CN105820634B - A kind of graphene-carbon black composite electrically-conducting paint and its preparation method and application - Google Patents
A kind of graphene-carbon black composite electrically-conducting paint and its preparation method and application Download PDFInfo
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- CN105820634B CN105820634B CN201510005132.8A CN201510005132A CN105820634B CN 105820634 B CN105820634 B CN 105820634B CN 201510005132 A CN201510005132 A CN 201510005132A CN 105820634 B CN105820634 B CN 105820634B
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Abstract
The invention discloses a kind of graphene carbon black composite electrically-conducting paints and its preparation method and application, wherein, the graphene carbon black composite electrically-conducting paint that the present invention is prepared by solution blended process contains graphene carbon black dispersion liquid, the first water-base resin and the first dispersant, on the basis of first water-base resin of 100 parts by weight, the content of the graphene carbon black dispersion liquid is 80 350 parts by weight, and the content of first dispersant is 3 10 parts by weight.And the conductive coating can be applicable on electrical heating, electromagnetic shielding, printed electronic circuit, thin film switch and lithium battery.The present invention improves the electric conductivity of the conductive coating；The compatibility of carbon black and resin is preferable simultaneously, and mechanical property increases, and cost is relatively low and the water-base resin is environmental protection type resin, pollution-free, for the conductive coating can practical application provide theoretical foundation and practical basis.
Description
Technical field
The invention belongs to conductive coating fields, in particular it relates to a kind of environment-friendly type graphene-carbon black composite conducting
Coating and preparation method thereof and the environment-friendly type graphene-carbon black composite electrically-conducting paint are in electromagnetic shielding, electronic circuit, film
The application in the fields such as switch and lithium battery.
Background technology
Addition type conductive coating develops fast because can be widely applied to the fields such as electromagnetic shielding, antistatic, electronic circuit
Speed develops a variety of strong electric conductivity conductive coatings in succession, such as conductive filler mainly has metal system (silver powder, copper powder, nickel powder), gold
Compound, carbon system (graphite, carbon black) of category/glass etc..But the mechanical property and electric conductivity of these current conductive coatings are difficult to carry simultaneously
Height limits its scope of application.
Graphene is a kind of new material for the individual layer laminated structure being made of carbon atom, has extremely low resistivity and excellent
Mechanical property, be very suitable for for preparing conductive material, and the conductive coating prepared using graphene as conductive filler has
Good electric conductivity, but industrialization is also not implemented in single-layer graphene at present, and only layer graphene slurry realizes industrialization less,
When applying in conductive coating, since graphene has lamellar structure, contact resistance is larger between lamella and lamella, between existing
The phenomenon that gap, conductive network can have certain defect, while will appear conductive coating and being easy to reunite, bad dispersibility, therefore meeting
Cause resistance larger, poorly conductive.There is researcher that a small amount of metal conductive particles, such as nano silver, nickel etc., but gold can be added
Belonging to conducting particles, that there are costs is higher, while the problem of with environmental protection type resin poor compatibility.
Therefore, how to prepare electric conductivity and conductive coating that mechanical property all improves need further to study and
Exploitation.
Invention content
It is an object of the invention to overcome, the Electrical Conductivity of Conductive Coating of the prior art is poor, mechanical property is low and of high cost
Defect, and improve a kind of graphene-carbon black composite electrically-conducting paint.
To achieve the goals above, the present invention provides a kind of graphene-carbon black composite electrically-conducting paint, wherein the graphene-
Carbon black composite electrically-conducting paint contains graphene-carbon black dispersion liquid, the first water-base resin and the first dispersant, with 100 parts by weight
On the basis of first water-base resin, the content of the graphene-carbon black dispersion liquid is 80-350 parts by weight, first dispersion
The content of agent is 3-10 parts by weight.
