CN109777214B

CN109777214B - Graphene static conductive primer and preparation method thereof

Info

Publication number: CN109777214B
Application number: CN201711126820.5A
Authority: CN
Inventors: 郑雅轩; 杨修宝; 赖健平; 葛明; 瞿研
Original assignee: SIXTH ELEMENT (CHANGZHOU) MATERIALS TECHNOLOGY CO LTD
Current assignee: SIXTH ELEMENT (CHANGZHOU) MATERIALS TECHNOLOGY CO LTD
Priority date: 2017-11-15
Filing date: 2017-11-15
Publication date: 2021-10-15
Anticipated expiration: 2037-11-15
Also published as: CN109777214A

Abstract

The invention provides a graphene static conductive primer and a preparation method thereof. The primer comprises the following components in parts by mass: 35-55 parts of film forming material, 0.01-0.8 part of graphene or graphene compound, 8-42 parts of composite conductive filler, 8-42 parts of titanium dioxide, 0.005-1.6 parts of dispersing agent I, 1.5-5 parts of dispersing agent II, 0.5-3 parts of auxiliary agent and 5-20 parts of solvent. The brightness (L value) of the primer exceeds 60, and the resistance is lower than 0.1M omega.

Description

Graphene static conductive primer and preparation method thereof

Technical Field

The invention belongs to the field of nano composite materials, relates to a graphene-containing primer, and particularly relates to a graphene static conductive primer and a preparation method thereof.

Background

The static conductive coating is formed by adding pigment and filler with a conductive function into a resin matrix to endow the composite coating with a charge transmission function. Conductive fillers are key materials for various static conductive coatings. At present, carbon black, metal powder (silver, copper and nickel), composite conductive filler (conductive mica, conductive titanium dioxide, conductive quartz powder) and the like are mainly used as more conductive fillers. The metal powder is expensive, easy to be oxidized, large in addition amount during use, easy to be precipitated and dark in color. Carbon black is less expensive, but when added to a primer, the color of the coating is darker, difficult to control, and difficult to disperse. Therefore, the composite conductive filler is developed at home and abroad, and the mica, the titanium dioxide and the quartz powder have conductivity by metal doping modification. At present, conductive titanium dioxide is the most widely applied composite conductive filler, however, the traditional conductive titanium dioxide has high degradation rate in practical application and cannot well meet the requirements of permanent conductivity and static resistance.

With the continuous enhancement of environmental awareness of people, the traditional air spraying process with high energy consumption and low energy efficiency is gradually eliminated, and novel spraying processes and facilities are continuously popularized and applied. The electrostatic spraying overcomes the defects of serious pollution, low utilization rate of paint, obvious dead angle in comprehensive coating of complex workpieces, high secondary cleaning cost and the like in the traditional air spraying, and has the advantages of good coating quality, good operation environment, paint saving and the like, so that the painting rate and the production efficiency are greatly improved, and the comprehensive benefit is very obvious. At present, the static conductive primer for electrostatic spraying is mainly prepared by compounding carbon black and titanium dioxide or adding composite conductive filler to meet the conductivity requirement of the primer. And the conductive titanium dioxide cannot be ground, and when the conductive titanium dioxide is added in a large amount, the requirement of the coating with higher fineness requirement cannot be met.

Chinese invention patent CN103923552B discloses a high-performance graphene-needle-shaped titanium dioxide conductive coating and a preparation method thereof, the method takes aqueous epoxy resin emulsion as a matrix and graphene-needle titanium dioxide dispersion as a conductive filler, firstly needle conductive titanium dioxide is added into deionized water to form slurry with solid content of 5-20%, the slurry is heated and stirred to 40-90 ℃, then adding graphene according to the mass ratio of the needle-shaped titanium dioxide to the graphene of 0.5: 1-2: 1, continuing to perform ultrasonic dispersion for 1-5 hours, preparing graphene-needle titanium dioxide dispersion, mixing and dispersing the dispersion with aqueous epoxy resin emulsion and other coating additives uniformly to prepare the conductive coating, in the method, the mass fraction of the graphene in the graphene-acicular titanium dioxide dispersion liquid is large, and the graphene is not easily subjected to ultrasonic dispersion. In the absence of a surfactant, graphene is extremely easy to agglomerate and re-stack during the dispersion process of an aqueous solution due to the extremely high specific surface area and van der waals force of graphene itself. Chinese invention patent CN106009984A discloses a graphene/acrylic acid static conductive coating and a preparation method thereof, wherein the mass ratio of graphene to a dispersant is (1-20):1, the mass ratio of graphene to acrylic resin is 1: (20-1000), and other additives are added to prepare the graphene/acrylic acid static conductive coating, the surface resistivity of the coating is 1 MOmega, but the static conductive coating discussed in the patent does not consider the color requirement of the coating, and according to the long-term experiments of documents and authors of the patent, the appearance of the primer prepared according to the patent is black, and the coating is not suitable for the field with higher requirement on color and whiteness.

At present, the development of the electrostatic conductive primer with good conductivity and high brightness is one of the important problems which are concerned by the material boundary at home and abroad for a long time, and related work needs to be strengthened. Accordingly, the present invention is directed to a method for manufacturing a semiconductor device.

The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.

Disclosure of Invention

The first purpose of the invention is to realize the uniform compounding of the graphene or the graphene compound and the conductive titanium dioxide by a simple process to obtain a conductive compound with excellent performance.

The primer claimed by the invention comprises the following components in parts by mass: 35-55 parts of film forming material, 0.01-0.8 part of graphene or graphene compound, 8-42 parts of composite conductive filler, 8-42 parts of titanium dioxide, 0.005-1.6 parts of dispersing agent I, 1.5-5 parts of dispersing agent II, 0.5-3 parts of auxiliary agent and 5-20 parts of solvent.

