CN104403397B - Automobile-used CNT composite primer and its preparation, application method - Google Patents

Automobile-used CNT composite primer and its preparation, application method Download PDF

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Publication number
CN104403397B
CN104403397B CN201410692570.1A CN201410692570A CN104403397B CN 104403397 B CN104403397 B CN 104403397B CN 201410692570 A CN201410692570 A CN 201410692570A CN 104403397 B CN104403397 B CN 104403397B
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cnt
composite primer
automobile
composite
spraying
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CN104403397A (en
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钟小华
李卫
王睿
刘安心
田小龙
张鑫明
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Dongfeng Commercial Vehicle Co Ltd
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Dongfeng Commercial Vehicle Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B05D7/26—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

A kind of automobile-used CNT composite primer, including vehicle paint base and its interior dispersed CNT, mass percent concentration of the CNT in composite primer is 0.1-1.5 wt.%, and the surface resistance for the CNT composite coating that the composite primer is formed after spraying is 103–109Ω/□.During preparation, first CNT is added in vehicle paint base, it is dispersed again to can obtain CNT composite primer, when using, first CNT composite primer is sprayed on non-metal workpiece to obtain CNT composite coating, after drying to be coated, then to the composite coating spray paint by the way of electrostatic spraying.The design can not only meet static determinacy spraying the need for, conductive additive easily disperse in primers, addition seldom, and production cost is relatively low, color interference is weaker, operation is simple, be easy to application.