The present invention also provides a kind of preparation method of graphene-carbon black composite electrically-conducting paint, this method includes following step
Suddenly：
(1) grinding matrix, watersoluble plumbago alkene and the second dispersant are stirred under the first stirring condition, are then added again
Enter carbon black and is stirred under the second stirring condition；
(2) mixture that will be obtained through step (1) is ground；
(3) the first water-base resin and first point will be added in the graphene-carbon black dispersion liquid obtained after step (2) grinding
Powder simultaneously stirs under third stirring condition.
The present invention also provides the graphene prepared by above-mentioned preparation method-carbon black composite electrically-conducting paints.
The present invention also provides the graphene-carbon black composite electrically-conducting paints in electrical heating, electromagnetic shielding, printed electronic line
Application on road, thin film switch and lithium battery.
Graphene-carbon black composite electrically-conducting paint of the present invention is formed as reticular structure, and the carbon black dispersion is in the net
In shape structure so that the carbon black serves as the node of the reticular structure of the conduction, and " point connects with adjacent graphene platelet progress
Touch ", that is, no longer " piece-piece " contacts between graphene platelet and graphene platelet, and is formed as " piece-point " contact, to increase
The quantity of graphene conductive network path, auxiliary improve graphite network, improve the electric conductivity of the conductive coating；
The compatibility of conductive black and resin is preferable simultaneously, and mechanical property increases, and cost is relatively low and this is first aqueous
Resin, the second water-base resin, filler and auxiliary agent etc. are environment-friendly type, pollution-free, being capable of practical application for the conductive coating
Provide theoretical foundation and practical basis.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the scanning electron microscope image of the 1 graphene-carbon black dispersion liquid prepared according to an embodiment of the invention；
Fig. 2 is the reticular structure signal of the 1 graphene-carbon black composite electrically-conducting paint prepared according to an embodiment of the invention
Figure；And
Fig. 3 is the scanning electron microscope image of the 1 graphene-carbon black composite electrically-conducting paint prepared according to an embodiment of the invention.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of graphene-carbon black composite electrically-conducting paints, wherein the graphene-carbon black composite guide electropaining
Material contains graphene-carbon black dispersion liquid, the first water-base resin and the first dispersant, with the described first aqueous tree of 100 parts by weight
On the basis of fat, the content of the graphene-carbon black dispersion liquid is 80-350 parts by weight, and the content of first dispersant is 3-10
Parts by weight.
According to the present invention, on the basis of first water-base resin of 100 parts by weight, the graphene-carbon black dispersion liquid
Content be preferably 200-320 parts by weight, more preferably 250-290 parts by weight, the content of first dispersant is preferably 4-8
Parts by weight, more preferably 5-7 parts by weight.
According to the present invention, the pH of the conductive coating can be 7-11, preferably 8-10, more preferably 8.5-9.5.
According to the present invention, first water-base resin can be selected from water-based acrylic resin, waterborne polyurethane resin, aqueous
It is one or more in acrylic emulsion and styrene-acrylic emulsion, preferably water-based acrylic resin, waterborne polyurethane resin and phenylpropyl alcohol
It is one or more in lotion, in the present invention, when second water-base resin is selected from water-based acrylic resin, aqueous polyurethane
When two or more in resin and water-soluble organosilicon acrylic resin, between selected arbitrary two kind of second water-base resin
The weight ratio of content be not particularly limited, for example, can be 0.1-40：1；And
First dispersant can be selected from polycarboxylic acids ammonium salt class dispersant, organic-silicon-modified polysiloxane-based dispersant,
Copolymer analog dispersant, quaternary ammonium salt dispersant and the Sulfonates point of sodium polycarboxylate salt dispersant, the affinity groups containing pigment
It is one or more in powder, it is preferable that first dispersant is selected from polycarboxylic acids ammonium salt class dispersant, organic-silicon-modified poly- silicon
It is one or more in oxygen alkanes dispersant and the copolymer analog dispersant of the affinity groups containing pigment, it is highly preferred that described first
Dispersant is selected from polycarboxylic acids ammonium salt class dispersant and/or the copolymer analog dispersant of the affinity groups containing pigment；In the present invention, when
First dispersant is selected from polycarboxylic acids ammonium salt class dispersant, organic-silicon-modified polysiloxane-based dispersant and the affine base containing pigment
