CN108192457A - A kind of conductive coating of graphene-containing high glaze watersoluble baking type and preparation method thereof - Google Patents
A kind of conductive coating of graphene-containing high glaze watersoluble baking type and preparation method thereof Download PDFInfo
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- CN108192457A CN108192457A CN201711476393.3A CN201711476393A CN108192457A CN 108192457 A CN108192457 A CN 108192457A CN 201711476393 A CN201711476393 A CN 201711476393A CN 108192457 A CN108192457 A CN 108192457A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
Abstract
The invention belongs to technical field of macromolecule polymerization, disclose a kind of conductive coating of graphene-containing high glaze watersoluble baking type and preparation method thereof.Based on the parts by weight of composition, which includes 30~40 parts of the water-based acrylic resin containing functionalization graphene；6~20 parts of amino curing agent melamine resin；5.5~14 parts of auxiliary agent；5~12 parts of pigment；30~40 parts of deionized water；Wherein, 1.5~4wt.% of the functionalization graphene content for conductive coating total amount in the water-based acrylic resin containing functionalization graphene.By the present invention in that with the silane coupler modified graphene containing double bond, it is made to participate in polymerisation with double bond, it is good with the compatibility of base resin, simultaneously resin can completely soluble and viscosity peak it is smaller, gloss is higher, so that the stability of the conductive coating prepared is good, be not in that standing time length the problem of reunion and difficulties in dispersion occurs, and with higher gloss and splendid performance.
Description
Technical field
The invention belongs to technical field of coatings, more particularly, to a kind of leading for graphene-containing high glaze watersoluble baking type
Electrocoating paint and preparation method thereof.
Background technology
Conductive coating is widely used in the fields such as electronic material, communication, military affairs, aerospace, and demand is presented always
Go out increased trend.With the development of industry, some base materials not only need paint spraying it are not corroded in surface protection, but also
It also needs to ensure the electric conductivity that paint film has higher glossiness and metalloid after application.Classify according to conductive mechanism, lead
Electrocoating paint can be divided into two kinds of intrinsically conducting coating (non-addition type) and doping type conductive coating.Intrinsically conducting coating is because depositing
In technical barrier height, the research and development and work of the problems such as cost remain high, therefore doping type conductive coating as conductive coating
The emphasis of industry.Traditional carbon series conductive material has the characteristics of cheap, convenient material drawing is easy to get, therefore always doping type is led
What the defects of important component part in electric material, but addition is big, difficulties in dispersion and poor stablizing effect limited it should
With.If patent CN101161743 discloses a kind of metal substrate conductive coating, conducting powder is mixed for graphite and metal conductive powder
Object is closed, conducting powder additive amount is higher (10%-70%), is not easy to disperse, poor storage stability.
Graphene is a kind of novel carbon series conductive material, compared with traditional carbon series conductive material, have size it is small, ratio
The characteristics of surface area is big, polarity is strong, the additive amount for there was only very little even if in coating, are readily formed reticular structure, are formed and passed
The channel of conductive son, so as to become the new lover of conductive material in the market.The patent of invention of Publication No. CN103897446A
Disclose it is a kind of graphene is combined with inorganic conductive material, prepare graphene composite conductive coating.This method is
Graphene is added to by simple physical blending in coating, but since graphene particle surface can be high, being long placed in can roll into a ball
It is poly-, so as to influence electric conductivity.
Invention content
In order to solve above-mentioned the shortcomings of the prior art, a kind of graphene-containing high glaze watersoluble baking type is provided
Conductive coating.The graphene additive amount of the conductive coating is few, and electric conductivity is excellent, good with Miscibility, and stability is good, light
Ze Dugao.
Another object of the present invention is to provide the preparation of the conductive coating of above-mentioned graphene-containing high glaze watersoluble baking type
Method.
The purpose of the present invention is realized by following technical proposals：
A kind of conductive coating of graphene-containing high glaze watersoluble baking type, based on the parts by weight of composition, including following components：
30~40 parts of water-based acrylic resin containing functionalization graphene；
6~20 parts of amino curing agent melamine resin；
5.5~14 parts of auxiliary agent；
5~12 parts of pigment；
30~40 parts of deionized water；
Wherein, the functionalization graphene content in the water-based acrylic resin containing functionalization graphene is conductive coating
1.5~4wt.% of total amount.