Description

Automobile-used CNT composite primer and its preparation, application method
Technical field
The present invention relates to a kind of vehicle priming paint, more particularly to a kind of automobile-used CNT composite primer and its preparation, use Method, it is particularly applicable to realize on nonmetallic parts on the basis of electrostatic spraying finish paint, mitigate the interference to basecoat color, and Reduce cost.
Background technology
Automobile finish is the performance directly perceived of automotive quality, the expensive of high-end automobile finish, in order to improve finish paint Service efficiency, electrostatic spraying is a kind of development trend for improving its service efficiency.Electrostatic spraying is to allow face using high-voltage electrostatic field Paint is sprayed on specified component surface in the presence of electric field, and the utilization rate of finish paint can be made to be up to 50% -70%, and aerial spraying Service efficiency just it is relatively low, typically only 20% -30%.Realize that electrostatic spraying needs parts conductive or static conductive, it is general to require The surface resistance of parts is less than 109Ω/, metal material conduction is excellent, rather than metallic element is mostly insulating materials, face electricity Resistance generally higher than 1014Ω/, therefore, nonmetallic parts to realize electrostatic spraying must be made into anti-static material or Non-metal material surface spray resists quiet coating.Have been reported that addition conductive additive is nonmetallic to improve in nonmetallic parts The electrical conductivity of material realizes electrostatic spraying, also has the coating for spraying one layer of static conductive in nonmetallic component surface to realize quiet Electrospray, it is clear that the conductive dosage needed for nonmetallic component surface sprays one layer of static conductive coating is few, and cost is low, has more preferably Market development prospect.
At present, the conductive agent applied to the face coat of nonmetallic parts is mainly conductive titanium white and carbon black, and these are led Electric agent content in coating typically can be only achieved anlistatig effect in 10-30wt.%, and conductive titanium white density is about 4g/cm3, And paint density typically about 1g/cm3, the different easily layerings of density, and more than 10wt.% carbon black, color of paint will be caused too Deep, difficulty meets vehicle priming paint use requirement.
Chinese patent, application publication number is CN102277057A, and data of publication of application is special for the invention on December 14th, 2011 Profit application discloses a kind of conductive priming paint for plastic substrate electrostatic painting and preparation method thereof, and raw material includes thermoset acrylics tree Fat 20-30, thermoplastic acrylic resin 10-20, conductive titanium dioxide pigment 20-40, carbon black pigment 0.3-2, dispersant 1-3, solvent 5-10, ground wetting agent 0.5-1, thermosetting acrylic resin, dispersant, 40-60wt% solvent, conductive titanium dioxide pigment, carbon It is added to after mineral black agitation grinding in thermoplastic acrylic resin, ground wetting agent and remaining solvent, it is well mixed to produce To conductive priming paint for plastic substrate electrostatic painting.Although the design has the advantages that electrostatic spraying can be realized, it still has Following defect：
First, the conductive additive that the design is used is mainly conductive titanium dioxide pigment, and its density is about 4g/cm3, and paint Density is typically about 1g/cm3, density is different to be easily layered, and causes conductive titanium dioxide pigment to be difficult to disperse in paint, it is difficult to which mixing is equal It is even, operation difficulty is not only increased, and improve usage amount, it is necessary to which electrostatic could be realized by adding many conductive titanium dioxide pigments Spraying, the unit price of conductive titanium dioxide pigment is higher in addition, and its production cost is higher.
Secondly, the design needs to use many conductive titanium dioxide pigments, very big to the Color influences of priming paint, the interference of color Property is stronger, is unfavorable for the use of finish paint.
The content of the invention
The purpose of the present invention be overcome conductive additive present in prior art to be difficult to disperse in primers, addition compared with Many, production cost is higher, and the defect that the interference of color is stronger is easily divided in primers with problem there is provided a kind of conductive additive Dissipate, addition seldom, production cost is relatively low, the weaker automobile-used CNT composite primer of the interference of color and its preparation, makes Use method.
To realize object above, technical solution of the invention is：A kind of automobile-used CNT composite primer, including vapour Underbody paint and its conductive additive of internal doping；
The conductive additive is CNT, and the CNT is dispersed in vehicle paint base, and CNT exists Mass percent concentration in composite primer is 0.1-1.5wt.%；
The surface resistance for the CNT composite coating that the composite primer is formed after spraying is 103–109Ω/□。
Mass percent concentration of the CNT in composite primer is 0.8wt.%；The composite primer is through spraying The surface resistance of the CNT composite coating formed afterwards is 5 × 106Ω/□。
The CNT is single wall or multi-walled carbon nanotube；The vehicle paint base is epoxylite or acrylic compounds tree Fat.
A kind of preparation method of above-mentioned automobile-used CNT composite primer, the preparation method comprises the following steps successively：