When two or more in the copolymer analog dispersant of group, between selected arbitrary two kinds of first dispersants
The weight ratio of content be not particularly limited, for example, can be 0.1-10：1；And
The polycarboxylic acids ammonium salt class dispersant can be the dispersant purchased from Sheng Nuopuke companies, trade mark SN-5027；
The copolymer analog dispersant of the affinity groups containing pigment can be the dispersant purchased from Di Gao companies, and the trade mark is
760W；
The copolymer analog dispersant of the affinity groups containing pigment can be the dispersant purchased from Bi Ke companies, and the trade mark is
BYK190。
According to the present invention, the graphene-carbon black dispersion liquid can contain grinding matrix, watersoluble plumbago alkene, carbon black and the
Two dispersants, and on the basis of the grinding matrix of 100 parts by weight, the content of the watersoluble plumbago alkene can be 50-250 weight
Part, preferably 100-230 parts by weight, more preferably 150-210 parts by weight, the content of the carbon black can be 20-140 weight
Part, preferably 30-110 parts by weight, more preferably 40-80 parts by weight, the content of second dispersant can be 2-30 weight
Part, preferably 5-20 parts by weight, more preferably 8-15 parts by weight；And the grinding matrix can be selected from water and/or the second water
Property resin, it is preferable that the grinding matrix is selected in water or the second water-base resin, in the present invention, when the grinding matrix is selected from
When water and the second water-base resin, the weight ratio of the content of the water and the second water-base resin is not particularly limited, for example, can be
0.1-25：1.
According to the present invention, second water-base resin can be identical or different with first water-base resin, in the present invention
In, second water-base resin can be in water-based acrylic resin, waterborne polyurethane resin and water-soluble organosilicon acrylic resin
It is one or more, it is preferable that second water-base resin is selected from water-based acrylic resin and/or waterborne polyurethane resin, at this
In invention, when second water-base resin is selected from water-based acrylic resin and waterborne polyurethane resin, the water soluble acrylic acid
The weight ratio of the content of resin and waterborne polyurethane resin is not particularly limited, for example, can be 0.1-40：1.
According to the present invention, second dispersant can be identical or different with first dispersant, in the present invention, institute
Polycarboxylic acids ammonium salt class dispersant, organic-silicon-modified polysiloxane-based dispersant, polycarboxylate sodium can be selected from by stating the second dispersant
One in class dispersant, the copolymer analog dispersant of the affinity groups containing pigment, quaternary ammonium salt dispersant and Sulfonates dispersant
Kind is a variety of, it is preferable that second dispersant is selected from organic-silicon-modified polysiloxane-based dispersant and/or the affine base containing pigment
The copolymer analog dispersant of group, it is highly preferred that second dispersant is selected from the copolymer analog dispersant of the affinity groups containing pigment；
In the present invention, when second dispersant is selected from being total to for organic-silicon-modified polysiloxane-based dispersant and the affinity groups containing pigment
When polymers class dispersant, containing between organic-silicon-modified polysiloxane-based dispersant and copolymer analog dispersant containing affinity groups
The weight ratio of amount is not particularly limited, for example, can be 0.1-15：1.
According to the present invention, the watersoluble plumbago alkene can be that commercially available letter receive the scientific and technological graphite of graphene slurry or ink west
Alkene slurry, in the present invention, the watersoluble plumbago alkene are that commercially available letter receives graphene slurry (model SC Pas2001).
According to the present invention, the graphene-carbon black dispersion liquid can also contain antifoaming agent, and with the grinding of 100 parts by weight
On the basis of matrix, the content of the antifoaming agent can be 0.5-10 parts by weight, preferably 2-8 parts by weight, more preferably 3-6 weight
Part；And the antifoaming agent can be selected from polysiloxane-based antifoaming agent, organic silicon antifoaming agent, silicone oil antifoaming agent and polyethers
It is one or more in antifoaming agent, it is preferable that the antifoaming agent is selected from polysiloxane-based antifoaming agent and/or organic silicon defoams
Agent, it is highly preferred that the antifoaming agent is selected from polysiloxane-based antifoaming agent；In the present invention, when the antifoaming agent is selected from poly- silica
When alkanes antifoaming agent and organic silicon antifoaming agent, the weight of the content between polysiloxane-based antifoaming agent and organic silicon antifoaming agent
Than being not particularly limited, for example, can be 0.1-10：1.
