CN110408306A - A kind of addition type conductive coating and preparation method thereof - Google Patents
A kind of addition type conductive coating and preparation method thereof Download PDFInfo
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- CN110408306A CN110408306A CN201910726526.0A CN201910726526A CN110408306A CN 110408306 A CN110408306 A CN 110408306A CN 201910726526 A CN201910726526 A CN 201910726526A CN 110408306 A CN110408306 A CN 110408306A
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- conductive coating
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/08—Anti-corrosive paints
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of addition type conductive coatings and preparation method thereof.The addition type conductive coating includes the following raw material: aqueous epoxy resin emulsion, aqueous alkide resin emulsion, modified nano metal oxide fiber, modified graphene, coalescing agent, defoaming agent, water surplus.The present invention is compound as base-material using aqueous epoxy resin emulsion and aqueous alkide resin emulsion, improve its distribution and structure in base-material by nanosizing and fibrosis metal oxide, it can be reduced the additive amount of conductive filler, reduce cost, negative effect of the filler to viscosity of the coating and coating performance is reduced, the corrosion resistance and electric conductivity of conductive coating are significantly improved；Nanosizing and fibrosis metal oxide and modified graphene can form uniform and stable network structure in base-material, improve the comprehensive performance of conductive coating.
Description
Technical field
The present invention relates to conductive coating technical field, in particular to a kind of addition type conductive coating and preparation method thereof.
Background technique
Conductive coating is a kind of features type coating of rising in recent years.Conductive coating leads to as a kind of fluent material
The energy for crossing body surface itself that cannot be conductive coated in, and then imparting the certain conduction electric current of the object, eliminating electrostatic charge
Power, while can accomplish to prevent the effect of electromagnetic radiation.Conductive coating due to preparation method it is relatively easy, it is easy for construction, can
Various labyrinth devices coating, it is low in cost the advantages that, be widely used in aerospace, petrochemical industry, electronics industry,
The multiple fields such as building industry, textile industry.
Most widely used at present is addition type conductive coating, addition type conductive coating be conductive filler and film forming matter,
The mixture of auxiliary agent, solvent, currently used addition type conductive coating mainly have carbon system, metal system, metal oxide system conductive
Coating.With the development of nanotechnology in recent years, the nanocrystallization technology of above-mentioned three kinds conductive systems, which has, substantially to improve, accordingly
Conductive Paints also obtain larger raising.But it yet there are no and nano-metal-oxide fiber is added to conductive coating
In research report.
Summary of the invention
The purpose of the present invention is intended to provide a kind of addition type conductive coating and preparation method thereof, is asked with solving above-mentioned technology
Topic.
To achieve the goals above, the technical solution of the present invention is as follows:
In a first aspect, a kind of addition type conductive coating provided by the invention, by weight percentage, including the following raw material:
Aqueous epoxy resin emulsion 45~65%, aqueous alkide resin emulsion 10~25%, modified nano metal oxide fiber 1~
10%, modified graphene 1~5%, coalescing agent 2~6%, defoaming agent 0.1~0.5%, water surplus.
Preferably, the modified nano metal oxide fiber is to be made using following methods: by soluble metallic salt, second
Acid is mixed with the ethanol solution of polymer, agitated to obtain colloidal sol, then obtains nano metal after electrostatic spinning, hydrolysis, calcining
Oxide fibre nano-metal-oxide fiber, the first silane coupling agent is added in the first organic solvent, at 40~60 DEG C
2~12h is stirred, through cooling, is filtered, washed, dries and obtain modified nano metal oxide fiber.
It is further preferred that the soluble metallic salt in titanium tetrachloride, butyl titanate, isopropyl titanate one
Kind is a variety of.
It is further preferred that the polymer is selected from one of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide
Or it is a variety of.
It is further preferred that the weight ratio of the soluble metallic salt and the polymer is 2~8:1.
It is further preferred that first silane coupling agent is selected from silane coupling agent KH540, Silane coupling agent KH550, silicon
One of alkane coupling agent KH560, silane coupling agent KH570 or a variety of.
It is further preferred that the weight ratio of first silane coupling agent and the nano-metal-oxide fiber is 0.01
~0.1:1.
Preferably, the modified graphene is to be made using following methods: graphene is added in the second organic solvent,
After ultrasonic wave disperses, the second silane coupling agent is added, ground, suction filtration, spray drying obtain modified graphene.