In the primer, the mass parts of the components are as follows:

the film-forming substance can be 35, 40, 41, 42, 45.2, 46, 47, 48, 50 or 52.45 parts;

the graphene or graphene composite can be specifically 0.01, 0.05, 0.08, 0.2, 0.4, 0.6, 0.65 and 0.8 parts;

the composite conductive filler can be 8, 9, 10, 17, 20, 35, 36, 30, 32.62 and 36 parts;

the titanium dioxide can be 8, 10, 12, 14, 16.5, 17, 18, 20, 23, 25, 26, 34, 35, 40 or 42 parts;

the dispersant I can be 0.02, 0.05, 0.1, 0.2, 0.4, 0.6, 1.0, 1.2, 1.4 or 1.6 parts;

the dispersant II can be 1.5, 1.6, 1.7, 1.8, 2, 2.4, 2.9, 3, 3.2, 4 or 4.5 parts;

the auxiliary agent can be 0.5, 0.8, 1, 1.2, 1.5, 1.6, 1.8, 2.5, 2.77, 2.8 or 3 parts;

the solvent may specifically be 5, 6, 7, 10, 14.5, 15 or 20 parts;

specifically, the primer claimed by the invention may comprise the following components in parts by mass: 40-50 parts of film forming substances, 0.1-0.5 part of graphene or graphene compounds, 10-35 parts of composite conductive fillers, 10-35 parts of titanium dioxide, 0.05-1 part of dispersing agents I, 2-4 parts of dispersing agents II, 1-2.5 parts of auxiliary agents and 5-15 parts of solvents;

more specifically, the primer comprises the following components in parts by mass: 45-50 parts of film forming substances, 0.05-0.2 part of graphene or graphene compounds, 25-35 parts of composite conductive fillers, 12-25 parts of titanium dioxide, 0.02-0.2 part of dispersing agent I, 2.4-5 parts of dispersing agent II, 1.5-3 parts of auxiliary agents and 15-20 parts of solvents;

more specifically, the primer comprises the following components in parts by mass: 44.6 parts of film forming material, 0.2 part of graphene or graphene compound, 25 parts of composite conductive filler, 25 parts of titanium dioxide, 0.2 part of dispersing agent I, 3 parts of dispersing agent II, 2 parts of auxiliary agent and 14.5 parts of solvent.

In the primer, the film-forming substance is at least one selected from acrylic resin, epoxy resin, fluorocarbon resin and perchloroethylene resin;

the graphene composite is a composite material of graphene and other carbon materials, wherein the other carbon materials comprise carbon nanotubes and/or conductive carbon black;

the composite conductive filler is conductive titanium dioxide, conductive mica powder or conductive quartz powder; the composite conductive filler is preferably conductive titanium dioxide;

the titanium dioxide is anatase titanium dioxide;

the dispersant I is an anionic dispersant, a cationic dispersant, an amphoteric dispersant or a high molecular dispersant;

the dispersant II is a macromolecular dispersant;

the auxiliary agent is at least one selected from an anti-settling agent, a leveling agent and a defoaming agent; the solvent is at least one selected from toluene, xylene, ethyl acetate, butyl acetate, N-dimethylformamide, N-dimethylacetamide, absolute ethyl alcohol, isopropanol and dibutyl phthalate.

In the film-forming material, the acrylic resin is thermoplastic acrylic resin with the weight-average molecular weight of 80000-90000;

the epoxy resin is an epoxy resin with a low epoxy value of < 0.5;

the fluorocarbon resin is thermoplastic fluorocarbon resin with the weight-average molecular weight of 20000-50000;

the perchloroethylene resin is medium-low viscosity perchloroethylene resin;

in the graphene compound, the mass fraction of graphene is 10% -90%; specifically 33%, 50%, 90%, 30% -60%, 40% -60% or 60% -90%;

specifically, the method for preparing the graphene composite comprises the following steps: compounding graphene and carbon nano tubes or conductive carbon black by a blending and/or modifying process;

more specifically, a method of preparing the graphene composite, comprising: uniformly stirring and mixing the modifier and the solvent, adding the graphene and the carbon nano tube or the conductive carbon black, and stirring and reacting to obtain the modified graphene/carbon nano tube/conductive carbon black;

more specifically, during the stirring and uniform mixing of the modifier and the solvent, the stirring speed is 500-1000 rpm; stirring for 10-30 min; stirring at 50-100 deg.C, specifically 80 deg.C; in the stirring reaction step of adding the graphene and the carbon nano tube or the conductive carbon black, the stirring speed is 2000-3000 rpm; the reaction time is 0.5-2h, and can be 1h specifically; the reaction temperature is 50-100 ℃, and can be 80 ℃;

the modifier is specifically selected from at least one of octadecylamine, dodecylbenzene sulfonic acid and oleic acid;

the solvent is specifically selected from at least one of xylene, ethyl acetate, N-dimethylformamide and absolute ethyl alcohol;

the dosage of the modifier is specifically 10-20% of the total mass of the graphene and the carbon nano tube or the carbon black; specifically, 13.3 percent;

in the dispersant I, the anionic dispersant I is at least one selected from carboxylate, sulfate, phosphate and sulfonate;

the cationic dispersant I is at least one selected from alkyl quaternary ammonium salt, aminopropylamine dioleate and quaternary ammonium salt;

the amphoteric dispersant I is carboxylate;

the macromolecular dispersant I is at least one selected from natural macromolecular dispersants and synthetic macromolecular dispersants;

the dispersant I is specifically selected from at least one of BYK163, BYK161, BYK110, BYK118, Disponer 9850, SOLSPERSE37500, SOLSPERSE V350, SOLSPERSE20000, SOLSPERSE44000, S-601, Silok-7423, Dispers 610S, S-4010B, DA-01, DA-168, DA-1040, Tech 6320, Tech-510, DA-703-50, WinSperse4900, WinSperse3030, WinSperse3050, WinSperse3300 and WinSperse 3204;

the dispersant II is specifically selected from at least one of BYK163, BYK161, BYK110, DA-P10, DA-01, DA-168, DA-1040, Tech-510, Disperbyk-180, WinSperse3030, WinSperse3050, WinSperse3300, WinSperse3204, Dispex Ultra FA 4420, ZetaSperse 370, Sokalan CP 9, Ecodis P90 and Tego Dispers 740W;