Preferably, the melamine resin is HMMM resin or molten containing isobutanol
The methyl etherified high imino group melmac of agent.
Preferably, the auxiliary agent includes levelling agent, wetting agent, anti-settling agent and antifoaming agent；The levelling agent, wetting
The mass ratio of agent, anti-settling agent and antifoaming agent is (3~5)：(1~3)：(1~3)：(0.5~3), the levelling agent change for alkyl
Property silicone levelling agent or polyester resin change properties of organic silicon levelling agent；The wetting agent is octyl phenol polyoxyethylene ether；Described
Anti-settling agent is highly polar polyurea thickener BYK-410 and/or organobentonite, the antifoaming agent for polymer-type antifoaming agent or
Organic silicon type antifoaming agent.
Preferably, the hydroxyl value in the water-based acrylic resin containing functionalization graphene be 27~71mgKOH/g, institute
Acid value in the water-based acrylic resin containing functionalization graphene stated is 97~160mgKOH/g, the graphite containing function
The number-average molecular weight of the water-based acrylic resin of alkene is 2000~4000.
Preferably, the pigment is titanium dioxide, bright red, iron oxide red, iron oxide yellow, chrome yellow, carbon black, phthalocyanine blue or group
It is green.
Preferably, the preparation method of the water-based acrylic resin containing functionalization graphene is as follows：
S1. by acrylate hard monomer, acrylate soft monomer, ester monomer containing carboxy acrylic, hydroxy acryl acid ester
It is equal that monomer, isobornyl methacrylate, 6-caprolactone, functionalization graphene, chain-transferring agent, solvent carry out ultrasonic disperse mixing
It is even；
S2. 1/20~1/15 above-mentioned mixed liquor is taken to add in into reactor, is reacted under 60~70 DEG C of stirring conditions,
1/5 initiator solution is added in when reacting initial, residual mixed liquor is added dropwise respectively when viscosity starts increase and remaining initiator is molten
It is kept the temperature after liquid；
S3. 45~55 DEG C are cooled the temperature to and then, dimethylethanolamine is added in and adjusts pH, reaction terminate to get to containing
The water-and acrylate of functionalization graphene.
Preferably, the acrylate hard monomer described in step S1, acrylate soft monomer, the list of ester containing carboxy acrylic
Body, hydroxy acryl acid ester monomer, isobornyl methacrylate, 6-caprolactone, functionalization graphene, chain-transferring agent, solvent
Mass ratio be (10~20)：(10~30)：(10~30)：(5~15)：(10~30)：(5~15)：(5~10)：(2~5)：
(30~50)；The acrylic acid hard monomer is methyl methacrylate, methyl acrylate, ethyl methacrylate or methyl-prop
Enoic acid ter-butyl ester more than one；The acrylic acid soft monomer is n-butyl acrylate, ethyl acrylate or acrylic acid are just pungent
One or more of ester；The ester monomer containing carboxy acrylic is methacrylic acid and/or acrylic acid；The hydroxyl third
Olefin(e) acid ester monomer is senecioate-hydroxypropyl acrylate and/or senecioate-hydroxyl ethyl ester；The chain-transferring agent for n- dodecyl mereaptan or
Stearyl mercaptan；The solvent is propylene glycol monomethyl ether, isopropanol or butanone；Initiator described in step S2 is azo
Two different heptonitriles or azodiisobutyronitrile, the solvent of the initiator solution is propylene glycol monomethyl ether, and the initiator adds
Enter amount be system total amount 1~0.5wt.%, a concentration of 5~10wt.% of the initiator solution, the dropwise addition when
Between for 2~4h, the time of the heat preservation is 2~3h；PH described in step S3 is 7~8.
Preferably, the preparation method of the functionalization graphene described in step S1 is as follows：Watersoluble plumbago is made in graphene
Ethyl alcohol is added in after alkene slurry and carries out ultrasonic disperse, under 75~85 DEG C of stirring conditions, γ-methacryloxypropyl three is added dropwise
It is kept the temperature after methoxy silane, reaction was completed, dry after product is centrifuged, and functionalization graphene powder is made.
