CN106868853A - A kind of anlistatig carbon black fibre rubber composite and preparation method thereof, antistatic products - Google Patents
A kind of anlistatig carbon black fibre rubber composite and preparation method thereof, antistatic products Download PDFInfo
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Abstract
The invention discloses a kind of anlistatig carbon black fibre rubber composite and preparation method thereof, antistatic products.The present invention is comprised the following steps：(1) it is cationized from conductive black particle and to particle, obtains cation carbon black particle；By the abundant shredding dispersion of fiber and fibrosis, and it is diluted to slurry；(2) to obtained cation carbon black particle is added in the slurry, fiber surface can be covered in；(3) again to addition latex and compounding ingredient in step (2) gained material, and latex and compounding ingredient is made to be fully contacted fiber；(4) then it is made to flocculate completely to addition flocculant in step (3) gained material；(5) step (4) gained material dehydrate and roll-in is to predetermined density, obtain final product product.Obtained composite property of the invention can keep dynamical conductivity level, and (such as conductance is 103~105Ω .cm), but the usage amount of conductive black can at least lower 60%.
Description
Technical field
The present invention relates to a kind of anlistatig carbon black fibre rubber composite and preparation method thereof, antistatic products.
Background technology
With the high development of China's science and technology and electronics industry, various electronic instruments, the making of equipment and use
Sensitivity is also constantly being improved.Electrostatic is the class that manufacture or must be worried using highly sensitive electronic instrument and electronic equipment
Topic.Electrostatic can be produced by the friction of different objects (such as sole and floor), when electronic working personnel in operating room back and forth
When walking about, up to ten thousand volts of voltage can be often accumulated with without feeling (because electric current is low).But when electronic product close to electrostatic
During the environment of electric field, the electric field of the special electrostatic of one or two hectovolt just can cause serious influence very to electronic instrument or electronic equipment
To cause destruction.There is random fault, bungle or operation mistake in electrostatic when not only can run computer, but also may
Some components can be caused, such as CMOS, MOS circuit, twin-stage circuit puncture and damage.In addition electrostatic is to the outer of computer
Portion's equipment also has obvious influence, and the display device with cathode-ray tube when by electrostatic interference, can cause image disorderly,
It is smudgy.Electrostatic can also cause the work such as Modem, network interface card, Fax not normal, the failure such as the printing of printer is abnormal.Electrostatic gathers
Electrostatic spark can be also produced after product, catastrophic failure is caused in inflammable and explosive Workplace.Therefore, between precision instrument and prevent fires
Higher ranked place, country is required to carry out antistatic process.A kind of effective antistatic or scattered consumption electrostatic can be provided
Product is that everybody is intended to.
In general, the resistivity of the antistatic material of the environment antistatic article requirements in industrial production place is 105~
109Ω .cm, the antistatic process that antistatic requirement environment higher, such as instrument place are used, such as antistatic floor requirement resistance
Rate is 103~105Ω.cm.Many equipment using in electronic instrument and electronic equipment be all rubber (such as floor, foot pad,
Desktop Cover Gasket or mouse pad), but the electrical property of ordinary rubber is that (resistivity is 10 to nonconducting insulator11~1015Ω .cm),
The elastomeric material of insulation is become conduction and add conductive material in elastomeric material, conventional conductive articles include metal
The antistatic activity agent of powder, conductive black and ionic.Metal powder is outstanding conductive material, but have the disadvantage it is expensive,
Also the elastic and flexibility of rubber can be influenceed, therefore is used few.Antistatic activity agent can make the conductance that rubber reaches only be
107~106Ω .cm, are not maximally effective conductive materials.Most conductive rubber material is manufactured using conductive black.With
The electrical conduction mechanism of the conductive rubber that conductive black is made has two：(1) electrical conductivity of percolation theory --- conductive material is filled out with conduction
The concentration of charge is relevant, and when conductive filler reaches a certain amount of (critical volume fraction), conducting particles can be formed in rubber bodies
The network of one conduction makes conductance special change occur and greatly improve.(2) tunnel conduction is theoretical --- in conducing composite material,
The electrical conductive behavior of conductive network does not simultaneously need the directly contact of particle to come conductive, but when the distance between conducting particles is close to one
It is fixed apart from when (relevant with critical volume fraction), the electronics of conducting particles can be conductive by " transition " between particle.It is comprehensive
The electrical conduction mechanism of the above is closed, available summary is：Conducting particles concentration in rubber bodies is bigger, and rubber electric conductivity is stronger,
Conducting particles needs to reach a certain amount of " critical volume fraction " that can be only achieved rubber electric conductivity, by theoretical calculation, if with one
As conductive black manufacture resistance 103~105The anti-static conductive rubber of Ω .cm, the volume of conductive black consumption needs to reach
The 35%~40% of whole rubber combined body just may be used.