the anti-settling agent is N-methyl pyrrolidone solution of modified polyurea, modified hydrogenated castor oil, titanate coupling agent or polyamide wax; a solution of N-methylpyrrolidone, preferably a modified polyurea;

the relative molecular mass of the polyamide wax is specifically 1500-3000;

the anti-settling agent is specifically selected from at least one of BYK-410, BYK-411, BYK-7411ES, FC-100, A630-SV, YB-301, EFKA 3777N, DAPRO BEZ 75, NDZ-201 and GHDY 920-20X;

the leveling agent is an organic silicon type leveling agent or an acrylate type leveling agent;

the flatting agent is specifically selected from at least one of BYK-323, BYK-352, BYK-354, BYK-333, BYK-3550, Silok-8358, Silok-8488 and EFKA 3777N;

the defoaming agent is a non-silicon defoaming agent, a polyether defoaming agent or a phosphate ester defoaming agent;

the antifoaming agent is specifically selected from at least one of BYK-017, BYK-018, BYK-051N, BYK-052N, BYK-1752, BYK-8821, B-224, B-225, Foamaster MO 2190AC, Tego Foamex 3062, XIAME ETER AFE-1430, Silok-4082, Silok-4084 and Silok-4075;

the mass ratio of the anti-settling agent to the leveling agent to the defoaming agent is 1.3-20: 1: 1-4; preferably, the ratio of 2: 1: 1.

in the primer, the graphene or graphene compound, the composite conductive filler and the graphene or graphene compound form a sheet-point-sheet structure conductive network; wherein the composite conductive filler is inserted into a sheet layer of the graphene or graphene composite;

the primer has an L value (lightness) of greater than 60; and/or the presence of a gas in the gas,

the electrical resistance of the primer is less than 0.1M Ω.

The second purpose of the invention is to provide a preparation method of the graphene static conductive primer. The primer prepared by the method has good conductivity and mechanical property and high brightness, and the primer prepared by the method has good interface combination with a substrate, long service life and good application value.

The preparation method of the primer claimed by the invention adopts the components in the ratio amount in the primer provided by the invention, and comprises the following steps:

uniformly stirring part of film forming substances and a solvent, sequentially adding a dispersing agent I and the graphene or the graphene compound, and grinding;

adding part of dispersant II and composite conductive filler, and uniformly stirring to obtain a component I;

stirring and uniformly mixing the rest of the film forming substances, the rest of the dispersing agent II and the titanium dioxide, and grinding the mixture to obtain a component II; and

and uniformly mixing the component I, the component II and the auxiliary agent to obtain the composition.

In the method, the part of the film forming material accounts for 30-75 wt% of the film forming material; specifically, it may be 40 wt%, 49 wt%, 53 wt%, 59 wt%, 60 wt%, 62 wt% or 65 wt%; preferably 50 wt%;

the partial dispersant II accounts for 20-75 wt% of the dispersant II; specifically, it may be 33 wt%, 37.5 wt%, 56 wt%, 62.5 wt%, 68 wt%, 69 wt% or 75 wt%; preferably 50% by weight.

In the step of uniformly stirring the partial film-forming substance and the solvent, the stirring time is 10-20min, and the stirring speed is 400-1200rpm, specifically 500rpm, 600rpm, 900rpm or 1100 rpm; preferably, the stirring time is 15min, and the stirring speed is 1000 rpm;

in the grinding step of adding the dispersing agent I and the graphene or the graphene compound, grinding until the fineness of the mixed material is less than 10 micrometers; preferably, the grinding time is 2-5h, and specifically can be 2.5h, 3.5h or 4 h; the grinding speed is 1500rpm-3500rpm, specifically 2300rpm, 2500rpm, 2800rpm or 3000 rpm; preferably, the milling time is 3h and the milling speed is 2000 rpm.

In the step of uniformly stirring after adding part of the dispersant II and the composite conductive filler, the stirring time is 20min to 60min, specifically 30min, 35min, 40min, 45min or 50 min; the stirring speed is 1000rpm-2000rpm, specifically 1400rpm, 1600rpm or 1800 rpm; preferably, the stirring time is 30min and the stirring speed is 1500 rpm.

In the step of uniformly stirring the residual film forming substances, the residual dispersing agent II and the titanium dioxide, the stirring time is 10-20min, specifically 16 min; the stirring speed is 200-1000rpm, specifically 300rpm or 500 rpm; preferably, the stirring time is 15 min; the stirring speed is 800 rpm;

in the grinding step after the residual film forming substances, the residual dispersing agent II and the titanium dioxide are uniformly stirred, grinding is carried out until the fineness of the obtained component II is less than 25 micrometers; preferably, the grinding time is 0.5-2h, and specifically can be 1.5 h; the grinding speed is 1500rpm-3500rpm, specifically 1600rpm, 2500rpm or 3000 rpm; further preferably, the milling time is 1 h; the grinding speed was 2000 rpm.

The third objective of the present invention is to protect the application of the primer provided by the present invention in preparing the electrostatic conductive primer and the electrostatic conductive primer containing the primer provided by the present invention.

The invention provides a graphene static conductive primer and a preparation method thereof, aiming at the defects in the static conductive primer aspect. The brightness (L value) of the primer exceeds 60, and the resistance is lower than 0.1M omega.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a coating prepared according to example 3 in the Chinese invention patent CN106009984A "graphene/acrylic acid static conductive coating and preparation method thereof";

FIG. 2 shows a coating prepared in example 10 of the present invention.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.