It is further preferable that γ-the methacryloxypropyl trimethoxy silane and the mass ratio of graphene are
0.5~1.5：1, time of the dropwise addition is 30~60min, and time of the heat preservation is 2~3h, the temperature of the drying
Spend is 30~50 DEG C.
The preparation method of the conductive coating of above-mentioned graphene-containing high glaze watersoluble baking type, be by deionized water add in
In reaction kettle, temperature is risen to 40~50 DEG C, the water-based acrylic resin containing functionalization graphene is added in, is stirred, treat institute
After the dissolving completely of the water-based acrylic resin containing functionalization graphene stated, auxiliary agent and amino curing agent are added in, stirs and keeps the temperature
1.5~2h adjusts pH to 7~8, obtains the conductive coating of graphene-containing high glaze watersoluble baking type.
The principle of the present invention is to carry active group, energy and silane coupling agent on (1) graphene aqueous slurry surface
KH570 is reacted.By using KH570 modified graphene aqueous slurries, graphene surface can be made with double bond, and with parent
Oiliness；Graphene with double bond can make graphene with carrying out solution polymerization with the acrylate monomer containing vinyl
In the segment for grafting on acrylate copolymer, the compatibility of graphene and coating base resin is greatly improved in this way.(2) add
A certain amount of isobornyl methacrylate is entered and has participated in copolymerization, there is water-based acrylic resin containing functionalization graphene higher
Hardness, assign resin higher glossiness；The special caged scaffold of isobornyl methacrylate has larger space simultaneously
Steric hindrance, can effectively reduce resin viscosity, be not in higher viscosity peak when being diluted with water.And the introducing of 6-caprolactone can assign
The preferable flexibility of water-based acrylic resin containing functionalization graphene is given, balance makes to contain due to introducing isobornyl methacrylate
There is the problem of really up to the mark in functionalization graphene water-based acrylic resin.
Compared with prior art, the invention has the advantages that：
1. the conductive coating of the watersoluble baking type of high glaze containing functionalization graphene of the present invention is unique using graphene
Structure and excellent mechanics electric property by using the silane coupler modified graphene containing double bond, make it carry double bond
Polymerisation is participated in, additive amount that obtained conductive coating contain less conducting powder and tool good with the compatibility of base resin
There is excellent electric conductivity；So that the stability of the conductive coating prepared is good, be not in that standing time length occurs reuniting and divide
Dissipate the problem of difficult..
2. water-based acrylic resin containing functionalization graphene has glossiness high in the present invention, flexibility is good, and resin
Can completely soluble and viscosity peak it is smaller, good water solubility is not in higher viscosity peak when being diluted with water.
Specific embodiment
The content further illustrated the present invention with reference to specific embodiment, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagent, method and apparatus.
The present invention can add in the pigment such as titanium dioxide, bright red, iron oxide red, iron oxide yellow, chrome yellow, carbon black, phthalocyanine blue, ultramarine
Coating is modulated, addition is preferably the 5~12% of conductive coating gross mass.The amino curing agent of the present invention is Qing Te companies
HMMM resin (CYMEL 303) or the methyl etherified high imino group melamine containing iso-butanol solvent
Resin (CYMEL325), antifoaming agent are the polymer-type antifoaming agent BYK-057 of Bi Ke companies, and anti-settling agent is the high pole of Bi Ke companies
Property polyurea thickener BYK-410, wetting agent be the Dow Chemical Company octyl phenol polyoxyethylene ether X-405, levelling agent be Bi Ke companies
Organic silicon surfactant BYK346.
The preparation of acrylate of the embodiment 1 containing functionalization graphene
1. 100g (graphene effective content is 10%) watersoluble plumbago alkene slurry is taken to be placed in beaker, the second of 100g is added in
Alcohol, ultrasonic disperse 30min, is then transferred into four-hole boiling flask, is heated to 75 DEG C, and γ-metering system is added dropwise under agitation
Acryloxypropylethoxysilane trimethoxy silane (KH-570) 5g, drips off in 30min, keeps the temperature 2h；Mixture after reaction is cooled to room
Temperature is centrifuged, is washed respectively 3 times with distilled water and isopropanol, is centrifuged, is put into 30 DEG C of freeze-day with constant temperature 12h in baking oven, is ground
Functionalization graphene is obtained for powder.