The content of the invention
For drawbacks described above, the conduction material containing carbon black is manufactured it is a primary object of the present invention to provide a kind of new technology
Material, new technology can produce the material of high-effect conductivity level in the case of the conductive black using a small amount of.
The present invention is achieved through the following technical solutions：
A kind of anlistatig carbon black fibre rubber composite, the composite is prepared from the following ingredients in percentage by system
Into：Fiber 70~92%, cationization conductive black particle 3~25%, latex 2~8%, compounding ingredient 0.1~1%；It is above-mentioned each
Weight percentages of components sum is 100%.
Further, the charge potential ＞ 25mv of the cationization conductive black particle.
A kind of preparation method of anlistatig carbon black fibre rubber composite, comprises the following steps：
(1) it is cationized from conductive black particle and to particle, obtains cation carbon black particle；Fiber is fully opened
Pine dispersion and fibrosis, and it is diluted to slurry；
(2) to obtained cation carbon black particle is added in the slurry, fiber surface can be covered in；
(3) again to addition latex and compounding ingredient in step (2) gained material, and latex and compounding ingredient is made to be fully contacted fibre
Dimension；
(4) then it is made to flocculate completely to addition flocculant in step (3) gained material；
(5) step (4) gained material dehydrate and roll-in is to predetermined density, obtain final product product.
Further, the conductive black particle is acetylene carbon black, conductive furnace black or conductive channel black.
Yet further, the particle diameter≤100nm of the conductive black particle, after its cationization, charge potential ＞ 25mv.
Specifically, the fiber is string or synthetic fibers.
Specifically, the compounding ingredient is one or more in vulcanizing agent, age resistor, dispersant or flocculant.
Specifically, the latex is the butyronitrile latex containing negative electricity, butadiene-styrene latex, neoprene latex, natural emulsion, polypropylene breast
One or more in glue.
Specifically, the string is wood pulp cellulose, bamboo fibre or flaxen fiber.
Specifically, the synthetic fibers are acrylic fibers, aramid fiber, polyester fiber or amine synthetic fibre.
A kind of antistatic products, be by anlistatig carbon black fibre rubber composite by shredding dispersion after, then with powder
Shape plastics or powder rubber mix, and heated pressurization is made anlistatig plastic product or rubber product, the conductive charcoal of the product
The carbon black that common (without described anlistatig carbon black fibre rubber composite) the carbon black antistatic products of black amount ratio are used
Reduce 4 to 6 times.
Theory of the invention is in the environment of doing medium with water, using by micro fibrillation or scattered fiber, first to build
It is in advance that (a kind of cationic microparticles are high for CN104231355B with notification number in another separate program into a network struction
The preparation method of performance encapsulant) patent in the improving particle surface method that discloses cationization carried out to conductive black change
Property.Because in the environment of aqueous medium, the surface of general fiber can all be presented negative electrical charge, modified positively charged (cation)
When conductive black is added to scattered network of fibers framework, carbon black particle will be close over the fiber table in network of fibers framework
Face, that is, conductive black can form an effective conduction framework by network of fibers framework.Increase carbon black and fiber
Between absorption affinity, latex can be in right amount added in a program, make the adhesion of carbon black and fiber surface tight.Carbon black/fibre structure is built
Cheng Hou, shredding and then can also be selectively added different rubber or plastics and then by roll-in, the rear operation of thermoplastic etc. again
It is formed in the product of different antistatic environmental applications.