The acrylic resins used in the following examples are available from Beacus crane paint, Inc., Van. under the product designation BHR822, and are thermoplastic acrylic resins having a weight average molecular weight of 80000-90000; the epoxy resin used is commercially available from the commonly used epoxy resin type E44, with a low epoxy value < 0.5; the perchloroethylene resin is medium-low viscosity perchloroethylene resin, can be purchased from Weifang high-confidence chemical technology Limited company, and has the product number of HCPE-L; the fluorocarbon resin can be purchased from the new chemical material company Limited of the well-done Sanefuzhonghao, and the product number is JF-2X (solid content is 50 percent) and is thermoplastic fluorocarbon resin with the weight-average molecular weight of 20000-50000. The titanium dioxide used is commercially available from dupont under the model number R901. The conductive titanium dioxide can be purchased from Shenzhen technology Limited, Mishengya, the model number of which is MTI-02; the conductive mica powder can be purchased from Shanghai Deyu trade company Limited, and has the model of TS-210; the conductive quartz powder used is available from xu state gold sub-powder llc.

Example 1:

(1) weighing 61.9g of acrylic resin (containing 46.5 percent of solid content), 5g of xylene and 5g of toluene, mechanically stirring for 10min at 600rpm, adding 0.005g of dispersing agent Tech 6320 and 0.01g of graphene, grinding for 2h at the rotating speed of 2500rpm until the fineness of the mixed material is 8-10 microns, and filtering to obtain the component A.

(2) And adding 1.0g of dispersant BYK161 and 36g of conductive titanium dioxide into the component A, and stirring for 30min at 1800rpm to obtain a component I.

(3) Weighing 41.29g of acrylic resin (solid content is 46.5%), adding 0.5g of dispersant BYK161 and 14g of titanium dioxide, mechanically stirring for 10min at the rotating speed of 1000rpm, then grinding the mixture for 1.5h at the rotating speed of 2000rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II, 0.3g of anti-settling agent BYK-411, 0.1g of flatting agent Silok-8358 and 0.1g of defoaming agent BYK-017 to obtain the graphene static conductive primer 1.

Example 2:

(1) 75.3g of acrylic resin (containing 46.5 percent of solid content), 2g of xylene and 4g of butyl acetate are weighed, mechanically stirred for 15min at 900rpm, then 0.15g of dispersant WinSperse3204 and 0.05g of graphene are added, ground for 3.5h at the rotation speed of 2300rpm until the fineness of the mixed material is 7-9 microns, and filtered to obtain the component A.

(2) And adding 1.5g of dispersant BYK163 and 25g of conductive titanium dioxide into the component A, and stirring for 40min at 1000rpm to obtain a component I.

(3) Weighing 32.3g of acrylic resin (solid content is 46.5%), adding 0.5g of dispersant BYK163 and 17g of titanium dioxide, mechanically stirring for 16min at the rotating speed of 800rpm, then grinding the mixture for 2h at the rotating speed of 1600rpm until the fineness is less than 25 microns, and obtaining a component II.

(4) And uniformly stirring and mixing the component I, the component II, 0.4g of anti-settling agent BYK-410, 0.2g of flatting agent BYK-333 and 0.2g of defoaming agent BYK-052N to obtain the graphene static conductive primer 2.

Example 3:

(1) 64.13g of acrylic resin (solid content is 46.5%), 5g of butyl acetate and 2g of toluene are weighed, mechanically stirred for 20min at 500rpm, then 0.4g of polymeric dispersant I WinSperse3300 and 0.1g of graphene are added, ground for 2.5h at the rotation speed of 2800rpm until the fineness of the mixed material is 7-9 microns, and the component A is obtained after filtration.

(2) And adding 1.0g of dispersant BYK110 and 26g of conductive titanium dioxide into the component A, and stirring for 40min at 1400rpm to obtain a component I.

(3) Weighing 42.75g of acrylic resin (solid content is 46.5%), adding 0.8g of dispersant BYK110 and 23g of titanium dioxide, mechanically stirring for 10min at the rotating speed of 800rpm, then grinding the mixture for 1.5h at the rotating speed of 2500rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II (48 parts), 0.5g of anti-settling agent FC-100, 0.25g of flatting agent Silok-8358 and 0.25g of defoaming agent Silok-4082 to obtain the graphene static conductive primer 3.

Example 4:

(1) 42.75g of acrylic resin (containing 46.5 percent of solid content) and 3g of dimethylbenzene and 2g of N, N-dimethylformamide are weighed, mechanically stirred for 15min at 1100rpm, then 1.0g of dispersant WinSperse4900 and 0.4g of graphene are added, grinding is carried out for 4h at 3000rpm until the fineness of the mixed material is 8-9 microns, and the component A is obtained after filtration.

(2) And (3) adding 0.8g of dispersant DA-01 and 20g of conductive titanium dioxide into the component A, and stirring for 45min at 1500rpm to obtain a component I.

(3) Weighing 64.13g of acrylic resin (solid content is 46.5%), adding 0.9g of dispersant DA-01 and 26g of titanium dioxide, mechanically stirring for 20min at the rotating speed of 800rpm, grinding the mixture for 1h at the rotating speed of 3000rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II, 0.8g of anti-settling agent BYK-7411ES, 0.2g of flatting agent BYK-3550 and 0.2g of defoaming agent Tego Foamex 3062 to obtain the graphene static conductive primer 4.

Example 5:

(1) weighing 48.6g of acrylic resin (containing 46.5 percent of solid content), 2g of xylene, 1g of ethyl acetate and 2g of absolute ethyl alcohol, mechanically stirring for 15min at 1200rpm, then adding 1.2g of dispersing agent SOLSPERSE20000 and 0.5g of graphene, grinding for 3h at the rotation speed of 3500rpm until the fineness of the mixed material is 8-10 microns, and filtering to obtain the component A.

(2) And (3) adding 1.0g of dispersant WinSperse3030 and 17g of conductive titanium dioxide into the component A, and stirring for 35min at 1600rpm to obtain a component I.

(3) Weighing 42.6g of acrylic resin (containing 46.5 percent of solid), adding 0.6g of dispersant WinSperse3030 and 34g of titanium dioxide, mechanically stirring for 20min at the rotating speed of 800rpm, then grinding the mixture for 1.5h at the rotating speed of 2500rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II, 1g of anti-settling agent NDZ-201, 0.2g of flatting agent Silok-8488 and 0.4g of defoaming agent BYK-1752 to obtain the graphene static conductive primer 5.