It is further preferred that second organic solvent is selected from one of ethyl alcohol, isopropanol, n-butanol, acetone or more
Kind.
It is further preferred that second silane coupling agent is selected from silane coupling agent KH540, Silane coupling agent KH550, silicon
One of alkane coupling agent KH560, silane coupling agent KH570 or a variety of.
It is further preferred that the weight ratio of second silane coupling agent and the graphene is 0.01~0.1:1.
Preferably, the coalescing agent is selected from one of dipropylene glycol monomethyl ether, Dipropylene glycol mono-n-butyl Ether, neopentyl glycol
Or it is a variety of.
Preferably, the defoaming agent is organic silicon defoaming agent.
Preferably, the addition type conductive coating, by weight percentage, including the following raw material: aqueous epoxy resins cream
Liquid 50~60%, aqueous alkide resin emulsion 15~23%, modified nano metal oxide fiber 2~5%, modified graphene 2
~3.5%, coalescing agent 2~4%, defoaming agent 0.1~0.5%, water surplus.
Second aspect, a kind of preparation method of addition type conductive coating as described in relation to the first aspect provided by the invention, packet
Include following steps:
(1) by nano-metal-oxide fiber, modified graphene, coalescing agent, water, formula ratio 30~50% aqueous ring
Oxygen resin emulsion, formula ratio 30~50% aqueous alkide resin emulsion mixing after carry out ultrasonic disperse, the ultrasonic disperse time is
10~60min obtains dispersion liquid；
(2) by the dispersion liquid warming-in-water of step (1) to 60~80 DEG C, remaining aqueous epoxy resin emulsion is added, remains
Remaining aqueous alkide resin emulsion, defoaming agent, after being stirred, cooling obtains addition type conductive coating.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is compound as base-material using aqueous epoxy resin emulsion and aqueous alkide resin emulsion, passes through nanosizing and fibre
Dimensionization metal oxide improves its distribution and structure in base-material, can be reduced the additive amount of conductive filler, reduces cost, reduces
Negative effect of the filler to viscosity of the coating and coating performance significantly improves the corrosion resistance and electric conductivity of conductive coating；It receives
Riceization and fibrosis metal oxide and modified graphene can form uniform and stable network structure in base-material, improve conductive
The comprehensive performance of coating.
Specific embodiment
Specific embodiments of the present invention will be further explained below.It should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, invention described below
Technical characteristic involved in each embodiment can be combined with each other as long as they do not conflict with each other.
Embodiment 1
The preparation method for present embodiments providing a kind of modified nano metal oxide fiber, includes the following steps:
The ratio that weight ratio according to butyl titanate, acetic acid, polyvinylpyrrolidone, ethyl alcohol is 5:1.5:1:12, will
Polyvinylpyrrolidone is dissolved in ethyl alcohol and obtains the ethanol solution of polyvinylpyrrolidone, and acetic acid and butyl titanate are sequentially added
It is agitated to obtain colloidal sol in the ethanol solution of polyvinylpyrrolidone, using the needle head electrostatic spinning (condition of electrostatic spinning
Are as follows: ejection of syringe pump speed 1mL/h, voltage 15kV receive distance 10cm, rotating cylinder revolving speed 50r/min) precursor fibre is obtained,
Precursor fibre is put into Muffle furnace, 500 DEG C of calcining 4h is warming up to and obtains nanometer titanium dioxide fiber, according to nanometer titanium dioxide
Titanium fiber, Silane coupling agent KH550, isopropanol weight ratio be 1:0.04:2.5 ratio, by nanometer titanium dioxide fiber, silicon
Alkane coupling agent KH550 is added in isopropanol, stirs 10h at 50 DEG C, through cooling, is filtered, washed, dries and obtain modified Nano two
Titanium dioxide fiber.
Embodiment 2
A kind of preparation method of modified graphene provided in this embodiment, includes the following steps:
The ratio that weight ratio according to graphene, Silane coupling agent KH550, isopropanol is 1:0.04:3, by graphene plus
Enter into isopropanol, after ultrasonic wave disperses, adds Silane coupling agent KH550, after continuing ultrasonic disperse 30min, be put into and grind
30min is ground with the revolving speed of 800r/min in grinding jar, filtered, be spray-dried to obtain modified graphene.