The preparation technology of conductive black cationization of the present invention is as follows：
With reference in patent of invention " a kind of preparation method of cationic microparticles high-performance sealed material, notification number：
The technique for disclosing mineral microparticle cationization in CN104231355B ", the program of conductive black cationization can use phase
Same technique；The chemical material that conducting particles cationization is used can be included into various water soluble polymer cationic polyelectrolytes
[such as poly dimethyl allyl ammonium chloride, such as epichlorohydrin (Epichlorohydrin) and polyurethane (such as amide-
Polymethyldiallylamine) blend and polyethyleneimine (Polyethylenimine)], it is also possible to use metal
Ionic electrolytes, such as aluminum chlorohydrate (Aluminum Chlorohydrate).The present invention can use above-mentioned chemicals,
The outer any polyelectrolyte that can be adsorbed in above-mentioned mineral particle of above-mentioned chemicals or metal ion electricity can be used
Xie Zhi, makes mineral microparticle be cationized.In case study on implementation of the invention, the present invention compares and has used epichlorohydrin
(Epichlorohydrin) with the compound of polyurethane (such as amide-polymethyldiallylami ne) and
Two kinds of water-soluble macromolecule electrolytes of polyethyleneimine (Polyethylenimine).The step of conductive black particulate cation
Measure with charge potential can be carried out by following procedure：
1st, the cationic polyelectrolyte selected is disperseed with the water stirring and dissolving of appropriate capacity, stirring the equipment that uses can be with
It is the mixer [such as slurry leaf agitator or Cauer this blade agitators (Cowles Blade Mixer)] for typically making coating.
2nd, allow cationic polyelectrolyte to be stirred 2~3 minutes in agitator, cationic polyelectrolyte is fully dissolved in water.
3rd, quantitative conductive black particle is blown slowly and adds the cationic polymer electrolyte solution of agitator, continue to stir agitator
Interior conductive black mix particles liquid, suitably adjusts and reform mixing speed, it is to avoid conductive black mix particles liquid produces flocculation sediment.Need
When wanting, appropriate dispersant can be added agitator in advance before conductive black particle is added, help dispersed electro-conductive carbon black particle.
4th, after adding all predetermined conductive black particulates, continue to stir mixed liquor about 30 minutes, make cationic polyelectrolyte
There is time enough to be adsorbed in conductive black particle surface.
5th, the charge potential number of degrees of sampling and testing conductive black mix particles liquid.
What deserves to be explained is：The conductive black particle of cationization is set effectively and stably tightly to invest the fiber of raw material
Surface, the charge potential of the conductive black particle of cationization is preferably more than 25mv.
The present invention has advantages below and beneficial effect：
The performance of composite of the present invention can keep dynamical conductivity level, and (such as conductance is 103~105Ω .cm),
But the usage amount of conductive black can at least lower 4 to 6 times.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of anlistatig carbon black fibre rubber composite, the composite by percentage by weight be 90% it is wooden
Fiber, 5% cationization conductive black particle, 4.5% butyronitrile latex (latex of butyronitrile 26), 0.5% compounding ingredient；Specifically
Prepare as follows：
The particle size for preparing cationization conductive black particle is the conductive black particle (acetylene carbon black) of 25nm sizes,
When the composite of embodiment 1 is prepared, first in the consumption of conductive black particle particulate the electrolyte of 0~1.0% ratio
(A1：Epichlorohydrin (Epichlorohydrin) and polyurethane (such as amide-polymethyldiallylamine)
Compound) slowly add the agitator for containing 150cc water, make A1 within 3~5 minutes with the rotating speed stir about not less than 250rpm
Electrolyte fully dissolves dispersion.To slowly adding conductive black particulate, dispersed with stirring 30 minutes in agitator.From particulate mixed liquor
The electric charge of middle sampling and measuring conductive black particulate, confirms that the electric charge of the conductive black particulate of cationization meets application claims.
