CN1944555A - Environment friendly nano static conductive paint and its preparing method - Google Patents
Environment friendly nano static conductive paint and its preparing method Download PDFInfo
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Abstract
The present invention is one kind of environment friendly nanometer static conductive paint and its preparation process. The static conductive paint has carbon nanotube or its composition with inorganic conducting filler as the conducting medium, and water soluble acrylate resin emulsion as the filming matter. It is prepared through three steps: 1. preparing dispersed liquid of carbon nanotube or its composition with inorganic conducting filler; 2. preparing pigment and filler slurry; and 3. compounding the slurry with the dispersed liquid. Compared with traditional static conductive paint, the present invention has the advantages of less added conducting filler, less conducting component deposition and separation, lasting conducting property, environment friendship, etc. The environment friendly nanometer static conductive paint is especially suitable for indoor use.
Description
Technical field
The present invention relates to a kind of environment friendly nano static conductive paint and preparation method thereof.This coating utilizes nano material or nano composite material as conducting medium, thereby makes coating have the special static function of leading, and belongs to functional paint and fields of nano material application.
Background technology
In recent years,, how to prevent the harm that static brings, become a problem that presses for solution along with develop rapidly, wide application of micro-electronic technology and the electromagnetic environment of science and technology becomes increasingly complex.On the one hand, the widespread use of the macromolecular material that some resistivity are very high such as the goods of plastics, rubber etc. and the high speed of modern production process make electrostatic energy run up to very high degree; On the other hand, the production of electrostatic sensitive material and use, as light-end products, gunpowder, solid electronic device etc., department of industrial and mining enterprises is subjected to electrostatic harm also more and more outstanding.Static hazard can cause quite serious consequence and loss, and it can cause electronic industry year with a toll of the over ten billion dollar inadvertently with the electron device puncture of costliness; Static discharge can also cause rocket and satellites transmits failure, disturbs the operation of emerging boat aircraft.Static hazard extensively is present in electronic industry, petroleum industry, weapon industry, textile industry, rubber industry and aerospace and military field.Because the manufacturing and the applied environment of electron device and equipment must possess the envrionment conditions that prevents static hazard, resists electronic jamming, so the anti-electrostatic of architecture indoor environment, the anti-interference important assurance that has also become the cyberage Economic development.
Utilize conducting electrostatic materials to lead away and eliminate static in time and just can prevent the harm that brings because of static.Wherein, static conductive coating is as a kind of conducting electrostatic materials of top layer, extremely payes attention to owing to have outstanding advantage such as selection is extensive, practical, cost performance is high, construction facility.Static conductive coating can be divided into two kinds of eigenmode and addition types, eigenmode is to prepare the macromole with conjugation ∏ key by molecular designing to obtain electroconductibility, as polyethylene, polypyrrole, polyaniline etc., the research of such conductive polymers at present also is in the laboratory study stage, subject matter is cost height, complicated process of preparation, control difficulty, and this base polymer generally dissolves difficulty in organic solvent, and usual way is difficult to construction; Addition type is to obtain electroconductibility by add some conducting material in coating, and substance comprises carbon system, metal system, metal oxide semiconductor system and the synthetic ionic antistatic agent of organism etc.At present, the addition type static conductive coating is the most general a kind of, and the part kind has realized commercialization, as carbon is main Antistatic Paint, its good electrical conductivity has obtained widespread use in every field, petrochemical complex aspect particularly, but its sticking power and oil-proofness are poor, decorate properties is poor; Use so that the static conductive coating of metal-powder is little at present, major cause is to cost an arm and a leg, and the easy oxidation of metallic surface is than great; Add the static conductive coating of conductor oxidate and also partly realize commercialization, but because shortcomings such as preparation cost height, the proportion height of oxide compound own, coating free settling are restricted its popularization; Organism compound particle type Antistatic Paint auxiliary agent is a kind of tensio-active agent, poor stability, slow, the poor durability of electric charge leakage rate, and it is used also significant limitation.Develop multiple novel static conductive coating; not only can be used for the effect that main equipments such as petroleum storage tank, network system play anticorrosion and antistatic; also make it to be widely used in occasions such as inner wall of building, terrace, floor; both played the effect of attractive, decorative, the function that has anti-electrostatic again has very positive meaning.At present, the antistatic material that is used for architecture indoor is mainly sheet materials such as the metal of anti-electrostatic, plastics, rubber, and leads static floor, terrace paint, and ubiquitous problem is that resource cost is big, cost is high, decorate properties difference etc.