Example 6:

(1) 60g of acrylic resin (solid content: 46.5%) and 3g of xylene are weighed, mechanically stirred for 15min at 1000rpm, then 0.6g of dispersing agent S-4010B and 0.6g of graphene are added, ground for 3.5h at 3000rpm until the fineness of the mixed material is 9-10 microns, and filtered to obtain the component A.

(2) And adding 1.5g of dispersing agent Tech-510 and 10g of conductive titanium dioxide into the component A, and stirring for 20min at 1000rpm to obtain the component I.

(3) 41.72g of acrylic resin (containing 46.5 percent of solid) is weighed, 2.5g of dispersing agent Tech-510 and 35g of titanium dioxide are added and mechanically stirred for 15min at the rotating speed of 800rpm, then the mixture is ground for 2h at the rotating speed of 2500rpm until the fineness is less than 25 microns, and the component II is obtained after filtration.

(4) And uniformly stirring and mixing the component I, the component II, 2g of anti-settling agent EFKA 3777N, 0.1g of flatting agent Silok-8488 and 0.4g of defoaming agent B-225 to obtain the graphene static conductive primer 6.

Example 7:

(1) 26.65g of acrylic resin (containing 46.5 percent of solid content), 3g of xylene and 3g of isopropanol are weighed, mechanically stirred for 15min at 1200rpm, then 1.6g of dispersing agent Silok-7423 and 0.8g of graphene are added, ground for 5h at the rotation speed of 3500rpm until the fineness of the mixed material is 7-10 microns, and filtered to obtain the component A.

(2) And adding 1.5g of dispersant DA-01 and 9g of conductive titanium dioxide into the component A, and stirring for 30min at 1000rpm to obtain a component I.

(3) Weighing 62.17g of acrylic resin (solid content is 46.5%), adding 3g of dispersant DA-01 and 40g of titanium dioxide, mechanically stirring for 20min at the rotation speed of 1000rpm, grinding the mixture for 2h at the rotation speed of 3500rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II, 2g of anti-settling agent A630-SV, 0.3g of flatting agent Silok-8488 and 0.5g of defoaming agent BYK-8821 to obtain the graphene static conductive primer 7.

Example 8:

(1) 45.91g of acrylic resin (containing 46.5 percent of solid content), 10g of xylene and 10g of dibutyl phthalate are weighed, mechanically stirred for 20min at 400rpm, then 1.4g of dispersant BYK118 and 0.65g of graphene are added, ground for 3h at the rotating speed of 2500rpm until the fineness of the mixed material is 7-10 microns, and filtered to obtain the component A.

(2) And adding 1.0g of dispersing agent Tech-510 and 8g of conductive titanium dioxide into the component A, and stirring for 20min at 2000rpm to obtain a component I.

(3) Weighing 40g of acrylic resin (solid content is 46.5%), adding 4g of dispersing agent Tech-510 and 42g of titanium dioxide, mechanically stirring for 15min at the rotation speed of 1000rpm, grinding the mixture for 1.5h at the rotation speed of 3000rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II, 2g of an anti-settling agent A630-SV, 0.5g of a leveling agent BYK-333 and 0.5g of a defoaming agent Foamaster MO 2190AC to obtain the graphene static conductive primer 8.

Example 9:

(1) mixing 0.1g of octadecylamine and 50 ml of absolute ethyl alcohol, stirring at 500rpm for 30min at 80 ℃, adding 0.9g of graphene and 0.1g of carbon nano tube, stirring at 2000rpm for reaction for 1h, stirring at 80 ℃, washing, filtering and drying to obtain the graphene and carbon nano tube composite.

(2) Weighing 75g of epoxy resin (40 percent of solid content) and 5g of xylene, mechanically stirring for 15min at 1000rpm, then adding 0.1g of dispersant WinSperse3030 and 0.15g of the graphene and carbon nanotube composite obtained in the step 1), grinding for 3h at 2000rpm until the fineness of the mixed material is 8-10 microns, and filtering to obtain the component A.

(3) 3.4g of dispersant BYK161 and 30g of conductive mica powder are added into the component A, and the mixture is stirred for 30min at 1800rpm to obtain a component I.

(4) Weighing 40g of epoxy resin (the solid content is 40%), adding 1.6g of dispersant BYK161 and 16.55g of titanium dioxide, mechanically stirring for 15min at the rotating speed of 800rpm, then grinding the mixture for 1h at the rotating speed of 2000rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(5) And uniformly stirring and mixing the component I, the component II, 1.6g of an anti-settling agent BYK-410, 0.2g of a leveling agent BYK-354 and 0.4g of a defoaming agent BYK-8821 to obtain the graphene static conductive primer 9.

Example 10:

(1) weighing 47.96g of acrylic resin (containing 46.5 percent of solid content) and 14.5g of xylene, mechanically stirring for 15min at 1000rpm, adding 0.2g of dispersant WinSperse3204 and 0.2g of graphene, grinding for 3h at the rotating speed of 2000rpm until the fineness of the mixed material is 8-10 microns to obtain the component A.

(2) And adding 1.5g of dispersant BYK161 and 25g of conductive titanium dioxide into the component A, and stirring for 30min at 1500rpm to obtain a component I.

(3) Weighing 47.96g of acrylic resin (containing 46.5 percent of solid), adding 1.5g of dispersant BYK161 and 25g of titanium dioxide, mechanically stirring for 15min at the rotating speed of 800rpm, and then grinding the mixture for 1h at the rotating speed of 2000rpm until the fineness is less than 25 microns to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II (48 parts), 1g of anti-settling agent BYK-410, 0.5g of flatting agent Silok-8488 and 0.5g of defoaming agent Silok-4082 to obtain the graphene static conductive primer 10.

