agent
For 1:1, silane coupler is KH550), the quality of compounding coupling agent is the montmorillonite and the quality sum of calcium carbonate added
0.5%, stir 1.5h ultrasonic cleaning tank 80 DEG C is ultrasonic, reduce pressure sucking filtration by scattered suspension, adds at 50 DEG C and dries, grinds to form
Homopolymerization granule is standby.
Described antistatic additive is selected from cationic antistatic agent.Described cationic antistatic agent is the polymerization of naphthenic acid salt high-molecular
Thing.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 180 DEG C.
Embodiment 2
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 100nm),
Zirconium aluminate, calcium carbonate (particle diameter is 100nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All with thermoplasticity
The mass percent of plastic master batch, antistatic additive is the 39.4% of thermoplastic plastic parent particles, and montmorillonite is that thermoplastic is female
The 8% of grain, zirconium aluminate is the 6.1% of thermoplastic plastic parent particles, and calcium carbonate is the 1.2% of thermoplastic plastic parent particles, dodecyl
Sodium sulfonate is the 18.3% of thermoplastic plastic parent particles, and glycol ester is the 11.9% of thermoplastic plastic parent particles, and stearate is heat
The 3.4% of thermoplastic plastic master batch, acetone is the 7.7% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 100 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
Connection agent (compounding coupling agent includes silane coupler and titanate coupling agent, silane coupler compounding selected from KH550 and KH560,
The mass ratio of KH550, KH560 and titanate coupling agent is 1:1:1), the quality of compounding coupling agent is the montmorillonite and carbon added
The 2% of the quality sum of acid calcium, stirs 3h ultrasonic cleaning tank 95 DEG C is ultrasonic, and reduce pressure sucking filtration by scattered suspension, 65 DEG C of interpolations
Dry, grind to form homopolymerization granule standby.
Described antistatic additive is anionic antistatic agents and the compound of N oxygen ethylization alkylamine, anion antistatic
The mass ratio of agent and N oxygen ethylization alkylamine is 2:1.
Described anionic antistatic agents is the compound of the alkali metal salt of phosphate and aminodithioformic acid, phosphate and
The mass ratio 0.3:1 of the alkali metal salt of aminodithioformic acid.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 200 DEG C.
Embodiment 3
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 60nm),
Zirconium aluminate, calcium carbonate (particle diameter is 60nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All mould with thermoplasticity
The mass percent of material master batch, antistatic additive is the 10% of thermoplastic plastic parent particles, and montmorillonite is thermoplastic plastic parent particles
1.5%, zirconium aluminate is the 1.5% of thermoplastic plastic parent particles, and calcium carbonate is the 0.6% of thermoplastic plastic parent particles, dodecyl sulphur
Acid sodium is the 1.5% of thermoplastic plastic parent particles, and glycol ester is the 0.5% of thermoplastic plastic parent particles, and stearate is thermoplasticity
The 0.5% of plastic master batch, acetone is the 1% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is selected from KH550, KH560 and KH570 in connection agent
Three kinds compound, the mass ratio of KH550, KH560, KH570 and titanate coupling agent is 2:1:1:1), the quality of compounding coupling agent
For the montmorillonite added and the 1% of the quality sum of calcium carbonate, stir 2h ultrasonic cleaning tank 85 DEG C is ultrasonic, scattered suspension is subtracted
Pressure sucking filtration, adds at 60 DEG C and dries, grind to form homopolymerization granule standby.
Described antistatic additive is oxirane epoxy third Anhui of dibutyl oleamide, HMPA, ethylenediamine
The compound of addition product, dibutyl oleamide, HMPA, oxirane epoxy the third Anhui addition product of ethylenediamine
Mass ratio is 1:0.4:0.7.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 4
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 70nm),
Zirconium aluminate, calcium carbonate (70nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All with thermoplastic plastic parent particles
Mass percent, antistatic additive is the 13.4% of thermoplastic plastic parent particles, and montmorillonite is thermoplastic plastic parent particles
2.5%, zirconium aluminate is the 2.5% of thermoplastic plastic parent particles, and calcium carbonate is the 0.7% of thermoplastic plastic parent particles, dodecyl sulphur
Acid sodium is the 2.1% of thermoplastic plastic parent particles, and glycol ester is the 1.9% of thermoplastic plastic parent particles, and stearate is thermoplasticity
The 1.1% of plastic master batch, acetone is the 1.5% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is selected from KH550, KH560 and KH570 in connection agent
Three kinds compound, the mass ratio of KH550, KH560, KH570 and titanate coupling agent is 2:1:2:1), the quality of compounding coupling agent
For the montmorillonite added and the 1% of the quality sum of calcium carbonate, stir 2h ultrasonic cleaning tank 85 DEG C is ultrasonic, scattered suspension is subtracted
Pressure sucking filtration, adds at 60 DEG C and dries, grind to form homopolymerization granule standby.