Embodiment 3
A kind of preparation method of addition type conductive coating provided in this embodiment, includes the following steps:
Weigh following raw materials by weight percentage: aqueous epoxy resin emulsion 52%, aqueous alkide resin emulsion
18%, the modified nano-titanium dioxide fiber 3.6% that is prepared Following the procedure of Example 1 is prepared Following the procedure of Example 2
Modified graphene 2.8%, Dipropylene glycol mono-n-butyl Ether 3%, dimethyl silicone polymer 0.2%, deionized water surplus.By nano-silica
Change titanium fiber, modified graphene, Dipropylene glycol mono-n-butyl Ether, deionized water, the aqueous epoxy resin emulsion of formula ratio 40%, formula
Ultrasonic disperse is carried out after the aqueous alkide resin emulsion mixing of amount 40%, the ultrasonic disperse time is 40min, obtains dispersion liquid；It will
The dispersion liquid warming-in-water of step to 75 DEG C, be added remaining aqueous epoxy resin emulsion, remaining aqueous alkide resin emulsion,
Dimethyl silicone polymer, after being stirred, cooling obtains addition type conductive coating.
Embodiment 4
A kind of preparation method of addition type conductive coating provided in this embodiment, includes the following steps:
Weigh following raw materials by weight percentage: aqueous epoxy resin emulsion 50%, aqueous alkide resin emulsion
20%, the modified nano-titanium dioxide fiber 4% that is prepared Following the procedure of Example 1, changing of being prepared Following the procedure of Example 2
Property graphene 3%, Dipropylene glycol mono-n-butyl Ether 3%, dimethyl silicone polymer 0.3%, water surplus.By nanometer titanium dioxide fiber,
The aqueous alcoholic of modified graphene, Dipropylene glycol mono-n-butyl Ether, water, the aqueous epoxy resin emulsion of formula ratio 40%, formula ratio 40%
Ultrasonic disperse is carried out after the mixing of acid resin lotion, the ultrasonic disperse time is 40min, obtains dispersion liquid；By the dispersion liquid water of step
Bath is warming up to 70 DEG C, and remaining aqueous epoxy resin emulsion, remaining aqueous alkide resin emulsion, polydimethylsiloxanes is added
Alkane, after being stirred, cooling obtains addition type conductive coating.
Embodiment 5
A kind of preparation method of addition type conductive coating provided in this embodiment, includes the following steps:
Weigh following raw materials by weight percentage: aqueous epoxy resin emulsion 55%, aqueous alkide resin emulsion
15%, the modified nano-titanium dioxide fiber 2% that is prepared Following the procedure of Example 1, changing of being prepared Following the procedure of Example 2
Property graphene 3.5%, Dipropylene glycol mono-n-butyl Ether 3%, dimethyl silicone polymer 0.2%, water surplus.By nano-titanium dioxide fibre
Dimension, modified graphene, Dipropylene glycol mono-n-butyl Ether, water, the aqueous epoxy resin emulsion of formula ratio 50%, formula ratio 50% it is aqueous
Ultrasonic disperse is carried out after alkide resin emulsion mixing, the ultrasonic disperse time is 50min, obtains dispersion liquid；By the dispersion liquid of step
Remaining aqueous epoxy resin emulsion, remaining aqueous alkide resin emulsion, polydimethylsiloxanes is added to 60 DEG C in warming-in-water
Alkane, after being stirred, cooling obtains addition type conductive coating.
Embodiment 6
A kind of preparation method of addition type conductive coating provided in this embodiment, includes the following steps:
Weigh following raw materials by weight percentage: aqueous epoxy resin emulsion 60%, aqueous alkide resin emulsion
15%, the modified nano-titanium dioxide fiber 5% that is prepared Following the procedure of Example 1, changing of being prepared Following the procedure of Example 2
Property graphene 2%, Dipropylene glycol mono-n-butyl Ether 3%, dimethyl silicone polymer 0.3%, water surplus.By nanometer titanium dioxide fiber,
The aqueous alcoholic of modified graphene, Dipropylene glycol mono-n-butyl Ether, water, the aqueous epoxy resin emulsion of formula ratio 40%, formula ratio 40%
Ultrasonic disperse is carried out after the mixing of acid resin lotion, the ultrasonic disperse time is 45min, obtains dispersion liquid；By the dispersion liquid water of step
Bath is warming up to 75 DEG C, and remaining aqueous epoxy resin emulsion, remaining aqueous alkide resin emulsion, polydimethylsiloxanes is added
Alkane, after being stirred, cooling obtains addition type conductive coating.