Example 11:

(1) 60g of perchloroethylene resin (solid content: 50%) and 10g of butyl acetate are weighed, mechanically stirred for 20min at 1000rpm, then 0.05g of dispersing agent Tech-6320 and 0.05g of graphene are added, ground for 4h at the rotating speed of 3000rpm until the fineness of the mixed material is 8-9 microns, and the component A is obtained after filtration.

(2) 1.5g of dispersant BYK161 and 35g of conductive quartz powder are added into the component A, and the mixture is stirred for 45min at 1500rpm to obtain a component I.

(3) Weighing 38g of perchloroethylene resin (solid content is 50%), adding 0.9g of dispersant BYK161 and 12g of titanium dioxide, mechanically stirring for 15min at the rotation speed of 1000rpm, grinding the mixture for 2h at the rotation speed of 2000rpm, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II, 1g of anti-settling agent BYK-411, 0.25g of flatting agent BYK-3550 and 0.25g of defoaming agent XIAMERETER AFE-1430 to obtain the graphene static conductive primer 11.

Example 12:

(1) mixing 0.4g of dodecylbenzene sulfonic acid with 100 ml of N, N-dimethylformamide, stirring at 60 ℃ for 10min at 1000rpm, adding 1g of graphene and 1g of conductive carbon black, stirring at 3000rpm for reaction for 0.5h, stirring at 60 ℃, washing, filtering and drying to obtain the compound of graphene and conductive carbon black.

(2) Weighing 78.87g of fluorocarbon resin (containing 50 percent of solid content) and 5g of xylene, mechanically stirring for 10min at 1200rpm, adding 0.1g of dispersing agent WinSperse3300 and 0.08g of the compound of the graphene obtained in the step 1) and the conductive carbon black, grinding for 3h at 2000rpm until the fineness of the mixed material is 9-10 microns, and filtering to obtain the component A.

(3) And adding 2g of dispersant BYK110 and 32.62g of conductive titanium dioxide into the component A, and stirring for 50min at 1500rpm to obtain a component I.

(4) Weighing 26.29g of fluorocarbon resin (solid content: 50%), adding 0.9g of dispersant BYK110 and 10g of titanium dioxide, mechanically stirring for 10min at the rotating speed of 300rpm, grinding the mixture for 2h at the rotating speed of 2000rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(5) And uniformly stirring and mixing the component I, the component II, 1g of anti-settling agent YB-301, 0.4g of flatting agent Silok-8488 and 0.4g of defoaming agent BYK-051N to obtain the graphene static conductive primer 12.

Example 13:

(1) and (2) uniformly mixing 0.4g of oleic acid and 100 ml of absolute ethyl alcohol, stirring at 50 ℃ for 10min at 1000rpm, adding 1g of graphene, 0.5g of conductive carbon black and 0.5g of carbon nano tube, stirring at 3000rpm, reacting for 1h, washing, filtering and drying after stirring at 50 ℃, so as to obtain the graphene composite.

(2) 67.53g of acrylic resin (containing 46.5 percent of solid) and 5g of xylene are weighed, mechanically stirred for 15min at 1200rpm, then 0.02g of dispersant WinSperse4900 and 0.01g of graphene compound obtained in the step 1) are added, the mixture is ground for 2.5h at the rotating speed of 2000rpm until the fineness of the mixed material is 7-10 microns, and the component A is obtained after filtration.

(3) And (3) adding 2g of dispersant BYK163 and 26g of conductive titanium dioxide into the component A, and stirring for 30min at 1500rpm to obtain a component I.

(4) Weighing 40g of acrylic resin (solid content is 46.5%), adding 1.2g of dispersant BYK163 and 18g of titanium dioxide, mechanically stirring for 10min at the rotation speed of 500rpm, grinding the mixture for 1h at the rotation speed of 2000rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(5) And stirring and uniformly mixing the component I, the component II, 1g of anti-settling agent BYK-411, 1g of flatting agent EFKA 3777N and 1g of defoaming agent BYK-018 to obtain the graphene static conductive primer 13.

Example 14:

(1) 46.02g of acrylic resin (containing 46.5 percent of solid) and 15g of xylene are weighed, mechanically stirred for 15min at 1000rpm, then 1.6g of dispersing agent S-601 and 0.4g of graphene are added, ground for 3h at the rotating speed of 2000rpm until the fineness of the mixed material is 7-10 microns, and filtered to obtain the component A.

(2) And (3) adding 1g of dispersing agent WinSperse3050 and 42g of conductive titanium dioxide into the component A, and stirring for 60min at 1500rpm to obtain a component I.

(3) Weighing 40g of acrylic resin (containing 46.5 percent of solid), adding 0.6g of dispersant WinSperse3050 and 8g of titanium dioxide, mechanically stirring for 15min at the rotating speed of 800rpm, then grinding the mixture for 1h at the rotating speed of 2000rpm until the fineness is less than 25 microns, and filtering to obtain a component II.

(4) And uniformly stirring and mixing the component I, the component II, 1g of anti-settling agent A630-SV, 0.77g of flatting agent BYK-3550 and 1g of defoaming agent BYK-8821 to obtain the graphene static conductive primer 14.

Example 15:

(1) and (2) uniformly mixing 0.2g of oleic acid, 50 ml of ethyl acetate and 50 ml of absolute ethyl alcohol, stirring at 50 ℃ for 10min at 1000rpm, adding 1g of graphene and 0.5g of carbon nano tube, stirring at 3000rpm for reaction for 1h, stirring at 50 ℃, washing, filtering and drying to obtain the graphene composite.

(2) Weighing 45.27g of acrylic resin (containing 46.5 percent of solid content) and 10g of xylene, mechanically stirring for 10min at 1000rpm, then adding 1.4g of dispersing agent WinSperse330 and 0.6g of the compound of the graphene and the carbon nano tube obtained in the step 1), grinding for 3h at 2000rpm until the fineness of the mixed material is 8-10 microns, and filtering to obtain the component A.

(3) And 3.5g of dispersant WinSperse3204 and 35g of conductive titanium dioxide are added into the component A, and the mixture is stirred for 30min at 1500rpm to obtain a component I.