Described antistatic additive is polyethers and the copolymer of polyamide, electrically conductive graphite, dibutyl oleamide and hempa
The compound of acyl triamine, described polyethers and the copolymer of polyamide, electrically conductive graphite, dibutyl oleamide and hexamethyl phosphinylidyne three
The mass ratio of amine is 1:3:5:2.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 5
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 80nm),
Zirconium aluminate, calcium carbonate (particle diameter is 80nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All mould with thermoplasticity
The mass percent of material master batch, antistatic additive is the 15% of thermoplastic plastic parent particles, and montmorillonite is thermoplastic plastic parent particles
3.5%, zirconium aluminate is the 3.5% of thermoplastic plastic parent particles, and calcium carbonate is the 0.8% of thermoplastic plastic parent particles, dodecyl sulphur
Acid sodium is the 3.3% of thermoplastic plastic parent particles, and glycol ester is the 3.9% of thermoplastic plastic parent particles, and stearate is thermoplasticity
The 1.5% of plastic master batch, acetone is the 2% of thermoplastic plastic parent particles.
Described antistatic additive be non-ionic antistatic agent, the modified copolymer of CNT, polyethers and polyamide, two
Butyl oleamide, the compound of HMPA.Non-ionic antistatic agent, modified CNT, polyethers and poly-
The copolymer of amide, dibutyl oleamide, the mass ratio of HMPA are 1:1:1:1:1.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is KH560, KH560 and titanate esters idol in connection agent
The mass ratio of connection agent is 2:1), the quality of compounding coupling agent is the 1% of the quality sum of montmorillonite and the calcium carbonate added, ultrasonic
Rinse bath 85 DEG C is ultrasonic stirs 2h, and reduce pressure sucking filtration by scattered suspension, adds at 60 DEG C and dries, grinds to form homopolymerization granule standby.
Described non-ionic antistatic agent is polyol fatty acid ester, monoglyceride monostearate, oleic acid monoglyceride, lauric acid list
Sweet ester, the compound of polyoxyethylene carboxylate.Polyol fatty acid ester, monoglyceride monostearate, oleic acid monoglyceride, lauric acid list
Sweet ester, the mass ratio of polyoxyethylene carboxylate are 0.3:0.3:0.7:3.4:1.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 6
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 90nm),
Zirconium aluminate, calcium carbonate (90nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All with thermoplastic plastic parent particles
Mass percent, antistatic additive is the 18% of thermoplastic plastic parent particles, and montmorillonite is the 4.5% of thermoplastic plastic parent particles,
Zirconium aluminate is the 4.5% of thermoplastic plastic parent particles, and calcium carbonate is the 0.9% of thermoplastic plastic parent particles, and dodecyl sodium sulfate is
The 5.3% of thermoplastic plastic parent particles, glycol ester is the 5.3% of thermoplastic plastic parent particles, and stearate is that thermoplastic is female
The 2.4% of grain, acetone is the 3.7% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is KH570, KH570 and titanate esters idol in connection agent
The mass ratio of connection agent is 2:1), the quality of compounding coupling agent is the 1% of the quality sum of montmorillonite and the calcium carbonate added, ultrasonic
Rinse bath 85 DEG C is ultrasonic stirs 2h, and reduce pressure sucking filtration by scattered suspension, adds at 60 DEG C and dries, grinds to form homopolymerization granule standby.
Described antistatic additive is non-ionic antistatic agent, modified CNT, dibutyl oleamide, hempa
Acyl triamine, oxirane epoxy the third Anhui addition product of ethylenediamine, the compound of N oxygen ethylization alkylamine.Nonionic resists quiet
Electricity agent, modified CNT, dibutyl oleamide, HMPA, oxirane epoxy third Anhui of ethylenediamine add
Becoming thing, the mass ratio of N oxygen ethylization alkylamine is 1:1.5:1:2.9:1.7:1.