At present, domestic static conductive coating generally is solvent-borne type, has not only wasted a large amount of useful resources but also has had pollution problem to environment.Therefore, the exploitation of environment-friendly type static conductive coating also is the trend of static conductive coating research field.Current, water-borne coatings had not both been saved resource owing to do not contain advantages such as organic solvent, zero VOC discharging, had reduced the pollution to environment again, and environmental-protecting performance is very outstanding.Current, the application of aqueous architectural coating is very extensive, and does not almost have at the water-based static conductive coating of building wall.Exploitation is applicable to the not only alternative existing expensive anti-electrostatic building and ornament materials of water-based static conductive coating of building wall, and aqueous coating system can reduce the harm to environment space, can be the solution that architecture indoor anti-electrostatic problem provides a kind of economy, environmental protection.
Summary of the invention
One of purpose of the present invention is to provide a kind of environment friendly nano static conductive paint of leading the static function that has.
Two of purpose of the present invention is to provide a kind of preparation method with the environment friendly nano static conductive paint of leading the static function.
One of purpose of the present invention can realize like this, designs a kind of environment friendly nano static conductive paint, comprises the following component of calculating content by mass percentage:
Aqueous acrylic emulsion 25～30
Conductive nano filler 0.2～10
Pigment 45～55
Coatings additive(s) 2～5
Solvent 15～20
Two of purpose of the present invention can realize like this, designs a kind of preparation method of environment friendly nano static conductive paint, comprises three phases: fs, the dispersion liquid of preparation CNT (carbon nano-tube); Subordinate phase, the slurry of preparation color stuffing; Phase III, the mixing preparation of slurry and resin emulsion;
The step of described fs preparation is as follows:
A, with CNT (carbon nano-tube) and wetting dispersing agent in 1: add 5～10 times solvent behind the ratio premix of (1～2.5), be made into mixed solution, arrest reaction 15～30 minutes;
B, mixed solution was carried out supersound process 20～30 minutes, leaches bottom settlings with 400～600 eye mesh screens, will precipitate again with dispersion agent by 1: the mixed of (0.1～0.2), carry out supersound process again after adding 5～10 times of solvent reactions; Repeat above-mentioned filtration, mixing, dispersion steps, up to dispersion liquid bottom do not have precipitation or precipitation weight less than initial CNT (carbon nano-tube) weight 10% till;
C, the mixed dispersion liquid that above-mentioned repeating dispersion is obtained are added solvent, are made into the CNT (carbon nano-tube) dispersion liquid of specified amount;
The step of described subordinate phase preparation is as follows:
D, based on the CNT (carbon nano-tube) dispersion liquid of fs preparation, add pigment, dispersion agent, defoamer and frostproofer, under 800～1600r/min rotating speed, grind dispersion 60～80 minutes at a high speed, obtain the slurry of color stuffing;
The step of described phase III preparation is as follows:
E, the color stuffing slurry that subordinate phase is prepared mix with ACRYLIC EMULSION in proportion, add defoamer, flow agent, film coalescence aid and pH regulator agent under the stirring at low speed of 300～500r/min, stir 20～30 minutes;
F, the back that stirs add thickening material, regulate dope viscosity 〉=25s (being coated with-4 glasss);
Obtain the nano static conductive paint finished product after G, the filtration.
The conductive filler material that the present invention uses the nano material of minute quantity to substitute traditional high addition realizes leading the electrostatic function, not only economizes on resources but also guarantee the lasting reliable of conductive coating performance, has improved the over-all properties of coating and has made coating be easy to the outward appearance that obtains to enrich.The employing of aqueous coating system more meets Sustainable development and environmental protection requirement.The present invention is mainly used in the metope of architecture indoor, the interior space that needs anti-electrostatic such as can be widely used between computer house, clean room, electronic product production plant, Operation theatre, military depot, hoolivan, can be the solution that architecture indoor anti-electrostatic problem provides a kind of economy, environmental protection.