In the present invention, the antifoaming agent can be the entitled polysiloxane-based antifoaming agent purchased from Di Gao companies, the trade mark
For 901W.
According to the present invention, the conductive coating also contains auxiliary agent, and using first water-base resin of 100 parts by weight as base
The content of standard, the auxiliary agent is 20-60 parts by weight, preferably 30-55 parts by weight, more preferably 35-50 parts by weight；And
The auxiliary agent can be selected from one kind in filler, film forming agent, dry accelerating agent, thickener and pH adjusting agent or more
Kind.
According to the present invention, the filler can selected from titanium dioxide, talcum powder, kaolin, coarse whiting and fine particle calcium carbonate one kind or
It is several, it is preferable that the filler is selected from titanium dioxide；It is described to fill out and on the basis of first water-base resin of 100 parts by weight
The content of material can be 4-20 parts by weight, preferably 4-15 parts by weight, more preferably 5-12 parts by weight.
According to the present invention, the film forming agent can be selected from alkoxide and/or alcohol ethers, wherein the alkoxide can be
Lauryl Alcohol ester, the alcohol ethers can be butyl glycol ether and/or propylene glycol phenylate；
The dry accelerating agent can be selected from one kind in n-butanol, isopropanol, glycerine and diethylene glycol ether or more
Kind, it is preferable that the dry accelerating agent is selected from isopropanol and/or diethylene glycol ether；
The thickener can be excellent selected from one or more in polyurethanes copolymer, cellulose family and silica
Selection of land, the thickener are selected from polyurethanes copolymer and/or cellulose family；In the present invention, the thickener can be purchased from
The entitled polyurethanes thickening agent of copolymer of Rhom and Hass, trade mark RM-8W, and
The film forming agent, dry accelerating agent and the respective content of thickener are not particularly limited, and can be art technology
The conventional selection of personnel, it is preferable that on the basis of first water-base resin of 100 parts by weight, the content of the film forming agent can
Think 18-35 parts by weight, the content of the dry accelerating agent can be 2-7 parts by weight, and the content of the thickener can be 1-8
Parts by weight.
According to the present invention, the pH adjusting agent can be selected from amine neutralizer and/or alkaline matter, wherein the amine
Neutralizer can be N, N- dimethylethanolamines and/or triethanolamine, and the alkaline matter can be ammonium hydroxide and/or hydroxide
Sodium；In the present invention, the pH adjusting agent can be the entitled amine neutralizer DMAE purchased from this company of hamming；And
In the present invention, the content of the pH adjusting agent is not particularly limited, as long as by the pH value control of the conductive coating
System is in above range.
The present invention also provides a kind of preparation method of graphene-carbon black composite electrically-conducting paint, this method includes following step
Suddenly：
(1) grinding matrix, watersoluble plumbago alkene and the second dispersant are stirred under the first stirring condition, are then added again
Enter carbon black and is stirred under the second stirring condition；
(2) mixture that will be obtained through step (1) is ground；
(3) the first water-base resin and first point will be added in the graphene-carbon black dispersion liquid obtained after step (2) grinding
Powder simultaneously stirs under third stirring condition.
According to the present invention, in step (1), first stirring condition includes：Stir speed (S.S.) can be 500-
1000rpm, preferably 700-1000rpm, mixing time can be 30-60min, preferably 40-60min；Second stirring
Condition includes：Stir speed (S.S.) can be 1000-1500rpm, and preferably 1200-1500rpm, mixing time can be 1.5-
2.5h, preferably 2.0-2.5h.