Described non-ionic antistatic agent is selected from ethoxylated fat race alkylamine, polyglycol ether, fatty acid ester, ethanol
Amide, fatty alcohol-polyoxyethylene ether, the compound of polyol fatty acid ester.Ethoxylated fat race alkylamine, polyglycol ether,
Fatty acid ester, glycollic amide, fatty alcohol-polyoxyethylene ether, the mass ratio of polyol fatty acid ester are 2.8:1.3:1:2:1.3:1.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 7
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 100nm),
Zirconium aluminate, calcium carbonate (particle diameter is 100nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All with thermoplasticity
The mass percent of plastic master batch, antistatic additive is the 25.4% of thermoplastic plastic parent particles, and montmorillonite is that thermoplastic is female
The 5.8% of grain, zirconium aluminate is the 5.5% of thermoplastic plastic parent particles, and calcium carbonate is the 1.0% of thermoplastic plastic parent particles, dodecane
Base sodium sulfonate is the 8.3% of thermoplastic plastic parent particles, and glycol ester is the 7.9% of thermoplastic plastic parent particles, and stearate is heat
The 2.6% of thermoplastic plastic master batch, acetone is the 4.8% of thermoplastic plastic parent particles.
Described antistatic additive is being total to of CNT, Graphene, polyethers and the polyamide of non-ionic antistatic agent, modification
Polymers, metal powder, dibutyl oleamide, the compound of HMPA.Non-ionic antistatic agent, modified carbon are received
The copolymer of mitron, Graphene, polyethers and polyamide, metal powder, dibutyl oleamide, the mass ratio of HMPA
For 1:1:0.3:0.5:1.1:2:1.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is selected from KH550, KH560 and KH570 in connection agent
Three kinds compound, the mass ratio of KH550, KH560, KH570 and titanate coupling agent is 2:1:1:2), the quality of compounding coupling agent
For the montmorillonite added and the 1% of the quality sum of calcium carbonate, stir 2h ultrasonic cleaning tank 85 DEG C is ultrasonic, scattered suspension is subtracted
Pressure sucking filtration, adds at 60 DEG C and dries, grind to form homopolymerization granule standby.
Described non-ionic antistatic agent is fatty acid ester, glycollic amide, fatty alcohol-polyoxyethylene ether, polyol fatty acid
Ester, monoglyceride monostearate, oleic acid monoglyceride are the compound of Glycerol Monolaurate.Fatty acid ester, glycollic amide, fatty alcohol polyoxy
Vinyl Ether, polyol fatty acid ester, monoglyceride monostearate, the mass ratio of oleic acid monoglyceride are 2:1:1.3:0.5:2:1.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 8
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 100nm),
Zirconium aluminate, calcium carbonate (particle diameter is 100nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All with thermoplasticity
The mass percent of plastic master batch, antistatic additive is the 30.1% of thermoplastic plastic parent particles, and montmorillonite is that thermoplastic is female
The 6.6% of grain, zirconium aluminate is the 5.8% of thermoplastic plastic parent particles, and calcium carbonate is the 1.1% of thermoplastic plastic parent particles, dodecane
Base sodium sulfonate is the 12% of thermoplastic plastic parent particles, and glycol ester is the 9% of thermoplastic plastic parent particles, and stearate is thermoplasticity
The 3% of plastic master batch, acetone is the 5% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is selected from KH550, KH560 and KH570 in connection agent
Three kinds compound, the mass ratio of KH550, KH560, KH570 and titanate coupling agent is 2:1:1.2:1), the matter of compounding coupling agent
Amount is the montmorillonite added and the 1% of the quality sum of calcium carbonate, at the ultrasonic 2h that stirs of ultrasonic cleaning tank 85 DEG C, by scattered suspension
Decompression sucking filtration, adds at 60 DEG C and dries, grind to form homopolymerization granule standby.