Embodiment
The invention will be further described below in conjunction with embodiment.
A kind of complex body with CNT (carbon nano-tube) or CNT (carbon nano-tube) and other inorganic conductive filler is a conducting medium, aqueous acrylic emulsion is that main film forming substance is prepared the environment friendly nano static conductive paint that is applicable to building wall, comprises the following component of calculating content by mass percentage:
Aqueous acrylic emulsion 25～30
Conductive nano filler 0.2～10
Pigment 45～55
Coatings additive(s) 2～5
Solvent 15～20
Described aqueous acrylic emulsion is phenylpropyl alcohol or pure-acrylic emulsion.
Described conductive nano filler is the complex body of CNT (carbon nano-tube) or CNT (carbon nano-tube) and other inorganic conductive filler.
Described wherein CNT (carbon nano-tube) be caliber between 10～100nm, length is the multiple-wall carbon nanotube of 5～15 μ m; The inorganic conductive filler is for a kind of in conduction mica or conduction titanium white or the conductive zinc oxide or two kinds or all, the granularity of inorganic conductive filler is 800～1200 orders.
Described pigment comprises first, second, the third three kinds of components, and wherein the first component is titanium dioxide or zinc sulfide white, and the second component is talcum powder or barium sulfate, and third component is coarse whiting or fine particle calcium carbonate, and the granularity of material is more than 600 orders.For example paint material is the combination of titanium dioxide, talcum powder and coarse whiting.
Described coatings additive(s) comprises wetting dispersing agent, defoamer, frostproofer, flow agent, film coalescence aid, thickening material and pH regulator agent; Wherein wetting dispersing agent is sodium, ammonium, the amine salt of alkenyl monomer and unsaturated carboxylic acid and lipin polymer thereof, newly grinds DS-111, China auxiliary agent HX5300 or dispersion agents such as HX5320 and Shanghai three positive CH-12B as Henkel KGaA 5040, Tianjin; Defoamer is an organic silicon modified by polyether, as: day peaceful NXZ of undergraduate course, China auxiliary agent HX5041 or HX5042, the beautiful YH-202 of the many hats in Guangzhou; Frostproofer is ethylene glycol or propylene glycol; Flow agent is the nonionic polyurethane rheology modifier, as: ROHM AND HAAS 2020; Film coalescence aid is an alcohol ester, as: alcohol ester 12 and TEXANOL film coalescence aid; Thickening material is acrylate cross linked type thickening material, as: beautiful SF-730 is marked in French high Supreme Being Si RHEO ATE-431, the beautiful AT-70 of the many hats in Guangzhou, Guangzhou; The pH regulator agent is a volatile alkali, as: ammoniacal liquor.
Described solvent is a water.Available ordinary tap water or process water.
A kind of preparation method of environment friendly nano static conductive paint comprises three phases: fs, the dispersion liquid of preparation CNT (carbon nano-tube); Subordinate phase, the slurry of preparation color stuffing; Phase III, the mixing preparation of slurry and resin emulsion;
The step of described fs preparation is as follows:
A, with CNT (carbon nano-tube) and wetting dispersing agent in 1: add 5～10 times solvent behind the ratio premix of (1～2.5), be made into mixed solution, arrest reaction 15～30 minutes;
B, mixed solution was carried out supersound process 20～30 minutes, leaches bottom settlings with 400～600 eye mesh screens, will precipitate again with dispersion agent by 1: the mixed of (0.1～0.2), carry out supersound process again after adding 5～10 times of solvent reactions; Repeat above-mentioned filtration, mixing, dispersion steps, up to dispersion liquid bottom do not have precipitation or precipitation weight less than initial CNT (carbon nano-tube) weight 10% till;
C, the mixed dispersion liquid that above-mentioned repeating dispersion is obtained are added solvent, are made into the CNT (carbon nano-tube) dispersion liquid of specified amount;
The step of described subordinate phase preparation is as follows:
D, based on the CNT (carbon nano-tube) dispersion liquid of fs preparation, add pigment, dispersion agent, defoamer and frostproofer, under 800～1600r/min rotating speed, grind dispersion 60～80 minutes at a high speed, obtain the slurry of color stuffing;
The step of described phase III preparation is as follows:
E, the color stuffing slurry that subordinate phase is prepared mix with ACRYLIC EMULSION in proportion, add defoamer, flow agent, film coalescence aid and pH regulator agent under the stirring at low speed of 300～500r/min, stir 20～30 minutes;
F, the back that stirs add thickening material, regulate dope viscosity 〉=25s (being coated with-4 glasss);
Obtain the nano static conductive paint finished product after G, the filtration.