According to the present invention, the fineness of the graphene-carbon black dispersion liquid can be less than 5 microns, preferably 0.2-2 microns.
According to the present invention, the equipment of the graphene-carbon black dispersion liquid grinding is not particularly limited, can be this field
The conventional selection of technical staff, such as can be grinder, and the condition of grinding is also not particularly limited, and can be this field
The conventional selection of technical staff, such as be ground using zirconium pearl.
According to the present invention, in step (3), the third stirring condition includes：Stir speed (S.S.) can be 500-
1000rpm, preferably 800-1000rpm, mixing time can be 0.5-2h, preferably 1-2h.
The present invention also provides the graphene prepared by above-mentioned preparation method (solution blended process)-carbon black composite guide electropaining
Material.
The present invention also provides the graphene-carbon black composite electrically-conducting paints in electrical heating, electromagnetic shielding, printed electronic line
Application on road, thin film switch and lithium battery.
In the present invention, the concrete application of the conductive coating is not particularly limited, for example, can be by above-mentioned conductive coating
The conductive coating of high conduction performance and physical and mechanical property is prepared after spraying, brushing, printing, so as to be applied to
Above-mentioned every field.
The present invention will be described in detail by way of examples below.
In following embodiment, volume resistivity parameter is by using the bis- electrical measurement four-point probes of RTS-9, specific test side
Method is as follows：
Sample is placed on tester operation console, operation probe station depresses probe, and turn-on current inputs film thickness, selective body
Product resistivity classification is tested；
Attachment force parameter passes through GB 1720-89《Paint film adhesion measuring method》It measures；
Flexibility parameter passes through GB/T 1731-93《Paint film flexibility measuring method》It measures；
Drying time parameter passes through GB/T 1728-1989《Paint film, putty membrane drying time measuring method》It measures；
Storage stability parameter passes through GB/T 6753.3-1986《Coating storage stability test method》It measures；And
Graphene raw material is to take in the fresh the commercially available product that the material Science and Technology Ltd. trade mark is SC Pas2001 purchased from letter.
Embodiment 1
The present embodiment is used for illustrating that method using the present invention prepares graphene-carbon black composite electrically-conducting paint
(1) by 300g water, 18g polycarboxylic acids ammonium salt class dispersant SN-5027,6g dispersant 760W and 450g watersoluble plumbago alkene
It is added in stirred tank, at room temperature, 40min is stirred under 700r/min rotating speeds, 120g conductive blacks are then added, in 1200r/
2h is stirred under min rotating speeds；
(2) and then by step (1) mixture be put into grinder, be ground to fineness be 0.2 μm, discharging obtain graphene/
Carbon black dispersion liquid；
(3) by 750g graphenes/carbon black dispersion liquid, the pH of 300g water-based acrylic resins, 15g dispersant Bs YK190,5g
Conditioning agent DMAE is added in reaction kettle, and adjustment pH is 8.5, and 1h is stirred under 800r/min rotating speeds, obtains environment-friendly type graphene-
Carbon black composite electrically-conducting paint T1；
As a result the conductive coating T1 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein coating
Thickness of dry film is 25 μm；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Embodiment 2
The present embodiment is used for illustrating that method using the present invention prepares graphene-carbon black composite electrically-conducting paint
(1) by 279g water-based acrylic resins, 21g water, 9.75g dispersants SN-5027,3.25g dispersant 760W, 4.5g
Antifoaming agent 901W and 570g watersoluble plumbago alkene is added in stirred tank, at room temperature, 50min is stirred under 800r/min rotating speeds, so
180g conductive blacks are added afterwards, 2h is stirred under 1250r/min rotating speeds；
(2) and then by step (1) mixture it is put into grinder, it is 1 μm to be ground to fineness, and discharging obtains graphene/charcoal