Described antistatic additive is selected from non-ionic antistatic agent, Graphene, metal powder, electrically conductive graphite, dibutyl oleic acid acyl
Amine, HMPA, oxirane epoxy the third Anhui addition product of ethylenediamine, the compound of N oxygen ethylization alkylamine.Non-
Ionic anti-static agent, Graphene, metal powder, electrically conductive graphite, dibutyl oleamide, HMPA, ethylenediamine
Oxirane epoxy the third Anhui addition product, the mass ratio of N oxygen ethylization alkylamine are 2:1:1.3:0.5:2:1:1:1.
Described non-ionic antistatic agent is polyglycol ether, glycollic amide, fatty alcohol-polyoxyethylene ether, polyol fat
Acid esters, monoglyceride monostearate, oleic acid monoglyceride, the compound of Glycerol Monolaurate.Polyglycol ether, glycollic amide, fatty alcohol
Polyoxyethylene ether, polyol fatty acid ester, monoglyceride monostearate, oleic acid monoglyceride, the mass ratio of Glycerol Monolaurate are 3:2:
1.3:0.5:2:1:1。
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 9
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 100nm),
Zirconium aluminate, calcium carbonate (particle diameter is 100nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All with thermoplasticity
The mass percent of plastic master batch, antistatic additive is the 35.4% of thermoplastic plastic parent particles, and montmorillonite is that thermoplastic is female
The 7.5% of grain, zirconium aluminate is the 6.1% of thermoplastic plastic parent particles, and calcium carbonate is the 1.2% of thermoplastic plastic parent particles, dodecane
Base sodium sulfonate is the 15% of thermoplastic plastic parent particles, and glycol ester is the 10% of thermoplastic plastic parent particles, and stearate is thermoplastic
The 3.2% of property plastic master batch, acetone is the 6% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is selected from KH550, KH560 and KH570 in connection agent
Three kinds compound, the mass ratio of KH550, KH560, KH570 and titanate coupling agent is 2:1:1:1), the quality of compounding coupling agent
For the montmorillonite added and the 1% of the quality sum of calcium carbonate, stir 2h ultrasonic cleaning tank 85 DEG C is ultrasonic, scattered suspension is subtracted
Pressure sucking filtration, adds at 60 DEG C and dries, grind to form homopolymerization granule standby.
Described antistatic additive is non-ionic antistatic agent, dibutyl oleamide, HMPA, ethylenediamine
Oxirane epoxy the third Anhui addition product, the compound of N oxygen ethylization alkylamine.Non-ionic antistatic agent, dibutyl oleic acid
Amide, HMPA, oxirane epoxy the third Anhui addition product of ethylenediamine, the mass ratio of N oxygen ethylization alkylamine
For 1:2:1:3:1.9.
Described non-ionic antistatic agent is glycollic amide, fatty alcohol-polyoxyethylene ether, polyol fatty acid ester, stearic acid
Monoglyceride, Glycerol Monolaurate, the compound of polyoxyethylene carboxylate.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 10
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 60nm),
Zirconium aluminate, calcium carbonate (particle diameter is 60nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All mould with thermoplasticity
The mass percent of material master batch, antistatic additive is the 22% of thermoplastic plastic parent particles, and montmorillonite is thermoplastic plastic parent particles
0.5%, zirconium aluminate is the 1.05% of thermoplastic plastic parent particles, and calcium carbonate is the 0.7% of thermoplastic plastic parent particles, dodecyl sulphur
Acid sodium is the 1.2% of thermoplastic plastic parent particles, and glycol ester is the 5.5% of thermoplastic plastic parent particles, and stearate is thermoplasticity
The 0.5% of plastic master batch, acetone is the 0.5% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is selected from KH550, KH560 and KH570 in connection agent
Three kinds compound, the mass ratio of KH550, KH560, KH570 and titanate coupling agent is 2:1:1:1), the quality of compounding coupling agent
For the montmorillonite added and the 1% of the quality sum of calcium carbonate, stir 2h ultrasonic cleaning tank 85 DEG C is ultrasonic, scattered suspension is subtracted
Pressure sucking filtration, adds at 60 DEG C and dries, grind to form homopolymerization granule standby.