2. by 10g n-butyl acrylates, 10g isobornyl methacrylates, 15g methyl methacrylates, 10g propylene
Acid, 5g senecioates-hydroxypropyl acrylate, functionalization graphene, 2g n- dodecyl mereaptans, 32.5 propylene glycol monomethyl ethers and 5 in 5g steps 1
Part 6-caprolactone is put into ultrasound 30min in beaker, and progress ultrasonic disperse is uniformly mixed, and 0.5g azodiisobutyronitriles are dissolved in the third two
The solution of 10% concentration is configured in alcohol monomethyl ether；1/20 above-mentioned mixed liquor is taken to add in into reactor, under 70 DEG C of stirring conditions
It is reacted, 1/5 azodiisobutyronitrile solution is added in when reacting initial, residual mixed liquor is added dropwise respectively when viscosity starts increase
It with remaining azodiisobutyronitrile solution, is dripped in 2h, keeps the temperature 2h；Then 50 DEG C are cooled the temperature to, adds in dimethylethanolamine
PH to 7~8 is adjusted, reaction terminates to get to the acrylate (A1) containing functionalization graphene.
The preparation of acrylate of the embodiment 2 containing functionalization graphene
1. 100g (graphene effective content is 10%) watersoluble plumbago alkene slurry is taken to be placed in beaker, the second of 100g is added in
Alcohol, ultrasonic disperse 30min, is then transferred into four-hole boiling flask, is heated to 75 DEG C, and γ-metering system is added dropwise under agitation
Acryloxypropylethoxysilane trimethoxy silane (KH-570) 10g, drips off in 30min, keeps the temperature 2h；Mixture after reaction is cooled to room
Temperature is centrifuged, is washed respectively 3 times with distilled water and isopropanol, is centrifuged, is put into 30 DEG C of freeze-day with constant temperature 12h in baking oven, is ground
Functionalization graphene is obtained for powder.
2. by 10g n-butyl acrylates, 10g ethyl acrylates, 15g isobornyl methacrylates, 10g methacrylic acids
Ethyl ester, 11g acrylic acid, 10g senecioates-hydroxyl ethyl ester, functionalization graphene, 3g Stearyl mercaptans, 20g in 5g steps 1
Isopropanol and 5 parts of 6-caprolactones are put into ultrasound 30min in beaker, carry out ultrasonic disperse and are uniformly mixed, by 1g azodiisobutyronitriles
It is dissolved in the solution that 10% concentration is configured in propylene glycol monomethyl ether；1/15 above-mentioned mixed liquor is taken to add in into reactor, 70 DEG C are stirred
It is reacted under the conditions of mixing, 1/5 azodiisobutyronitrile solution is added in when reacting initial, be added dropwise respectively when viscosity starts increase surplus
Remaining mixed liquor and remaining azobisisoheptonitrile solution, drip in 3h, keep the temperature 2h；Then 50 DEG C are cooled the temperature to, adds in diformazan
Ethylethanolamine adjusts pH to 7~8, and reaction terminates to get to the acrylate (A2) containing functionalization graphene.
The preparation of acrylate of the embodiment 3 containing functionalization graphene
1. 100g (graphene effective content is 10%) watersoluble plumbago alkene slurry is taken to be placed in beaker, the second of 100g is added in
Alcohol, ultrasonic disperse 30min, is then transferred into four-hole boiling flask, is heated to 75 DEG C, and γ-metering system is added dropwise under agitation
Acryloxypropylethoxysilane trimethoxy silane (KH-570) 15g, drips off in 30min, keeps the temperature 2h；Mixture after reaction is cooled to room
Temperature is centrifuged, is washed respectively 3 times with distilled water and isopropanol, is centrifuged, is put into 30 DEG C of freeze-day with constant temperature 12h in baking oven, is ground
It is broken to obtain functionalization graphene powder.