Black dispersion liquid；
(3) pH of 810g graphenes/carbon black dispersion liquid, 300g styrene-acrylic emulsions, 18g dispersant Bs YK190,5.3g are adjusted
Agent DMAE, 78g film forming agent Lauryl Alcohol ester, 4g drying accelerating agent diethylene glycol ethers and 4g thickeners RM-8W are added to reaction
In kettle, adjustment pH is 9.0, and 1.5h is stirred under 800r/min rotating speeds, obtains environment-friendly type graphene-carbon black composite electrically-conducting paint
T2；
As a result the conductive coating T2 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein coating
Thickness of dry film is 25 μm；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Embodiment 3
The present embodiment is used for illustrating that method using the present invention prepares graphene-carbon black composite electrically-conducting paint
(1) 300g water-based acrylic resins, 45g dispersant 760W, 18g antifoaming agent 901W, 630g watersoluble plumbago alkene are added
Enter in stirred tank, at room temperature, 60min is stirred under 1000r/min rotating speeds, 240g conductive blacks then will be added,
2.5h is stirred under 1500r/min rotating speeds；
(2) and then by step (1) mixture it is put into grinder, is ground to 2 μm of fineness, discharging obtains graphene/carbon black
Dispersion liquid；
(3) by 870g graphenes/carbon black dispersion liquid, 300g waterborne polyurethane resins, 15.8g dispersants SN-5027,5.2g
PH adjusting agent DMAE, 30g titanium dioxide, 105g film forming agent Lauryl Alcohols ester, the 7g of dispersant 760W, 5.8g dry accelerating agent isopropyl
Alcohol and 1g thickeners RM-8W are added in reaction kettle, and adjustment pH is 9.5, and 2h is stirred under 1000r/min rotating speeds, obtains environmental protection
Type graphene/carbon black composite electrically-conducting paint T3；
As a result the conductive coating T3 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein coating
Thickness of dry film is 25 μm；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Embodiment 4
The present embodiment is used for illustrating that method using the present invention prepares graphene-carbon black composite electrically-conducting paint
(1) 300g water-based acrylic resins, 15g dispersant 760W, 6g antifoaming agent 901W and 300g watersoluble plumbago alkene are added
Enter in stirred tank, at room temperature, 30min is stirred under 500r/min rotating speeds, 60g conductive blacks is then added, in 1500r/min
2h is stirred under rotating speed；
(2) and then by step (1) mixture it is put into grinder, is ground to 5 μm of fineness, discharging obtains graphene/carbon black
Dispersion liquid；
(3) by 600g graphenes/carbon black dispersion liquid, the pH of 300g water-based acrylic resins, 12g dispersant Bs YK190,5g
Conditioning agent DMAE, 54g film forming agent Lauryl Alcohol ester, 6g drying accelerating agent isopropanols and 24g thickeners RM-8W are added to reaction kettle
In, adjustment pH is 8.5, and 1.5h is stirred under 800r/min rotating speeds, obtains environment-friendly type graphene/carbon black composite electrically-conducting paint T4.
As a result the conductive coating T4 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass, wherein coating dry
Film thickness is 25 μm；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Embodiment 5
Graphene-carbon black composite electrically-conducting paint is prepared according to the method for embodiment 2, except that pH value is adjusted to 8；
As a result the conductive coating T5 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein coating
Thickness of dry film is 25 μm；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Embodiment 6
Graphene-carbon black composite electrically-conducting paint is prepared according to the method for embodiment 2, the difference is that grinding graphene-charcoal
Fineness that is black and making graphene-carbon black is 5 μm；
As a result the conductive coating T5 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein coating
Thickness of dry film is 25 μm；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Comparative example 1
Graphene-carbon black composite electrically-conducting paint is prepared according to the method for embodiment 1, the difference is that carbon black is not added,
Obtain environment-friendly type graphene-carbon black composite electrically-conducting paint DT1.