Described antistatic additive is quaternary ammonium alkyl and the HMPA of long-chain, the quaternary ammonium alkyl of long-chain and hempa
The mass ratio of acyl triamine is 20:1.5.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Embodiment 11
A kind of antistatic material easy to clean, including thermoplastic plastic parent particles, antistatic additive, montmorillonite (particle diameter is 60nm),
Zirconium aluminate, calcium carbonate (particle diameter is 60nm), dodecyl sodium sulfate, glycol ester, stearate and acetone；All mould with thermoplasticity
The mass percent of material master batch, antistatic additive is the 18% of thermoplastic plastic parent particles, and montmorillonite is thermoplastic plastic parent particles
0.5%, zirconium aluminate is the 0.56% of thermoplastic plastic parent particles, and calcium carbonate is the 0.5% of thermoplastic plastic parent particles, dodecyl sulphur
Acid sodium is the 1.2% of thermoplastic plastic parent particles, and glycol ester is the 1.5% of thermoplastic plastic parent particles, and stearate is thermoplasticity
The 0.5% of plastic master batch, acetone is the 0.5% of thermoplastic plastic parent particles.
Described montmorillonite is surface treated montmorillonite, and described calcium carbonate is surface treated calcium carbonate；Can
To use following operation: first pass through drainage screen screening montmorillonite and calcium carbonate, the montmorillonite after screening and the carbonic acid of 80 mesh
Calcium is poured in the aqueous solution of ethanol (volume fraction of ethanol is 98%, and the volume fraction of water is 2%), instills a certain amount of compounding idol
(compounding coupling agent includes silane coupler and titanate coupling agent, and silane coupler is selected from KH550, KH560 and KH570 in connection agent
Three kinds compound, the mass ratio of KH550, KH560, KH570 and titanate coupling agent is 2:1:1:1), the quality of compounding coupling agent
For the montmorillonite added and the 1% of the quality sum of calcium carbonate, stir 2h ultrasonic cleaning tank 85 DEG C is ultrasonic, scattered suspension is subtracted
Pressure sucking filtration, adds at 60 DEG C and dries, grind to form homopolymerization granule standby.
Described antistatic additive is the quaternary ammonium alkyl of long-chain, fatty acid ester and the compound of N oxygen ethylization alkylamine, long-chain
The mass ratio of quaternary ammonium alkyl, fatty acid ester and N oxygen ethylization alkylamine be 5:1:3.
During preparation, method below can be used: mix compounding for each component in formula, pelletize by proportioning together,
Injection mo(u)lding, the temperature of injection mo(u)lding is 190 DEG C.
Comparative example 1
With thermoplastic plastic parent particles as material, the purest ABS material.
Comparative example 2
Without montmorillonite on the basis of embodiment 3, remaining is the most same as in Example 3.
Comparative example 3
Without calcium carbonate on the basis of embodiment 3, remaining is the most same as in Example 3.
Comparative example 4
Without dodecyl sodium sulfate on the basis of embodiment 3, remaining is the most same as in Example 3.
Comparative example 5
Without glycol ester on the basis of embodiment 3, remaining is the most same as in Example 3.
Comparative example 6
Without stearate on the basis of embodiment 3, remaining is the most same as in Example 3.
Comparative example 7
Without acetone on the basis of embodiment 3, remaining is the most same as in Example 3.
Each embodiment and each comparative example are carried out effect detection respectively.
1, the detection method of surface resistivity is:
Surface resistivity is parallel to by the electric potential gradient of the sense of current on material surface and surface unit width
The ratio of electric current.
Surface resistivity can use sheet resistance tester directly to detect, and operational approach may refer to description.
The surface resistivity test instrunment of all Data Detection is QUICK 499D.
During use, measuring instrument is placed in testee surface, presses feeler switch, then show the sheet resistance of testee
Coefficient surface resistivity uses ASTM standard D-257 parallel pole method for sensing, uses the integrated amplification of high-precision OP-AMP
Device is measured automatically.
Surface resistivity: this parameter is for the certain thin-film material of thickness, and it is defined as the straight of unit length on surface
Stream pressure drop and unit width flow through the ratio of electric current.
The numerical value of surface resistivity is the smaller the better.The numerical value the least explanation antistatic effect of surface resistivity is strong, does not more allow
Easily it is stained with ash.
Experimental result is shown in Table 1.
2, the detection method of surface energy is:
The tolerance that intermolecular chemical bond is destroyed when can be and create material surface by surface.First first with contact angle detection instrument
After the contact angle on the surface that device detects object to be measured, it is possible to use YGG equation, harmonic equation or geometric equation carry out computational chart
Face energy.The numerical value of surface energy is the smaller the better, and interface does not more adhere to Organic substance and water, and dust-proof effect will be the best.Surface energy value
The least explanation is less susceptible to be stained with ash.Experimental result is shown in Table 1.