2. by 10g n-octyls, 10g methyl acrylates, 10g isobornyl methacrylates, 20g metering systems
Acid, 5g senecioates-hydroxyl ethyl ester, functionalization graphene, 4.3g n- dodecyl mereaptans, 20g butanone and 10 parts of ε in 10g steps 1-
Caprolactone is put into ultrasound 30min in beaker, carries out ultrasonic disperse and is uniformly mixed, 0.7g azobisisoheptonitrile is dissolved in propylene glycol list
The solution of 10% concentration is configured in methyl ether；1/18 above-mentioned mixed liquor is taken to add in into reactor, is carried out under 70 DEG C of stirring conditions
Reaction, adds in 1/5 azobisisoheptonitrile solution when reacting initial, residual mixed liquor is added dropwise respectively when viscosity starts increase and remains
Remaining azobisisoheptonitrile solution, drips in 3h, keeps the temperature 2h；Then 50 DEG C are cooled the temperature to, dimethylethanolamine is added in and adjusts
PH to 7~8, reaction terminate to get to the acrylate (A3) containing functionalization graphene.
The preparation of acrylate of the embodiment 4 containing functionalization graphene
1. 100g (graphene effective content is 10%) watersoluble plumbago alkene slurry is taken to be placed in beaker, the second of 100g is added in
Alcohol, ultrasonic disperse 30min, is then transferred into four-hole boiling flask, is heated to 75 DEG C, and γ-metering system is added dropwise under agitation
Acryloxypropylethoxysilane trimethoxy silane (KH-570) 10g, drips off in 30min, keeps the temperature 2h；Mixture after reaction is cooled to room
Temperature is centrifuged, is washed respectively 3 times with distilled water and isopropanol, is centrifuged, is put into 30 DEG C of freeze-day with constant temperature 12h in baking oven, is ground
It is broken to obtain functionalization graphene powder.
2. by 10g ethyl acrylates, 10g Tert-butyl Methacrylates, 10g isobornyl methacrylates, 10g methyl-props
Olefin(e) acid, 5g senecioates-hydroxypropyl acrylate, functionalization graphene, 5g n- dodecyl mereaptans, 40g propylene glycol monomethyl ethers in 5g steps 1 and
5g 6-caprolactones are put into ultrasound 30min in beaker, carry out ultrasonic disperse and are uniformly mixed, and 0.5g azobisisoheptonitrile is dissolved in the third two
The solution of 10% concentration is configured in alcohol monomethyl ether；1/18 above-mentioned mixed liquor is taken to add in into reactor, under 70 DEG C of stirring conditions
It is reacted, 1/5 azobisisoheptonitrile solution is added in when reacting initial, residual mixed liquor is added dropwise respectively when viscosity starts increase
It with remaining azobisisoheptonitrile solution, is dripped in 3h, keeps the temperature 2h；Then 50 DEG C are cooled the temperature to, adds in dimethylethanolamine
PH to 7~8 is adjusted, reaction terminates to get to the acrylate (A4) containing functionalization graphene.
The molecular weight of the acrylate containing functionalization graphene, hydroxyl value and acid value are as shown in table 1 in embodiment 1-4.
Molecular weight, hydroxyl value and the acid value of acrylate of the table 1 containing functionalization graphene
The preparation of 5 conductive coating of embodiment
23g deionized waters are added in into reaction kettle, temperature is risen to 40 DEG C, are slowly added to 56g containing functionalization graphene
Water-based acrylic resin A1 (is scaled 35g) with solid constituent, is stirred with 300 revs/min of mixing speed, functionalization to be contained
(viscosity after dilution is 500mpa.s after graphene water-based acrylic resin A1 dissolvings completely-1), addition 5g levelling agents BYK346,
2g wetting agent X-405,1g anti-settling agent BYK-410,2g antifoaming agent BYK-057,12g titanium dioxides and 20g amino curing agents CYMEL
325, it stirs and keeps the temperature 2h, adjust pH to 7~8, obtain the conductive coating of graphene-containing high glaze watersoluble baking type.