(4) 30g of acrylic resin (containing 46.5 percent of solid content) is weighed, 1.5g of dispersing agent WinSperse3204 and 20g of titanium dioxide are added and mechanically stirred for 15min at the rotating speed of 800rpm, then the mixture is ground for 1h at the rotating speed of 2000rpm until the fineness is less than 25 microns, and the component II is obtained after filtration.

(5) And uniformly stirring and mixing the component I, the component II, 2g of anti-settling agent BYK-410, 0.5g of flatting agent Silok-8488 and 0.5g of defoaming agent Silok-4082 to obtain the graphene static conductive primer 15.

The graphene primers prepared in examples 1 to 15 were electrostatically sprayed on the surfaces of the plastic substrate and the tin plate substrate. After the coating has dried, the resistance of the coating is tested using a multimeter, the L value of the coating is tested using a model NR-10 colorimeter, the water resistance of the coating is tested according to GB/T1733-1993 paint film water resistance test, the adhesion of the coating is tested according to GB/T9286-1998 cut and paint film scratch test, and the impact resistance of the coating is tested according to GB/T1732-1993 paint film impact resistance test.

The performance test results of the graphene primer of each example are shown in table 1 below.

TABLE 1 graphene primer Performance test results

From the analysis of the performance test results, the graphene primer prepared by the process has the advantages of low resistance, high brightness, good water resistance and good mechanical properties.

As can be seen from a comparison between fig. 1 and fig. 2, the primer prepared according to CN106009984A, a graphene/acrylic static conductive coating and a preparation method thereof, is pure black, whereas the primer prepared in example 10 of the present invention has a light color and a wider application range.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A primer characterized by: the primer consists of the following components in parts by mass: 40-50 parts of film forming substances, 0.1-0.5 part of graphene or graphene compounds, 10-35 parts of composite conductive fillers, 10-35 parts of titanium dioxide, 0.05-1 part of dispersing agents I, 2-4 parts of dispersing agents II, 1-2.5 parts of auxiliary agents and 5-15 parts of solvents;

the film forming substance is at least one of acrylic resin, epoxy resin, fluorocarbon resin and perchloroethylene resin; wherein the acrylic resin is thermoplastic acrylic resin with the weight-average molecular weight of 80000-90000; the epoxy resin is an epoxy resin with a low epoxy value of < 0.5; the fluorocarbon resin is thermoplastic fluorocarbon resin with the weight-average molecular weight of 20000-50000; the perchloroethylene resin is medium-low viscosity perchloroethylene resin;

the primer is prepared by the following method:

uniformly mixing the component I, the component II and the auxiliary agent to obtain the composition;

wherein the part of the film forming material accounts for 30-75 wt% of the film forming material; the partial dispersant II accounts for 20-75 wt% of the dispersant II;

the dispersant I is an anionic dispersant, a cationic dispersant, an amphoteric dispersant or a high molecular dispersant; the dispersant II is a high molecular dispersant.

2. The primer of claim 1, wherein: the primer consists of the following components in parts by mass: 44.6 parts of film forming material, 0.2 part of graphene or graphene compound, 25 parts of composite conductive filler, 25 parts of titanium dioxide, 0.2 part of dispersing agent I, 3 parts of dispersing agent II, 2 parts of auxiliary agent and 14.5 parts of solvent.

3. The primer according to claim 1 or 2, characterized in that: the graphene composite is a composite material of graphene and other carbon materials, wherein the other carbon materials comprise carbon nanotubes and/or conductive carbon black.

4. A primer according to claim 3, characterized in that: in the graphene compound, the mass fraction of graphene is 10% -90%.

5. The primer of claim 4, wherein: in the graphene compound, the mass fraction of graphene is 30-90%.

6. A primer according to claim 3, characterized in that: a method of making the graphene composite, comprising: compounding graphene and carbon nano tubes or conductive carbon black by a blending and/or modifying process; or,

a method of making the graphene composite, comprising: and uniformly stirring the modifier and the solvent, adding the graphene and the carbon nano tube or the conductive carbon black, and stirring to react to obtain the graphene/carbon nano tube/conductive carbon black composite material.

7. The primer of claim 6, wherein: during the stirring and uniform mixing of the modifier and the solvent, the stirring speed is 500-1000 rpm; stirring for 10-30 min; the stirring temperature is 50-100 ℃.

8. The primer of claim 6, wherein: in the stirring reaction step of adding the graphene and the carbon nano tube or the conductive carbon black, the stirring speed is 2000-3000 rpm; the reaction time is 0.5-2 h; the reaction temperature is 50-100 ℃.

9. The primer of claim 6, wherein: the modifier is specifically selected from at least one of octadecylamine, dodecylbenzene sulfonic acid and oleic acid.

10. The primer of claim 6, wherein: the dosage of the modifier is 10-20% of the total mass of the graphene and the carbon nano tube or the carbon black.

11. The primer according to claim 1 or 2, characterized in that: the composite conductive filler is conductive titanium dioxide.

12. The primer according to claim 1 or 2, characterized in that: the titanium dioxide is anatase titanium dioxide.

13. The primer according to claim 1 or 2, characterized in that: the anionic dispersant I is at least one selected from carboxylate, sulfate, phosphate and sulfonate.

14. The primer according to claim 1 or 2, characterized in that: the cationic dispersant I is at least one selected from alkyl quaternary ammonium salt, aminopropylamine dioleate and quaternary ammonium salt.

15. The primer according to claim 1 or 2, characterized in that: the amphoteric dispersant I is carboxylate.

16. The primer according to claim 1 or 2, characterized in that: the polymeric dispersant I is at least one selected from natural polymeric dispersants and synthetic polymeric dispersants.

17. The primer according to claim 1 or 2, characterized in that: the auxiliary agent is at least one selected from an anti-settling agent, a leveling agent and an antifoaming agent.