The electric charge of the cationization conductive black particle of embodiment 1 is 31.5mv.
With another electronic leaf agitator (Warren Blender China logical sequence electric mixer), add 700cc water with it is wooden
Fiber, wood pulp cellulose is stirred about 1 minute with (about 400~450rpm) at a high speed, disperses the abundant shredding of fiber.Stirred slurry is kept
In the state of mixing, add with the cationization conductive black particle got ready slowly, be kept stirring for making within 30 minutes cationization conductive
Carbon black particle has sufficient time and fiber contacts and covers on its surface.
During compounding ingredient is added (be diluted with water to 25% solid content) butyronitrile latex in advance, stirring makes compounding ingredient be mixed with latex
Close (compounding ingredient includes sulphur, zinc oxide, vulcanization accelerator, age resistor and stabilizer etc.).The stirring of the container containing slurry
Speed increases to 600rpm, adds latex compound, continues stir about 20 minutes.Now slurry should be reached and approach what is flocculated completely
State (flocculation is that latex is separated with aqueous medium completely completely, and the aqueous solution is changed into clear from muddiness), adds the sulphur of a small amount of on demand
Sour aluminium completely flocculates slurry shaping.With handsheet machine (container comprising screen cloth and vacuum pumping device) de-watering of slurries
Shaping, then presses density requirements handsheet roll-in to certain thickness being dried into the handsheet opened with dryer with roll squeezer
Degree, so as to obtain conductive material of the invention (materials A).The sheet resistance for measuring materials A obtains 4.5x105Ω/sq, materials A
Density is 0.86gm/cc.
The measure of the surface resistivity of materials A is carried out by ASTM (American National Standard method of testing) D-257 standards, tool
Body method is that (two gold-plated electrodes of circular concentric --- interior electrode is in the form of annular discs, and external electrode is round packing ring by two electrodes
Shape) surface of test sample is placed on, it is the contact for enabling electrode and sample surfaces to keep good, one 5 pounds can be placed on electrode
The weights of (about 2.2 kilograms).Add a 500V volts of (DC) voltage in interior electrode during test, determined with electrometer after being powered one minute
Two interelectrode steady resistances, [/L is (outward for W (distance between resistance) for the physical dimension function for being multiplied by using electrode with the resistance readings
Resistance girth)] surface resistivity of sample, i.e. ohm/sq or Ω/sq can be calculated.
Embodiment 2 is to embodiment 7
Embodiment 2 is just the same with embodiment 1 to the preparation method of embodiment 7, the latex (butyronitrile 26) that uses and coordinates
Agent is also in the same manner as in Example 1, while consumption is same, to be a difference in that the consumption of cationization conductive black particle is different,
Wood fibre also with cationization conductive black particle increase and decrease and relative adjustment (being shown in Table 1)：
Table 1
Upper table is shown the surface resistivity of the sample that embodiment 2 is made to embodiment 7 by the preparation method of embodiment 1
And density.
Embodiment 8
The preparation method of embodiment 8 is same as Example 1, but the latex for using is butadiene-styrene latex (butylbenzene 33), each raw material
Consumption it is same as Example 1, the sheet resistance of the sample of embodiment 8 prepared is 9.2 × 104Ω/sq。
Embodiment 9
A kind of anlistatig carbon black fibre rubber composite, the composite is by aramid fiber that percentage by weight is 80%
Fiber, 15% cationization conductive black particle, 4.5% butyronitrile latex (latex of butyronitrile 26), 0.5% compounding ingredient, system
Preparation Method is same as Example 1, and the sheet resistance of the sample prepared is 3.2 × 103Ω/sq。
Embodiment 10
A kind of anlistatig carbon black fibre rubber composite, the composite is by acrylic fibers that percentage by weight is 80%
Fiber, 15% cationization conductive black particle, 4.5% butyronitrile latex (latex of butyronitrile 26), 0.5% compounding ingredient, system
Preparation Method is same as Example 1, and the sheet resistance of the sample prepared is 6.1 × 103Ω/sq。
Embodiment 11
Embodiment 11 is the case of the plastic products that the conductive fiber being made using the present invention manufactures antistatic.It is real preparing
Before applying the sample of example 11, the method for being described with embodiment 1 in advance is made the conductive fiber that cation carbon black is covered with following formula：
71.1 grams of wood fibre, 20.2 grams of acetylene carbon black of cationization, 8.2 grams of 26 latex of butyronitrile, 0.5 gram of compounding ingredient, operation moisture are (total
Amount) 4000cc.