First CNT is added in vehicle paint base to obtain mixture, then scatter operation is carried out to the mixture so that CNT is dispersed in vehicle paint base, and dispersed to can obtain described CNT composite primer afterwards, this is combined The mass percent concentration of CNT is 0.1-1.5wt.% in priming paint, and the carbon nanometer that the composite primer is formed after spraying The surface resistance of pipe composite coating is 103–109Ω/□。
The scatter operation refers to ultrasonic disperse or ball milling is scattered.
When the scatter operation is ultrasonic disperse, the size of ultrasonic wave is 20-25Hz, and ultrasonic time is 60min.
The state when CNT is added to vehicle paint base is powdered or slurry.
A kind of application method of above-mentioned automobile-used CNT composite primer, the application method comprises the following steps successively：
First described CNT composite primer is sprayed on non-metal workpiece to obtain CNT composite coating, treated After CNT composite coating is dried, then to the composite coating spray paint by the way of electrostatic spraying, with nonmetallic zero The electrostatic spraying of finish paint is realized on part.
The drying mode of the CNT composite coating is：1h is dried at 80 DEG C.
Compared with prior art, beneficial effects of the present invention are：
1st, in a kind of automobile-used CNT composite primer of the present invention and its preparation, application method, CNT is used as conduction Additive is dispersed in CNT composite primer, now, and CNT can form three-dimensional conductive in composite primer Network, can not only improve the electrical conductivity of composite primer, its surface resistance is met the requirement of electrostatic spraying, while can also improve multiple The thermal conductivity of priming paint is closed, so as to improve the ageing resistace of composite primer.Therefore, the present invention can not only meet electrostatic spraying Need, and ageing resistace is stronger.
2nd, in a kind of automobile-used CNT composite primer of the present invention and its preparation, application method, the density of CNT with The density of vehicle paint base is very close to the density of CNT is about 1.4g/cm3, the general 1g/cm of density of vehicle paint base3, density Close to can ensure that CNT be difficult in vehicle paint base layering, be easy to CNT dispersed in vehicle paint base, So as on the basis of composite primer electric conductivity is improved, reduce the unit usage amount of CNT, this can not only reduce cost, And it is avoided that interference of the excessive CNT to basecoat color.Therefore, not only conductive additive easily divides the present invention in primers Scattered, addition is seldom, and production cost is relatively low, color interference is weaker.
3rd, in a kind of automobile-used CNT composite primer of the present invention and its preparation, application method, when preparing composite primer, Only need to CNT being added in vehicle paint base, then carry out dispersed, step is few, operation is simple, can save Substantial amounts of time and manpower.Therefore, the present invention is not only convenient for operation, and production cost is relatively low.
4th, in a kind of automobile-used CNT composite primer of the present invention and its preparation, application method, when using composite primer, Composite primer need to be only sprayed on non-metal workpiece, the composite coating can be sprayed by the way of electrostatic spraying after re-dry Paint, so as to improve the service efficiency of finish paint, not only operate simply, and the color of finish paint will not be interfered, applied Scope is wider.Therefore, the present invention is not only operated simply, and is easy to application.
Brief description of the drawings
When Fig. 1 is that the mass percent concentration of CNT is 0.1wt.%, composite primer produced by the present invention is through spraying The outward appearance picture of the CNT composite coating formed afterwards.
Fig. 2 is the scanned picture of CNT composite coating in Fig. 1.
When Fig. 3 is that the mass percent concentration of CNT is 1.5wt.%, composite primer produced by the present invention is through spraying The scanned picture of the CNT composite coating formed afterwards.
Embodiment
Below in conjunction with brief description of the drawings, the present invention is further detailed explanation with embodiment.
Referring to Fig. 1, Fig. 2 and Fig. 3, a kind of automobile-used CNT composite primer, including vehicle paint base and its internal doping Conductive additive；
The conductive additive is CNT, and the CNT is dispersed in vehicle paint base, and CNT exists Mass percent concentration in composite primer is 0.1-1.5wt.%；
The surface resistance for the CNT composite coating that the composite primer is formed after spraying is 103–109Ω/□。
Mass percent concentration of the CNT in composite primer is 0.8wt.%；The composite primer is through spraying The surface resistance of the CNT composite coating formed afterwards is 5 × 106Ω/□。
The CNT is single wall or multi-walled carbon nanotube；The vehicle paint base is epoxylite or acrylic compounds tree Fat.
A kind of preparation method of above-mentioned automobile-used CNT composite primer, the preparation method comprises the following steps successively：
First CNT is added in vehicle paint base to obtain mixture, then scatter operation is carried out to the mixture so that CNT is dispersed in vehicle paint base, and dispersed to can obtain described CNT composite primer afterwards, this is combined The mass percent concentration of CNT is 0.1-1.5wt.% in priming paint, and the carbon nanometer that the composite primer is formed after spraying The surface resistance of pipe composite coating is 103–109Ω/□。