18. The primer according to claim 1 or 2, characterized in that: the solvent is at least one selected from toluene, xylene, ethyl acetate, butyl acetate, N-dimethylformamide, N-dimethylacetamide, absolute ethyl alcohol, isopropanol and dibutyl phthalate.

19. The primer according to claim 1 or 2, characterized in that: the dispersant I is specifically selected from at least one of BYK163, BYK161, BYK110, BYK118, Disponer 9850, SOLSPERSE37500, SOLSPERSE V350, SOLSPERSE20000, SOLSPERSE44000, S-601, Silok-7423, Dispers 610S, S-4010B, DA-01, DA-168, DA-1040, Tech-6320, Tech-510, DA-703-50, WinSperse4900, WinSperse3030, WinSperse3050, WinSperse3300 or WinSperse 3204.

20. The primer according to claim 1 or 2, characterized in that: the dispersant II is specifically selected from at least one of BYK163, BYK161, BYK110, DA-P10, DA-01, DA-168, DA-1040, Tech-510, Disperbyk-180, WinSperse3030, WinSperse3050, WinSperse3300, WinSperse3204, Dispex Ultra FA 4420, ZetaSperse 370, Sokalan CP 9, Ecodis P90 or Tego Dispers 740W.

21. The primer of claim 17, wherein: the anti-settling agent is N-methyl pyrrolidone solution of modified polyurea, modified hydrogenated castor oil, titanate coupling agent or polyamide wax.

22. The primer of claim 21, wherein: the relative molecular mass of the polyamide wax is specifically 1500-3000.

23. The primer of claim 21, wherein: the anti-settling agent is specifically selected from at least one of BYK-410, BYK-411, BYK-7411ES, FC-100, A630-SV, YB-301, EFKA 3777N, DAPRO BEZ 75, NDZ-201 and GHDY 920-20X.

24. The primer of claim 17, wherein: the leveling agent is an organic silicon type leveling agent or an acrylate type leveling agent.

25. The primer of claim 24, wherein: the leveling agent is specifically selected from at least one of BYK-323, BYK-352, BYK-354, BYK-333, BYK-3550, Silok-8358, Silok-8488 and EFKA 3777N.

26. The primer of claim 17, wherein: the defoaming agent is a non-silicon defoaming agent.

27. The primer of claim 26, wherein: the defoaming agent is specifically selected from at least one of BYK-017, BYK-018, BYK-051N, BYK-052N, BYK-1752, BYK-8821, B-224, B-225, Foamaster MO 2190AC, Tego Foamex 3062, XIAMERETER AFE-1430, Silok-4082, Silok-4084 or Silok-4075.

28. The primer of claim 17, wherein: the mass ratio of the anti-settling agent to the leveling agent to the defoaming agent is 1.3-20: 1: 1-4.

29. The primer of claim 28, wherein: the mass ratio of the anti-settling agent to the leveling agent to the defoaming agent is 2: 1: 1.

30. the primer according to claim 1 or 2, characterized in that: in the primer, the graphene or graphene compound, the composite conductive filler and the graphene or graphene compound form a sheet-point-sheet structure conductive network; wherein the composite conductive filler is inserted into a sheet layer of the graphene or graphene composite.

31. The primer of claim 30, wherein: the lightness L value of the primer is greater than 60.

32. The primer of claim 30, wherein: the surface resistance of the primer is less than 0.1 MOmega.

33. The primer according to claim 1 or 2, characterized in that: the portion of the film-forming material is 50 wt% of the film-forming material.

34. The primer according to claim 1 or 2, characterized in that: the partial dispersant II accounts for 50 wt% of the dispersant II.

35. The primer according to claim 1 or 2, characterized in that: in the step of uniformly stirring the part of the film-forming substances and the solvent, the stirring time is 10-20min, and the stirring speed is 400-1200 rpm.

36. The primer of claim 35, wherein: in the step of uniformly stirring the part of the film forming substances and the solvent, the stirring time is 15min, and the stirring speed is 1000 rpm.

37. The primer according to claim 1 or 2, characterized in that: and in the step of grinding by adding the dispersing agent I and the graphene or the graphene compound, grinding until the fineness of the mixed material is less than 10 micrometers.

38. The primer of claim 37, wherein: in the grinding step of adding the dispersing agent I and the graphene or the graphene compound, the grinding time is 2-5h, and the grinding speed is 1500-3500 rpm.

39. The primer of claim 38, wherein: the grinding time is 3h, and the grinding speed is 2000 rpm.

40. The primer according to claim 1 or 2, characterized in that: in the step of uniformly stirring after adding part of the dispersant II and the composite conductive filler, the stirring time is 20min-60min, and the stirring speed is 1000rpm-2000 rpm.

41. The primer of claim 40, wherein: in the step of uniformly mixing and stirring after adding part of the dispersant II and the composite conductive filler, the stirring time is 30min, and the stirring speed is 1500 rpm.

42. The primer according to claim 1 or 2, characterized in that: in the step of uniformly stirring and mixing the residual film-forming substance, the residual dispersing agent II and the titanium dioxide, the stirring time is 10-20min, and the stirring speed is 200-1000 rpm.

43. The primer of claim 42, wherein: in the step of uniformly stirring and mixing the residual film forming substances, the residual dispersing agent II and the titanium dioxide, the stirring time is 15 min; the stirring speed was 800 rpm.

44. The primer according to claim 1 or 2, characterized in that: and in the grinding step after the residual film forming substances, the residual dispersing agent II and the titanium dioxide are uniformly stirred, grinding is carried out until the fineness of the obtained component II is less than 25 micrometers.

45. The primer of claim 44, wherein: in the grinding step after the residual film forming substances, the residual dispersing agent II and the titanium dioxide are uniformly stirred, the grinding time is 0.5-2h, and the grinding speed is 1500-3500 rpm.

46. The primer of claim 45, wherein: in the grinding step after the residual film forming substances, the residual dispersing agent II and the titanium dioxide are uniformly stirred, the grinding time is 1 h; the grinding speed was 2000 rpm.

47. An electrostatically conductive primer comprising the primer of any one of claims 1-46.