As a result the conductive coating DT1 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein apply
It is 25 μm to cover thickness of dry film；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Comparative example 2
Graphene-carbon black composite electrically-conducting paint is prepared according to the method for embodiment 3, except that：
(1) 300g water, 3g dispersant SN5027,0.8g antifoaming agent 901W, 120g watersoluble plumbago alkene are added in stirred tank,
At room temperature, 30min is stirred under 500r/min rotating speeds, and 200g conductive blacks then will be added, stirred under 1500r/min rotating speeds
Mix 2h；
(2) and then by step (1) mixture it is put into grinder, is ground to 30 μm of fineness, discharging obtains graphene/carbon black
Dispersion liquid；
(3) by 210g graphenes/carbon black dispersion liquid, the pH tune of 300g waterborne polyurethane resins, 6g dispersant Bs YK190,5g
Save agent DMAE, 45g titanium dioxide, 45g film forming agent Lauryl Alcohols ester, 3g drying accelerating agent diethylene glycol ethers and 3g thickeners RM-
8W is added in reaction kettle, and adjustment pH is 8.0, and 1.5h is stirred under 800r/min rotating speeds, and it is multiple to obtain environment-friendly type graphene-carbon black
Close conductive coating DT2.
As a result the conductive coating DT2 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein apply
It is 25 μm to cover thickness of dry film；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Comparative example 3
Graphene-carbon black composite electrically-conducting paint is prepared according to the method for embodiment 2, the difference is that by conductive coating
PH value is adjusted to 11, obtains environment-friendly type graphene-carbon black composite electrically-conducting paint DT3.
As a result the conductive coating DT3 of above-mentioned preparation is respectively coated on tinplate, on glass plate, wherein coating dry film
Thickness is 25 μm；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Comparative example 4
Graphene-carbon black composite electrically-conducting paint is prepared according to the method for embodiment 2, the difference is that by graphene-carbon black
Fineness be adjusted to 50 μm, obtain environment-friendly type graphene-carbon black composite electrically-conducting paint DT4.
As a result the conductive coating DT4 of above-mentioned preparation is respectively coated on ABS plates, tinplate, on glass plate, wherein apply
It is 25 μm to cover thickness of dry film；
Then test is coated in volume resistivity, the adhesive force coated in dry film on tinplate of the dry film on ABS plates
With flexibility, the coating drying time of dry film and storage stability on a glass, as shown in table 1.
Table 1
Remarks：" good " refers to that appearance and performance are substantially unchanged；
Drying time：It is to be carried out under the conditions of 120 DEG C.
From above-described embodiment 1-6 and comparative example 1-4's as a result, and Fig. 1-3 it can be seen that：Method using the present invention is such as
The scanning electron microscope image of graphene-carbon black dispersion liquid prepared by embodiment 1 is as shown in Figure 1, it is seen that graphene and carbon black are well
It mixes, does not reunite；The electron microscope of graphene-carbon black composite electrically-conducting paint prepared by method using the present invention such as embodiment 1
Picture is as shown in figure 3, the conductive coating is formed as reticular structure, and the carbon black dispersion is in the reticular structure；For another example Fig. 2 institutes
The reticular structure schematic diagram of the 1 graphene-carbon black composite electrically-conducting paint prepared according to an embodiment of the invention shown, it is known that, institute
The node that carbon black serves as the reticular structure of the conduction is stated, carries out " point contact " with adjacent graphene platelet, that is, graphene platelet
No longer " piece-piece " contacts between graphene platelet, and is formed as " piece-point " contact, to increase graphene conductive network
The quantity of access, auxiliary improve graphite network, to improve the electric conductivity of the conductive coating as shown in table 1, simultaneously
The compatibility of conductive black and resin is preferable, and mechanical property (flexibility) increases, and adhesive force is good and storage stability is good
It is good, and cost is relatively low and first water-base resin, the second water-base resin, filler and auxiliary agent etc. are environment-friendly type, no dirt
Dye, for the conductive coating can practical application on electrical heating, electromagnetic shielding, printed electronic circuit, thin film switch and lithium battery
Provide theoretical foundation and practical basis.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (14)
1. a kind of graphene-carbon black composite electrically-conducting paint, which is characterized in that the graphene-carbon black composite electrically-conducting paint contains stone
Black alkene-carbon black dispersion liquid, the first water-base resin and the first dispersant, on the basis of first water-base resin of 100 parts by weight,
The content of the graphene-carbon black dispersion liquid is 80-350 parts by weight, and the content of first dispersant is 3-10 parts by weight, institute
It states graphene-carbon black dispersion liquid and contains grinding matrix, watersoluble plumbago alkene, carbon black and the second dispersant, and grinding with 100 parts by weight
On the basis of grinding matrix, the content of the watersoluble plumbago alkene is 50-250 parts by weight, and the content of the carbon black is 20-140 parts by weight,
The content of second dispersant is 2-30 parts by weight；And the grinding matrix is selected from water and/or the second water-base resin.