3, the detection method of imperial ash is:
Respectively prepared by each comparative example and each embodiment example fan and puts into inside the ducting system of a connection, the most past
Add the standard dust of the true dust of simulated atmosphere inside ducting system, every 2 hours, inside ducting system, add standard
Dust 20g.Fan stops a period of time after running a period of time, is considered as a cycle.Each cycle, soot blowing 10 minutes, quiet
Putting 10 minutes, soot blowing speed is 1-2m/s.Cycle is continuously 2 days.After experiment terminates, add up the ash quantity of being stained with of each testing sample
Summation.Repeatedly and carry out statistical analysis.And calculating imperial ash effect, imperial ash effect refers to modified flabellum at material prescription
It is stained with ash quantity down ratio above relatively primitive flabellum (i.e. comparative example 1) in the case of change.Imperial ash effect numerical value is the bigger the better.Experiment
The results are shown in Table 1.
Table 1 testing result.
In table 1, " Ω/ " refers to square resistance.
By the data of table 1 it can be seen that by add antistatic additive, montmorillonite, zirconium aluminate, calcium carbonate, dodecyl
Sodium sulfonate, glycol ester, stearate and acetone can reduce surface resistivity and surface energy, improve the effect of imperial ash.
Inventor further have adjusted the particle diameter of montmorillonite and calcium carbonate on the basis of embodiment 3, in each experiment,
Montmorillonite is identical with the particle diameter of calcium carbonate, and after multiple adjustment, the particle diameter of the montmorillonite in experiment and calcium carbonate is followed successively by: 10nm,
20nm, 30nm, 40nm, 50nm, 70nm, 71nm, 80nm, 90nm, 91nm, 95nm, 100nm, 110nm and 120nm, result of study
Showing, the particle diameter at montmorillonite and calcium carbonate is in the range of 50-100nm, and the antistatic imperial ash effect preparing material is preferable.When
The particle diameter of described montmorillonite is 50-70nm, and when the particle diameter of described calcium carbonate is 50-70nm, less addition just can be notable
Improve the performance of material.When the particle diameter of described montmorillonite is 71-90nm, when the particle diameter of described calcium carbonate is 71-90nm, be conducive to
Surface processes and dispersed.When the particle diameter of described montmorillonite is 91-100nm, when the particle diameter of described calcium carbonate is 91-100nm,
Have and easily disperse and be easy to the advantages such as industrialized production.
Fig. 4 and Fig. 5 is the results of comparison being stained with ash situation of comparative example and embodiment.Fig. 4 and Fig. 5 is all at the imperial ash of same detection
System in carry out the result that detects.This intrasystem amount of dust and concentration are very big, add dust the most inside, when testing one section
Between material surface be stained with the ash picture effect of dynamic bind static state dust stratification (test be), concrete operating procedure is with above-mentioned imperial ash
Detection method.According to Fig. 4 it can be seen that comparative example is stained with grey more, and embodiment 8 is stained with grey fewer, and embodiment 8 is when shorter
In even imperial ash.According to Fig. 5 it can be seen that comparative example is stained with grey more, and embodiment 1 is stained with grey fewer, and embodiment 1 is shorter
The most non-sticky ash in time.
Inventor has attempted again with acrylonitritrile-styrene resin, PA plastics, polyethylene, polypropylene, polrvinyl chloride, has gathered
Compounding as thermoplasticity of one or more in styrene, acronitrile-butadiene-styrene co-polymer and Merlon
Plastic master batch, also can obtain conclusion consistent with the above.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (12)
1. an antistatic material easy to clean, it is characterised in that include thermoplastic plastic parent particles, antistatic additive, montmorillonite, aluminic acid
Zirconium, calcium carbonate, dodecyl sodium sulfate, glycol ester, stearate and acetone；All with the percent mass of thermoplastic plastic parent particles
Than meter, antistatic additive is the 8%-39.4% of thermoplastic plastic parent particles, and montmorillonite is the 0.5%-8% of thermoplastic plastic parent particles,
Zirconium aluminate is the 0.5%-6.1% of thermoplastic plastic parent particles, and calcium carbonate is the 0.5%-1.2% of thermoplastic plastic parent particles, 12
Sodium alkyl sulfonate is the 1.2%-18.3% of thermoplastic plastic parent particles, and glycol ester is the 0.2%-of thermoplastic plastic parent particles
11.9%, stearate is the 0.1%-3.4% of thermoplastic plastic parent particles, and acetone is the 0.5%-of thermoplastic plastic parent particles
7.7%.