The preparation method of the fiber in the sample of embodiment 11 is completely the same with embodiment 1, is uniquely a difference in that by reality
Apply example 11 and be formulated the fibre stuff that is made after dewatering, after pulpboard (material B) drying and need not move through such as (the material of embodiment 1
A) the further roll-in program of description.
The specific preparation method of the sample of embodiment 11 is as follows：
1. from the conductive fiber material B of above-mentioned preparation weigh 10 grams (or equal weigh ratio) it is standby, another 140 grams of preparation (or
It is equal weigh than) powdery HDPE high density polyethylene (HDPE)s (Qatar HDPE that the plastics market as can have been bought, model
MG70, mesh number 80 to 120).
2. stirred with middling speed (300-350rpm) and mixed (about 45 seconds) to material B and HDPE are full and uniform.
3. the conductive fiber and HDPE that stirring are mixed move and are put in another standby square stainless steel and touch tool, with 135 DEG C of temperature,
4MPa pressure, 10 minutes are compressing conductive fiber and HDPE blend compositions.Be prepare embodiment 11 sample.
The conductive fiber content of the sample of embodiment 11 is the 6.7% of sample total amount, and conductive black content is sample total amount
1.7%, the sheet resistance of the sample of embodiment 11 measurement is 7.5 × 106Ω/sq。
Embodiment 12 is to embodiment 16
Embodiment 12 is completely the same with embodiment 11 to the preparation method of the sample of embodiment 16, is a difference in that in embodiment
In the sample of 12 to embodiment 16, conductive black fiber rubber composite (abbreviation conductive fiber) content (is also conductive black
Content), specific as follows table 2 different with the sample of embodiment 11：
Table 2
The above-mentioned conductive fiber content (being also the content of conductive black) that sample obtained in embodiment 11~16 is shown
With the sheet resistance for being made sample.
Embodiment 17
The preparation method of the conductive fiber in the sample of embodiment 17 and completely the same [the conductive fiber content of embodiment 13
20% (content 5% of conductive black), the content of remaining raw material is same as Example 1], preparation method and the embodiment 13 of sample
Also it is identical, it is a difference in that the plastics in embodiment 17 are polyvinyl chloride (PVC, 120 mesh), rather than embodiment 13
In high density polyethylene, the sheet resistance measured after the sample being made is 7.2 × 104Ω/sq。
Embodiment 18
The preparation method of the conductive fiber in the sample of embodiment 18 [conductive fiber content 20% consistent with embodiment 13
(content 5% of conductive black), the content of remaining raw material is same as Example 1], the preparation method of sample is also complete with embodiment 13
It is exactly the same, do not exist together be in embodiment 18 be the rubber of powdery butyronitrile 26 (200 mesh), rather than embodiment 13 in it is highly dense
Degree polyethylene HDPE, the sheet resistance measured after the sample being made is 3.1x104Ω/sq。
Embodiment 19 is to embodiment 23
Embodiment 19 to embodiment 23 shows with conductive black (acetylene carbon black that i.e. foregoing case is used), without system
Into conductive fiber, the electric conductivity of conductive black X fillings HDPE samples (sample C) prepared after mixing with powdery HDPE, sample
Mixed method carried out completely in accordance with the description in embodiment 11 with compression moulding preparation method, table 3 below is shown with different amounts of
The sample surfaces resistivity that the HDPE sample measurements that conductive black is made draw.