2. conductive coating according to claim 1, wherein the pH of the conductive coating is 7-11.
3. conductive coating according to claim 2, wherein the pH of the conductive coating is 8-10.
4. conductive coating according to claim 1, wherein first water-base resin is selected from water-based acrylic resin, water
It is one or more in property polyurethane resin, aqueous acrylic emulsion and styrene-acrylic emulsion；And first dispersant is selected from and gathers
Carboxylic acid ammonium's salt dispersant, organic-silicon-modified polysiloxane-based dispersant, sodium polycarboxylate salt dispersant, affinity groups containing pigment
Copolymer analog dispersant, one or more in quaternary ammonium salt dispersant and Sulfonates dispersant.
5. conductive coating according to claim 1, wherein second water-base resin is selected from water-based acrylic resin, water
Property polyurethane resin and water-soluble organosilicon acrylic resin in it is one or more；And second dispersant is selected from polycarboxylic acids ammonium salt class
The copolymer analog of dispersant, organic-silicon-modified polysiloxane-based dispersant, sodium polycarboxylate salt dispersant, the affinity groups containing pigment
It is one or more in dispersant, quaternary ammonium salt dispersant and Sulfonates dispersant.
6. conductive coating according to claim 1, wherein the graphene-carbon black dispersion liquid also contains antifoaming agent, and with
On the basis of the grinding matrix of 100 parts by weight, the content of the antifoaming agent is 0.5-10 parts by weight；And the antifoaming agent is organic
Silicon class antifoaming agent and/or polyethers antifoaming agent.
7. conductive coating according to claim 1 or 2, wherein the conductive coating also contains auxiliary agent, and with 100 weight
On the basis of first water-base resin of part, the content of the auxiliary agent is 20-60 parts by weight；And the auxiliary agent be selected from filler,
It is one or more in film forming agent, dry accelerating agent, thickener and pH adjusting agent.
8. the preparation method of graphene-carbon black composite electrically-conducting paint described in any one of claim 1-7, this method include
Following steps：
(1) grinding matrix, watersoluble plumbago alkene and the second dispersant are stirred under the first stirring condition, then add charcoal
It is black and be stirred under the second stirring condition；
(2) mixture that will be obtained through step (1) is ground；
(3) the first water-base resin and the first dispersant will be added in the graphene-carbon black dispersion liquid obtained after step (2) grinding
And it is stirred under third stirring condition.
9. according to the method described in claim 8, wherein, in step (1), first stirring condition includes：Stir speed (S.S.)
For 500-1000rpm, mixing time 30-60min；Second stirring condition includes：Stir speed (S.S.) is 1000-1500rpm,
Mixing time is 1.5-2.5h.
10. according to the method described in claim 8, wherein, the fineness of the graphene-carbon black dispersion liquid is less than 5 microns.
11. according to the method described in claim 10, wherein, the fineness of the graphene-carbon black dispersion liquid is 0.2-2 microns.
12. according to the method described in claim 8, wherein, in step (3), the third stirring condition includes：Stir speed (S.S.)
For 500-1000rpm, mixing time 0.5-2h.
13. graphene-carbon black composite electrically-conducting paint prepared by the preparation method described in any one of claim 8-12.
14. graphene-carbon black composite electrically-conducting paint described in any one of claim 1-7 and 13 is in electrical heating, electromagnetism
Application on shielding, printed electronic circuit, thin film switch and lithium battery.
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