The scatter operation refers to ultrasonic disperse or ball milling is scattered.
When the scatter operation is ultrasonic disperse, the size of ultrasonic wave is 20-25Hz, and ultrasonic time is 60min.
The state when CNT is added to vehicle paint base is powdered or slurry.
A kind of application method of above-mentioned automobile-used CNT composite primer, the application method comprises the following steps successively：
First described CNT composite primer is sprayed on non-metal workpiece to obtain CNT composite coating, treated After CNT composite coating is dried, then to the composite coating spray paint by the way of electrostatic spraying, with nonmetallic zero The electrostatic spraying of finish paint is realized on part.
The drying mode of the CNT composite coating is：1h is dried at 80 DEG C.
The principle of the present invention is described as follows：
At present, the conductive additive applied to the face coat of nonmetallic parts is mainly conductive titanium white and carbon black, this The a little contents of conductive additive in primers typically can be only achieved anlistatig effect in 10-30wt.%, and usage amount is very big, no It improve only production cost (especially conductive titanium white, its unit price is higher), more crucially excessive conductive additive can influence The color of priming paint, so as to limit the color of the finish paint sprayed on priming paint, the color of finish paint has to push down the color ability of priming paint It can use, greatly reduce its application.In addition, conductive titanium white density is about 4g/cm3, and priming paint density is typically about 1g/ cm3, density is different to be easily layered, and is caused conductive titanium white to be difficult to disperse in primers, it is difficult to well mixed, is not only increased operation difficult Degree, and usage amount is improved, it is necessary to which electrostatic spraying could be realized by adding many conductive titanium whites, conductive titanium white is more, and its is right The influence of basecoat color is bigger, and the interference of color is stronger, more can limit the use of finish paint.
To overcome disadvantages described above, the present invention provides a kind of automobile-used CNT composite primer and its preparation, application method, its Core is that addition CNT is as conductive additive in primers, and after addition, CNT can be formed in composite primer Three-dimensional conductive network, this kind of three-dimensional conductive network can not only improve the electrical conductivity of composite primer, its surface resistance is met electrostatic The requirement of spraying, while the thermal conductivity of composite primer can also be improved, so as to improve the ageing resistace of composite primer.In addition, carbon The density of nanotube is approached with priming paint density, CNT is difficult layering in primers, and this is easy to CNT in primers Dispersed, more easy to be dispersed, the unit addition of CNT is fewer, and addition is fewer, more can reduce cost, More it is avoided that the use of finish paint will not be hindered by also getting over to the formation interference of the color of priming paint, its color to finish paint will not after all Formed and hindered.
Embodiment 1：
A kind of automobile-used CNT composite primer, including vehicle paint base and its conductive additive of internal doping；It is described to lead Electric additive is CNT, and the CNT is dispersed in vehicle paint base, and matter of the CNT in composite primer It is 0.1wt.% to measure percent concentration；The surface resistance for the CNT composite coating that the composite primer is formed after spraying is 109Ω/□。
A kind of preparation method of above-mentioned automobile-used CNT composite primer, the preparation method comprises the following steps successively： First CNT is added in vehicle paint base to obtain mixture, then scatter operation is carried out so that CNT to the mixture It is dispersed in vehicle paint base, it is dispersed to can obtain carbon in described CNT composite primer, the composite primer afterwards The mass percent concentration of nanotube is 0.1wt.%.
A kind of application method of above-mentioned automobile-used CNT composite primer, the application method comprises the following steps successively： First described CNT composite primer is sprayed on non-metal workpiece to obtain CNT composite coating (referring to Fig. 1), After after the drying of CNT composite coating, the surface resistance that CNT composite coating is measured with sheet resistance instrument is 109Ω/, Meet electrostatic spraying requirement, CNT composite coating surface is smooth, have no carbon in obvious clustered particles, display composite coating Nanotube is well dispersed.CNT composite coating is observed with SEM, CNT is uniformly dispersed (Fig. 2), coating surface in coating CNT is had no, then to the composite coating spray paint by the way of electrostatic spraying, so as to be realized on non-metal workpiece The electrostatic spraying of finish paint.
Embodiment 2：
Substance be the same as Example 1, difference is：Mass percent of the CNT in composite primer is dense Degree is 0.8wt.%；The surface resistance for the CNT composite coating that the composite primer is formed after spraying is 5 × 106Ω/□。
Embodiment 3：
Substance be the same as Example 1, difference is：Mass percent of the CNT in composite primer is dense Degree is 1.5wt.%；The surface resistance for the CNT composite coating that the composite primer is formed after spraying is 103Ω/□.With SEM observes CNT in CNT composite coating, coating and is uniformly dispersed (Fig. 3), and coating surface has no CNT.