Table 3
The result of comparison sheet 2 and table 3 can fully prove to be made the excellent of antistatic article using conductive fiber of the invention
More property；The carbon black loading that the antistatic sample that general conductive black filling HDPE is made is used is with the carbon black loading of conductive fiber
4~6 times can be only achieved equal conductive effect.In addition it is worth mentioning that：The antistatic sample of fibre-bearing is because the benefit of fiber
Pretend use, no matter intensity, wearability, or ageing resistance is all stronger than not fibrous antistatic sample.
It should be noted that above example is only used to illustrative and not limiting technical scheme, although with reference to upper
Embodiment is stated to be described in detail the present invention, it will be understood by those within the art that：
The present invention can still be modified or equivalent, without departing from the spirit and scope of the present invention any
Modification or local replacement, it all should cover in scope of the presently claimed invention.
Claims (10)
1. a kind of anlistatig carbon black fibre rubber composite, it is characterised in that the composite is by following weight percent
The component of ratio is made：Fiber 70~92%, cationization conductive black particle 3~25%, latex 2~8%, compounding ingredient 0.1~
1%；Above-mentioned each component percentage by weight sum is 100%.
2. a kind of anlistatig carbon black fibre rubber composite according to claim 1, it is characterised in that the sun from
The charge potential ＞ 25mv of sonization conductive black particle.
3. a kind of preparation method of anlistatig carbon black fibre rubber composite, it is characterised in that comprise the following steps：
(1) it is cationized from conductive black particle and to particle, obtains cation carbon black particle；By the abundant shredding of fiber point
Dissipate and fibrosis, and be diluted to slurry；
(2) to obtained cation carbon black particle is added in the slurry, fiber surface can be covered in；
(3) again to addition latex and compounding ingredient in step (2) gained material, and latex and compounding ingredient is made to be fully contacted fiber；
(4) then it is made to flocculate completely to addition flocculant in step (3) gained material；
(5) step (4) gained material dehydrate and roll-in is to predetermined density, obtain final product product.
4. a kind of preparation method of anlistatig carbon black fibre rubber composite according to claim 3, its feature exists
In the conductive black particle is acetylene carbon black, conductive furnace black or conductive channel black.
5. a kind of preparation method of anlistatig carbon black fibre rubber composite according to claim 3, its feature exists
In, the particle diameter≤100nm of the conductive black particle, after its cationization, charge potential ＞ 25mv.
6. a kind of preparation method of anlistatig carbon black fibre rubber composite according to claim 3, its feature exists
In the fiber is string or synthetic fibers.
7. a kind of preparation method of anlistatig carbon black fibre rubber composite according to claim 3, its feature exists
In the compounding ingredient is one or more in vulcanizing agent, age resistor, dispersant or flocculant.
8. a kind of preparation method of anlistatig carbon black fibre rubber composite according to claim 3, its feature exists
In, the latex be one kind in the butyronitrile latex containing negative electricity, butadiene-styrene latex, neoprene latex, natural emulsion, polypropylene emulsion or
It is various.
9. a kind of preparation method of anlistatig carbon black fibre rubber composite according to claim 3, its feature exists
In the string is wood pulp cellulose, bamboo fibre or flaxen fiber；The synthetic fibers are acrylic fibers, aramid fiber, polyester fiber or amine
Synthetic fibre.
10. a kind of antistatic products, it is characterised in that disperseed by shredding by anlistatig carbon black fibre rubber composite
Afterwards, then with powdered plastic or powder rubber mix, heated pressurization is made anlistatig plastic product or rubber product.
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| CN111500080A (en) * | 2020-05-09 | 2020-08-07 | 广东华凯科技股份有限公司 | Antistatic latex fiberboard, preparation method thereof and shoe sole |
| CN114753024A (en) * | 2022-04-08 | 2022-07-15 | 广东国兴乳胶丝有限公司 | Preparation method and device of telescopic conductive latex yarn |
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Application publication date: 20170620 |