Add the inorganic conductive filler in the described steps A, the gross weight of CNT (carbon nano-tube) and inorganic conductive filler accounts for 0.2～10% of coating gross weight.
Embodiment 1:
Taking by weighing 0.8 gram caliber is 10～30nm, and length is multiple-wall carbon nanotube and the 1 gram CH-12B hyper-dispersant premix of 5～15 μ m, adds 10 gram water again and is made into mixed solution, arrest reaction 15 minutes; Above-mentioned mixed solution supersound process was filtered out bottom settlings with 400 order fine screen mesh after 30 minutes, add 0.1 gram CH-12B hyper-dispersant and 10 gram water in precipitation, arrest reaction carries out supersound process again after 15 minutes.Repeat above-mentioned filtration, mixing, dispersion steps 2 times, add suitable quantity of water at last and obtain the few CNT (carbon nano-tube) dispersion liquid of 80 gram precipitation capacities.Based on above-mentioned CNT (carbon nano-tube) dispersion liquid, add NXZ defoamer 1 gram, ethylene glycol 7.5 grams, 5040 dispersion agents, 1 gram, titanium dioxide 65 grams, talcum powder 65 grams and coarse whiting 65 grams under the whipped state successively.Add under the high-speed stirring of 1000r/mn, to grind behind an amount of glass sphere and disperseed 1 hour, filter out the slurry that obtains color stuffing behind the glass sphere.Get above-mentioned slurry 210 gram addings 90 gram benzene emulsions, add NXZ defoamer 1 gram, 2020 flow agents, 1.5 grams, alcohol ester 12 film coalescence aid 5 grams successively under the stirring at low speed of 500r/min, dripping proper ammonia adjusting coating pH value again is 8～9.The slow ATE-431 of adding thickening material 0.2 gram is adjusted dope viscosity after evenly stirring 20min, obtains the nano static conductive paint finished product at last again behind screen filtration.The every performance index of this coating all reach the premium grads performance requriements among the GB/T 9756-2001 " synthetic resin emulsion interior wall coating ", and wherein contrast ratio reaches 0.98, and abrasion resistance reaches more than 10000 times; VOC content in the coating≤80 gram/L meets in the environmental protection product technical requirements to water-borne coatings.Be coated with material samples and measurement by GB/T 16906-1997 " Oil Tank static conductive coating determination of resistivity method " making, the surface resistivity of coating is 10
7～10
8Ω/ meets the requirement of the conductivity of static conductive coating.
Embodiment 2
Taking by weighing 0.2 gram caliber is 40～60nm, and length is multi-walled carbon nano-tubes and the 0.5 gram CH-12B hyper-dispersant premix of 5～15 μ m, adds 10 gram water again and is made into mixed solution, arrest reaction 15 minutes; Above-mentioned mixed solution supersound process was filtered out bottom settlings with 400 order fine screen mesh after 30 minutes, add 0.1 gram CH-12B hyper-dispersant and 10 gram water in precipitation, arrest reaction carries out ultrasonication again after 15 minutes.Repeat above-mentioned filtration, mixing, dispersion steps 2 times, add suitable quantity of water at last and obtain the few carbon nanotube dispersion liquid of 80 gram precipitation capacities, add 15 gram conductive mica powders in dispersion liquid, the 500r/min rotating speed stirs static again placement 15min behind the 20min down.Based on the mixed dispersion liquid of above-mentioned carbon nanotube and conductive mica powder, add various coatings additive(s)s and pigment successively, except that the titanium dioxide addition was 50 grams, the addition manner of other composition and ratio were with embodiment 1.The follow-up slurry and the mixing preparation of resin emulsion until the method that obtains the static conductive coating finished product also with embodiment 1.The every performance index of this coating all reach the premium grads performance requriements among the GB/T 9756-2001 " synthetic resin emulsion interior wall coating ", and wherein contrast ratio reaches 0.96, and abrasion resistance reaches more than 10000 times; VOC content in the coating≤80 gram/L meets in the environmental protection product technical requirements to water-borne coatings.Be coated with material samples and measurement by GB/T 16906-1997 " Oil Tank static conductive coating determination of resistivity method " making, the surface resistivity of coating is 10
6～10
7Ω/ meets the requirement of the conductivity of static conductive coating.