Claims (8)

1. a kind of automobile-used CNT composite primer, including vehicle paint base and its conductive additive of internal doping, its feature exist In：
The conductive additive is CNT, and the CNT is dispersed in vehicle paint base, and CNT is compound Mass percent concentration in priming paint is 0.1-1.5 wt.%；
The surface resistance for the CNT composite coating that the composite primer is formed after spraying is 103–109Ω/, CNT The color of composite coating is shallower than automobile finish；
The CNT is single wall or multi-walled carbon nanotube, and the vehicle paint base is epoxylite or acrylic resin, The density of the CNT is 1.4 g/cm3, the density of vehicle paint base is 1 g/cm3；
The automobile-used CNT composite primer is prepared according to following step：First CNT is added in vehicle paint base to obtain To mixture, then to the mixture carry out scatter operation so that CNT in vehicle paint base it is dispersed, it is dispersed after The mass percent concentration that can obtain CNT in described CNT composite primer, the composite primer is 0.1-1.5 Wt.%, and the surface resistance of CNT composite coating that the composite primer is formed after spraying is 103–109 Ω/□。
2. a kind of automobile-used CNT composite primer according to claim 1, it is characterised in that：The CNT is multiple The mass percent concentration closed in priming paint is 0.8 wt.%；The CNT composite coating that the composite primer is formed after spraying Surface resistance be 5 × 106 Ω/□。
3. a kind of preparation method of the automobile-used CNT composite primer described in claim 1, it is characterised in that the preparation side Method comprises the following steps successively：
First CNT is added in vehicle paint base to obtain mixture, then scatter operation is carried out so that carbon is received to the mixture Mitron is dispersed in vehicle paint base, dispersed to can obtain described CNT composite primer, the composite primer afterwards The mass percent concentration of middle CNT is 0.1-1.5 wt.%, and the CNT that the composite primer is formed after spraying is multiple The surface resistance for closing coating is 103–109 Ω/□。
4. a kind of preparation method of automobile-used CNT composite primer according to claim 3, it is characterised in that：Described point Scattered operation refers to ultrasonic disperse or ball milling is scattered.
5. a kind of preparation method of automobile-used CNT composite primer according to claim 4, it is characterised in that：Described point When scattered operation is ultrasonic disperse, the size of ultrasonic wave is 20-25 Hz, and ultrasonic time is 60 min.
6. a kind of preparation method of automobile-used CNT composite primer according to claim 3, it is characterised in that：The carbon State when nanotube is added to vehicle paint base is powdered or slurry.
7. a kind of application method of the automobile-used CNT composite primer described in claim 1, it is characterised in that the user Method comprises the following steps successively：
First described CNT composite primer is sprayed on non-metal workpiece to obtain CNT composite coating, treats that carbon is received After mitron composite coating is dried, then to the composite coating spray paint by the way of electrostatic spraying, with non-metal workpiece Realize the electrostatic spraying of finish paint.
8. a kind of application method of automobile-used CNT composite primer according to claim 7, it is characterised in that：The carbon The drying mode of nano-pipe composite coating layer is：1h is dried at 80 DEG C.
CN201410692570.1A 2014-11-26 2014-11-26 Automobile-used CNT composite primer and its preparation, application method Active CN104403397B (en)

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Cited By (1)

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RU2765132C1 (en) * 2020-11-30 2022-01-25 МСД Текнолоджис С.а р.л. Priming compound for creating a light conductive priming coating of a part prior to electrostatic colouring, method for preparing the priming compound, and priming coating

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CN106243941B (en) * 2016-07-29 2018-08-07 东风商用车有限公司 A kind of carbon system can spot welding conductive coating and preparation method thereof
CN107573779A (en) * 2017-09-27 2018-01-12 芜湖春风新材料有限公司 A kind of CNT electrostatic spraying priming paint, preparation method and applications
CN115093741A (en) * 2022-07-18 2022-09-23 常州光辉化工有限公司 Carbon nanotube automobile coating self-repairing coating, coating and self-repairing method
TR2022014241A2 (en) * 2022-09-14 2022-10-21 Kanat Boyacilik Ticaret Ve Sanayi Anonim Sirketi A SURFACE PRIMER WITH LIGHT COLOR AND ELECTRICAL CONDUCTIVITY FOR APPLICATION TO AUTOMOTIVE PLASTIC SURFACES

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CN103108923A (en) * 2010-07-12 2013-05-15 韩华石油化学株式会社 Conductive coating composition and method for manufacturing a conductive layer using same
CN104011141A (en) * 2011-12-20 2014-08-27 昭和电工株式会社 Resin molded body for electrostatic coating
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RU2765132C1 (en) * 2020-11-30 2022-01-25 МСД Текнолоджис С.а р.л. Priming compound for creating a light conductive priming coating of a part prior to electrostatic colouring, method for preparing the priming compound, and priming coating

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