A kind of antistatic material easy to clean, it is characterised in that described thermoplastic plastic parent particles is selected from
Acrylonitritrile-styrene resin, PA plastics, polyethylene, polypropylene, polrvinyl chloride, polystyrene, acrylonitrile butadiene benzene
One or more in ethylene copolymer and Merlon.
A kind of antistatic material easy to clean, it is characterised in that the particle diameter of described montmorillonite is: 50-
100nm；The particle diameter of described calcium carbonate is: 50-100nm.
A kind of antistatic material easy to clean, it is characterised in that the particle diameter of described montmorillonite is 50-
70nm, the particle diameter of described calcium carbonate is 50-70nm；Or the particle diameter of described montmorillonite is 71-90nm, the particle diameter of described calcium carbonate is
71-90nm；Or the particle diameter of described montmorillonite is 91-100nm, the particle diameter of described calcium carbonate is 91-100nm.
5. according to antistatic material easy to clean a kind of described in any one of claim 1-4, it is characterised in that described montmorillonite is warp
Crossing the montmorillonite that surface processes, described calcium carbonate is surface treated calcium carbonate；The treating method comprises following steps:
Montmorillonite and calcium carbonate are mixed with ethanol solution, instills compounding coupling agent, compounding coupling agent and the montmorillonite of interpolation and carbonic acid
Calcareous amount sum mass percent be 0.5-2%, described compounding coupling agent is compounded by silane coupler and titanate coupling agent
Form, ultrasonic agitation, sucking filtration, dry, grind to form homopolymerization granule.
A kind of antistatic material easy to clean, it is characterised in that described antistatic additive is selected from cation
Antistatic additive, anionic antistatic agents, non-ionic antistatic agent, modified CNT, Graphene, polyethers and polyamide
Copolymer, metal powder, electrically conductive graphite, dibutyl oleamide, HMPA, oxirane epoxy third Anhui of ethylenediamine
Compounding of one or more in addition product, N oxygen ethylization alkylamine.
A kind of antistatic material easy to clean, it is characterised in that described cationic antistatic agent is selected from
In the quaternary ammonium alkyl of long-chain, phosphate and naphthenic acid salt high-molecular polymer, one or more is compounding.
A kind of antistatic material easy to clean, it is characterised in that described anionic antistatic agents is selected from
Answering of one or more in the alkali metal salt of alkyl sulfonic acid, alkyl sodium sulfate, carboxylate, phosphate and aminodithioformic acid
Join.
A kind of antistatic material easy to clean, it is characterised in that described non-ionic antistatic agent selects
From ethoxylated fat race alkylamine, macrogol ester or ether, fatty acid ester, glycollic amide, fatty alcohol-polyoxyethylene ether, polynary
One or several in alcohol fatty acid ester, monoglyceride monostearate, oleic acid monoglyceride, Glycerol Monolaurate, polyoxyethylene carboxylate
That plants is compounding.
10. the preparation method of an antistatic material easy to clean, it is characterised in that comprise the following steps: according to claim 1-9
Each component is compounded together by the proportioning described in any one, mixing, pelletize.
11. 1 kinds of antistatic products easy to clean, it is characterised in that the material of this product includes described in any one of claim 1-9
Antistatic material easy to clean.