Claims (9)
1, a kind of environment friendly nano static conductive paint is characterized in that comprising the following component of calculating content by mass percentage:
Aqueous acrylic emulsion 25～30
Conductive nano filler 0.2～10
Pigment 45～55
Coatings additive(s) 2～5
Solvent 15～20
2, environment friendly nano static conductive paint according to claim 1 is characterized in that: described aqueous acrylic emulsion is phenylpropyl alcohol or pure-acrylic emulsion.
3, environment friendly nano static conductive paint according to claim 1 is characterized in that: described conductive nano filler is the complex body of CNT (carbon nano-tube) or CNT (carbon nano-tube) and other inorganic conductive filler.
4, environment friendly nano static conductive paint according to claim 3 is characterized in that: described wherein CNT (carbon nano-tube) be caliber between 10～100nm, length is the multiple-wall carbon nanotube of 5～15 μ m; The inorganic conductive filler is for a kind of in conduction mica or conduction titanium white or the conductive zinc oxide or two kinds or all, the granularity of inorganic conductive filler is 800～1200 orders.
5, environment friendly nano static conductive paint according to claim 1 is characterized in that: described pigment comprises first, second, the third three kinds of components, and wherein the first component is titanium dioxide or zinc sulfide white, and the second component is talcum powder or barium sulfate, and third component is coarse whiting or fine particle calcium carbonate; Material particle size is more than 600 orders.
6, environment friendly nano static conductive paint according to claim 1 is characterized in that: described coatings additive(s) comprises wetting dispersing agent, defoamer, frostproofer, flow agent, film coalescence aid, thickening material and pH regulator agent; Wherein wetting dispersing agent is sodium, ammonium, the amine salt of alkenyl monomer and unsaturated carboxylic acid and lipin polymer thereof, defoamer is an organic silicon modified by polyether, frostproofer is ethylene glycol or propylene glycol, flow agent is the nonionic polyurethane rheology modifier, film coalescence aid is an alcohol ester, thickening material is acrylate cross linked type thickening material, and the pH regulator agent is a volatile alkali.
7, environment friendly nano static conductive paint according to claim 1 is characterized in that: described solvent is a water.
8, a kind of preparation method of environment friendly nano static conductive paint is characterized in that comprising three phases: fs, the dispersion liquid of preparation CNT (carbon nano-tube); Subordinate phase, the slurry of preparation color stuffing; Phase III, the mixing preparation of slurry and resin emulsion;
The step of described fs preparation is as follows:
A, with CNT (carbon nano-tube) and wetting dispersing agent in 1: add 5～10 times solvent behind the ratio premix of (1～2.5), be made into mixed solution, arrest reaction 15～30 minutes;
B, mixed solution was carried out supersound process 20～30 minutes, leaches bottom settlings with 400～600 eye mesh screens, will precipitate again with dispersion agent by 1: the mixed of (0.1～0.2), carry out supersound process again after adding 5～10 times of solvent reactions; Repeat above-mentioned filtration, mixing, dispersion steps, up to dispersion liquid bottom do not have precipitation or precipitation weight less than initial CNT (carbon nano-tube) weight 10% till;
C, the mixed dispersion liquid that above-mentioned repeating dispersion is obtained are added solvent, are made into the CNT (carbon nano-tube) dispersion liquid of specified amount;
The step of described subordinate phase preparation is as follows:
D, based on the CNT (carbon nano-tube) dispersion liquid of fs preparation, add pigment, dispersion agent, defoamer and frostproofer, under 800～1600r/min rotating speed, grind dispersion 60～80 minutes at a high speed, obtain the slurry of color stuffing;
The step of described phase III preparation is as follows:
E, the color stuffing slurry that subordinate phase is prepared mix with ACRYLIC EMULSION in proportion, add defoamer, flow agent, film coalescence aid and pH regulator agent under the stirring at low speed of 300～500r/min, stir 20～30 minutes;
F, the back that stirs add thickening material, regulate dope viscosity 〉=25s (being coated with-4 glasss);
Obtain the nano static conductive paint finished product after G, the filtration.