The preparation of 6 conductive coating of embodiment
40g deionized waters are added in into reaction kettle, temperature is risen to 50 DEG C, is slowly added to functionalization graphene containing 50g
Water-based acrylic resin A2 (is scaled 40g) with solid constituent, is stirred with 500 revs/min of mixing speed, functionalization to be contained
(viscosity after dilution is 300mpa.s after graphene water-based acrylic resin A2 dissolvings completely-1), addition 3g levelling agents BYK346,
3g wetting agent X-405,1.5g anti-settling agent BYK-410 and 1g bentonite, the bright red toners of 0.5g antifoaming agent BYK-057,5g and 6g ammonia
Base curing agent CYMEL303 is stirred and is kept the temperature 2h, is adjusted pH to 7~8, is obtained the conduction of graphene-containing high glaze watersoluble baking type
Coating.The preparation of 7 conductive coating of embodiment
38g deionized waters are added in into reaction kettle, temperature is risen to 45 DEG C, are slowly added to the graphite of function containing 37.5g
Alkene water-based acrylic resin A3 (is scaled 30g) with solid constituent, is stirred with 500 revs/min of mixing speed, function to be contained
(viscosity after dilution is 380mpa.s after graphite alkene water-based acrylic resin A3 dissolvings completely-1), add in 4g levelling agents
BYK346,1g wetting agent X-405,3g anti-settling agent BYK-410,3g antifoaming agent BYK-057,8g carbon black and 13g amino curing agents
CYMEL303 is stirred and is kept the temperature 2h, is adjusted pH to 7~8, is obtained the conductive coating of graphene-containing high glaze watersoluble baking type.
The preparation of 8 conductive coating of embodiment
30g deionized waters are added in into reaction kettle, temperature is risen to 45 DEG C, is slowly added to functionalization graphene containing 60g
Water-based acrylic resin A4 (is scaled 36g) with solid constituent, is stirred with 500 revs/min of mixing speed, functionalization to be contained
(viscosity after dilution is 430mpa.s after graphene water-based acrylic resin A4 dissolvings completely-1), addition 3g levelling agents BYK346,
2.5g wetting agent X-405,2g anti-settling agent BYK-410,1.5g antifoaming agent BYK-057,10g phthalocyanine blues and 15g amino curing agents
CYMEL303 is stirred and is kept the temperature 2h, is adjusted pH to 7~8, is obtained the conductive coating of graphene-containing high glaze watersoluble baking type.
The performance of 9 conductive coating of embodiment
Using tinplate as breadboard, applied according to the conduction by above-mentioned graphene-containing high glaze watersoluble baking type is required
Material is sprayed on breadboard, is toasted at 130~180 DEG C, and baking time is 20~60min.Using breadboard to implementing
Example 5~8 carries out performance evaluation, and evaluation result is as shown in table 2.
The performance of conductive coating in 2 5-8 of the embodiment of the present invention of table
By table 2, it can be seen that, the coating that the present invention is prepared has good performance, and specific volume resistance is small, adhesive force
Good, flexibility is good, excellent in stability, and water resisting time is long, there is higher glossiness.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine and simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of conductive coating of graphene-containing high glaze watersoluble baking type, which is characterized in that based on the parts by weight of composition, including
Following components：
30~40 parts of water-based acrylic resin containing functionalization graphene；
6~20 parts of amino curing agent melamine resin；
5.5~14 parts of auxiliary agent；
5~12 parts of pigment；
30~40 parts of deionized water；
Wherein, functionalization graphene content is conductive coating total amount in the water-based acrylic resin containing functionalization graphene
1.5~4wt.%.
2. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 1, which is characterized in that described
Melamine resin is HMMM resin or the methyl etherified high imino group containing iso-butanol solvent
Melmac.
3. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 1, which is characterized in that described
Auxiliary agent includes levelling agent, wetting agent, anti-settling agent and antifoaming agent；The levelling agent, wetting agent, anti-settling agent and antifoaming agent quality
Than for (3~5)：(1~3)：(1~3)：(0.5~3), the levelling agent are alkyl-modified silicone levelling agent or polyester
Modified organic silicon class levelling agent；The wetting agent is octyl phenol polyoxyethylene ether；The anti-settling agent increases for highly polar polyureas
Thick dose of BYK-410 and/or organobentonite, the antifoaming agent are polymer-type antifoaming agent or organic silicon type antifoaming agent.
4. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 1, which is characterized in that described
Hydroxyl value in water-based acrylic resin containing functionalization graphene is 27~71mgKOH/g, described containing functionalization graphene
Acid value in water-based acrylic resin is 97~160mgKOH/g, the water-based acrylic resin containing functionalization graphene
Number-average molecular weight is 2000~4000.
5. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 1, which is characterized in that described
Pigment is titanium dioxide, bright red, iron oxide red, iron oxide yellow, chrome yellow, carbon black, phthalocyanine blue or ultramarine.
6. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 1, which is characterized in that described
The preparation method of water-based acrylic resin containing functionalization graphene is as follows：
S1. by acrylate hard monomer, acrylate soft monomer, ester monomer containing carboxy acrylic, hydroxy acryl acid ester monomer,
Isobornyl methacrylate, 6-caprolactone, functionalization graphene, chain-transferring agent, solvent carry out ultrasonic disperse and are uniformly mixed；
S2. 1/20~1/15 above-mentioned mixed liquor is taken to add in into reactor, is reacted under 60~70 DEG C of stirring conditions, is reacted
1/5 initiator solution is added in when initial, after residual mixed liquor and remaining initiator solution is added dropwise respectively when viscosity starts increase
Heat preservation；
S3. and then 45~55 DEG C are cooled the temperature to, addition dimethylethanolamine adjusting pH is reacted and terminated to get to containing functional
The water-and acrylate of graphite alkene.
7. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 6, which is characterized in that step S1
Described in acrylate hard monomer, acrylate soft monomer, ester monomer containing carboxy acrylic, hydroxy acryl acid ester monomer,
Isobornyl methacrylate, 6-caprolactone, functionalization graphene, chain-transferring agent, solvent mass ratio be (10~20)：(10
~30)：(10~30)：(5~15)：(10~30)：(5~15)：(5~10)：(2~5)：(30~50)；The acrylic acid
Hard monomer is more than one of methyl acrylate, base methyl acrylate, ethyl methacrylate or Tert-butyl Methacrylate；Institute
The acrylic acid soft monomer stated is one or more of n-butyl acrylate, ethyl acrylate or n-octyl；Described contains
Carboxy acrylic ester monomer is methacrylic acid and/or acrylic acid；The hydroxy acryl acid ester monomer is senecioate-hydroxyl
Propyl ester and/or senecioate-hydroxyl ethyl ester；The chain-transferring agent is n- dodecyl mereaptan or Stearyl mercaptan；The solvent
For propylene glycol monomethyl ether, isopropanol or butanone；Initiator described in step S2 is azobisisoheptonitrile or azodiisobutyronitrile,
The solvent of the initiator solution is propylene glycol monomethyl ether, the addition of the initiator for system total amount 1~
0.5wt.%, a concentration of 5~10wt.% of the initiator solution, time of the dropwise addition are 2~4h, the guarantor
The time of temperature is 2~3h；PH described in step S3 is 7~8.
8. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 6, which is characterized in that step S1
Described in functionalization graphene preparation method it is as follows：Addition ethyl alcohol surpasses after graphene is made watersoluble plumbago alkene slurry
Sound disperses, and under 75~85 DEG C of stirring conditions, keeps the temperature, terminates after γ-methacryloxypropyl trimethoxy silane is added dropwise
Reaction, it is dry after product is centrifuged, functionalization graphene powder is made.
9. the conductive coating of graphene-containing high glaze watersoluble baking type according to claim 8, which is characterized in that described
The mass ratio of γ-methacryloxypropyl trimethoxy silane and graphene is 0.5~1.5：1, the dropwise addition when
Between for 30~60min, the time of the heat preservation is 2~3h, and the temperature of the drying is 30~50 DEG C.
10. according to the preparation side of the conductive coating of claim 1~9 any one of them graphene-containing high glaze watersoluble baking type
Method, which is characterized in that be to add in deionized water into reaction kettle, temperature is risen to 40~50 DEG C, adds in graphite containing function
The water-based acrylic resin of alkene is stirred, after the dissolving completely of the water-based acrylic resin containing functionalization graphene,
Auxiliary agent and amino curing agent are added in, stirs and keeps the temperature 1.5~2h, pH to 7~8 is adjusted, obtains the aqueous baking of graphene-containing high glaze
The conductive coating of roasting type.
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