12. according to antistatic product easy to clean a kind of described in claim 11, it is characterised in that described product be fan, impeller,
The aerofoil fan of air-conditioning, steam cleaner dust stratification bucket, electric appliance casing, plastic sheeting or electric plastics device.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018200138A (en) * | 2017-05-26 | 2018-12-20 | コンティニューム株式会社 | Air conditioner operation method and net-like resin molding |
| JP2019085583A (en) * | 2019-02-18 | 2019-06-06 | コンティニューム株式会社 | Net resin molding |
| WO2020105184A1 (en) * | 2018-11-22 | 2020-05-28 | コンティニューム株式会社 | Reticular resin molding and air-conditioner operating method using same |
| CN113773718A (en) * | 2020-06-10 | 2021-12-10 | 海信（山东）空调有限公司 | Cross flow fan and air conditioner regulator |
| CN114072284A (en) * | 2019-07-08 | 2022-02-18 | 株式会社Tbm | Printing paper and method for manufacturing printing paper |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033316A (en) * | 2006-03-08 | 2007-09-12 | 天津乐金塑钢门窗有限公司 | Polyvinyl chloride antistatic dust-proof modified window section bar and producing method thereof |
| CN102993567A (en) * | 2011-09-09 | 2013-03-27 | 合肥杰事杰新材料股份有限公司 | Antistatic low haze polypropylene composite material, preparation method and application |
| JP2013199611A (en) * | 2012-03-26 | 2013-10-03 | Toppan Forms Co Ltd | Antistatic composition and molding |
| CN103709627A (en) * | 2012-09-29 | 2014-04-09 | 青岛欣展塑胶有限公司 | Anti-static and flame-retardant reinforcing and toughening type PBT master batch |
| CN103849028A (en) * | 2012-12-04 | 2014-06-11 | 青岛三利中德美水设备有限公司 | Antistatic flame-retardant reinforcing and toughening master batch |
| JP5647908B2 (en) * | 2011-01-31 | 2015-01-07 | トッパン・フォームズ株式会社 | Antistatic composition and molded article |
| CN105885206A (en) * | 2014-11-05 | 2016-08-24 | 安徽邦尼新材料有限公司 | Automobile interior trim part material and preparation method thereof |
-
2016
- 2016-09-30 CN CN201610876555.1A patent/CN106317757B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033316A (en) * | 2006-03-08 | 2007-09-12 | 天津乐金塑钢门窗有限公司 | Polyvinyl chloride antistatic dust-proof modified window section bar and producing method thereof |
| JP5647908B2 (en) * | 2011-01-31 | 2015-01-07 | トッパン・フォームズ株式会社 | Antistatic composition and molded article |
| CN102993567A (en) * | 2011-09-09 | 2013-03-27 | 合肥杰事杰新材料股份有限公司 | Antistatic low haze polypropylene composite material, preparation method and application |
| JP2013199611A (en) * | 2012-03-26 | 2013-10-03 | Toppan Forms Co Ltd | Antistatic composition and molding |
| CN103709627A (en) * | 2012-09-29 | 2014-04-09 | 青岛欣展塑胶有限公司 | Anti-static and flame-retardant reinforcing and toughening type PBT master batch |
| CN103849028A (en) * | 2012-12-04 | 2014-06-11 | 青岛三利中德美水设备有限公司 | Antistatic flame-retardant reinforcing and toughening master batch |
| CN105885206A (en) * | 2014-11-05 | 2016-08-24 | 安徽邦尼新材料有限公司 | Automobile interior trim part material and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018200138A (en) * | 2017-05-26 | 2018-12-20 | コンティニューム株式会社 | Air conditioner operation method and net-like resin molding |
| WO2020105184A1 (en) * | 2018-11-22 | 2020-05-28 | コンティニューム株式会社 | Reticular resin molding and air-conditioner operating method using same |
| CN113348336A (en) * | 2018-11-22 | 2021-09-03 | 肯梯钮穆株式会社 | Net-shaped resin molded article and method for operating air conditioner using same |
| CN113348336B (en) * | 2018-11-22 | 2022-11-15 | 肯梯钮穆株式会社 | Net-shaped resin molded article and method for operating air conditioner using same |
| JP2019085583A (en) * | 2019-02-18 | 2019-06-06 | コンティニューム株式会社 | Net resin molding |
| CN114072284A (en) * | 2019-07-08 | 2022-02-18 | 株式会社Tbm | Printing paper and method for manufacturing printing paper |
| CN114072284B (en) * | 2019-07-08 | 2024-01-05 | 株式会社Tbm | Method for manufacturing printing paper Zhang Ji |
| CN113773718A (en) * | 2020-06-10 | 2021-12-10 | 海信（山东）空调有限公司 | Cross flow fan and air conditioner regulator |
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|---|---|
| CN106317757B (en) | 2018-11-13 |
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