9, the preparation method of environment friendly nano static conductive paint according to claim 8 is characterized in that: add the inorganic conductive filler in the described steps A, the gross weight of CNT (carbon nano-tube) and inorganic conductive filler accounts for 0.2～10% of coating gross weight.
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| CN102372971A (en) * | 2011-10-11 | 2012-03-14 | 徐梅 | Process for preparing static conductive inner wall paint |
| CN103080255A (en) * | 2010-08-31 | 2013-05-01 | 三菱重工业株式会社 | Antistatic coating, and structure made of composite material using same and production method therefor |
| CN103756465A (en) * | 2013-12-30 | 2014-04-30 | 刘真 | Anti-static emulsion paint |
| CN103971784A (en) * | 2013-01-24 | 2014-08-06 | 上海九鹏化工有限公司 | Novel organic/inorganic nano-composite electric conduction slurry and preparing method of novel organic/inorganic nano-composite electric conduction slurry |
| CN104387922A (en) * | 2014-11-24 | 2015-03-04 | 廊坊立邦涂料有限公司 | Water-based static conductive paint and preparation method thereof |
| CN105802402A (en) * | 2016-04-12 | 2016-07-27 | 湖州新奥克化工有限公司 | Environment-friendly and efficient anti-static coating and preparation method thereof |
| CN106883709A (en) * | 2017-03-24 | 2017-06-23 | 大余松瀛化工有限公司 | A kind of novel environment-friendly water-based paint preparation method with anti-static function |
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| CN102372971A (en) * | 2011-10-11 | 2012-03-14 | 徐梅 | Process for preparing static conductive inner wall paint |
| CN103971784B (en) * | 2013-01-24 | 2016-08-17 | 上海九鹏化工有限公司 | A kind of novel organic/inorganic nano composite conducting slurry and preparation method thereof |
| CN103971784A (en) * | 2013-01-24 | 2014-08-06 | 上海九鹏化工有限公司 | Novel organic/inorganic nano-composite electric conduction slurry and preparing method of novel organic/inorganic nano-composite electric conduction slurry |
| CN103756465A (en) * | 2013-12-30 | 2014-04-30 | 刘真 | Anti-static emulsion paint |
| CN104387922A (en) * | 2014-11-24 | 2015-03-04 | 廊坊立邦涂料有限公司 | Water-based static conductive paint and preparation method thereof |
| CN105802402A (en) * | 2016-04-12 | 2016-07-27 | 湖州新奥克化工有限公司 | Environment-friendly and efficient anti-static coating and preparation method thereof |
| CN106883709A (en) * | 2017-03-24 | 2017-06-23 | 大余松瀛化工有限公司 | A kind of novel environment-friendly water-based paint preparation method with anti-static function |
| CN107881810A (en) * | 2017-11-29 | 2018-04-06 | 苏州润弘贸易有限公司 | A kind of preparation method of the printing and dyeing assistant of antistatic |
| CN107956148A (en) * | 2017-11-29 | 2018-04-24 | 苏州润弘贸易有限公司 | A kind of printing and dyeing assistant of antistatic |
| CN111718630A (en) * | 2020-06-23 | 2020-09-29 | 中国石油天然气集团有限公司 | Water-based static conductive coating and preparation method thereof |
| CN115725212A (en) * | 2022-11-29 | 2023-03-03 | 沈阳航空航天大学 | Conductive anticorrosive paint and preparation method thereof |
| CN116355473A (en) * | 2023-04-21 | 2023-06-30 | 广州青萍新材料有限公司 | Nanocomposite coating with anti-reflection, dustproof and/or antifouling functions, preparation method thereof and application thereof in photovoltaic panel |
| CN116355473B (en) * | 2023-04-21 | 2024-04-19 | 广州青萍新材料有限公司 | Nanocomposite coating with anti-reflection, dustproof and/or antifouling functions, preparation method thereof and application thereof in photovoltaic panel |
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Open date: 20070411 |