Embodiment 7
A kind of preparation method of addition type conductive coating provided in this embodiment, includes the following steps:
Weigh following raw materials by weight percentage: aqueous epoxy resin emulsion 45%, aqueous alkide resin emulsion
25%, the modified nano-titanium dioxide fiber 10% that is prepared Following the procedure of Example 1 is prepared Following the procedure of Example 2
Modified graphene 1%, Dipropylene glycol mono-n-butyl Ether 3%, dimethyl silicone polymer 0.3%, water surplus.By nano-titanium dioxide fibre
Dimension, modified graphene, Dipropylene glycol mono-n-butyl Ether, water, the aqueous epoxy resin emulsion of formula ratio 40%, formula ratio 40% it is aqueous
Ultrasonic disperse is carried out after alkide resin emulsion mixing, the ultrasonic disperse time is 40min, obtains dispersion liquid；By the dispersion liquid of step
Remaining aqueous epoxy resin emulsion, remaining aqueous alkide resin emulsion, polydimethylsiloxanes is added to 70 DEG C in warming-in-water
Alkane, after being stirred, cooling obtains addition type conductive coating.
Embodiment 8
A kind of preparation method of addition type conductive coating provided in this embodiment, includes the following steps:
Weigh following raw materials by weight percentage: aqueous epoxy resin emulsion 65%, aqueous alkide resin emulsion
10%, the modified nano-titanium dioxide fiber 1% that is prepared Following the procedure of Example 1, changing of being prepared Following the procedure of Example 2
Property graphene 5%, Dipropylene glycol mono-n-butyl Ether 3%, dimethyl silicone polymer 0.4%, water surplus.By nanometer titanium dioxide fiber,
The aqueous alcoholic of modified graphene, Dipropylene glycol mono-n-butyl Ether, water, the aqueous epoxy resin emulsion of formula ratio 40%, formula ratio 40%
Ultrasonic disperse is carried out after the mixing of acid resin lotion, the ultrasonic disperse time is 40min, obtains dispersion liquid；By the dispersion liquid water of step
Bath is warming up to 75 DEG C, and remaining aqueous epoxy resin emulsion, remaining aqueous alkide resin emulsion, polydimethylsiloxanes is added
Alkane, after being stirred, cooling obtains addition type conductive coating.
Comparative example 1
The ratio that weight ratio according to spherical nano TiO 2, Silane coupling agent KH550, isopropanol is 1:0.04:2.5
Spherical nano TiO 2, Silane coupling agent KH550 are added in isopropanol, 10h are stirred at 50 DEG C, through cooling, mistake by example
Filter, washing, drying obtain modified nano-titanium dioxide.Beneficial effect in order to further illustrate the present invention repeats embodiment 3
" modified nano-titanium dioxide fiber " in embodiment 3 is substituted for " modified nano-titanium dioxide " by step, and obtained addition type is led
Electrocoating paint.
Comparative example 2
It is conductive that addition type is made using step similar to Example 3 in beneficial effect in order to further illustrate the present invention
The difference of coating, this comparative example and embodiment 3 is only that: modified nano-titanium dioxide fibre is not added in the formula of this comparative example
Dimension.
Performance test:
Beneficial effect in order to further illustrate the present invention carries out performance to above-described embodiment and comparative example resulting product
Test, test result is as follows shown in table:
Above the embodiments of the present invention are described in detail, but the present invention is not limited to described embodiments.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out more
Kind change, modification, replacement and modification, still fall in protection scope of the present invention.
Claims (10)
1. a kind of addition type conductive coating, which is characterized in that by weight percentage, including the following raw material: aqueous epoxy resins
Lotion 45~65%, aqueous alkide resin emulsion 10~25%, modified nano metal oxide fiber 1~10%, modified graphite
Alkene 1~5%, coalescing agent 2~6%, defoaming agent 0.1~0.5%, water surplus.
2. addition type conductive coating according to claim 1, which is characterized in that the modified nano metal oxide fiber
To be made using following methods: soluble metallic salt, acetic acid are mixed with the ethanol solution of polymer, it is agitated to obtain colloidal sol,
Nano-metal-oxide fiber is obtained after electrostatic spinning, hydrolysis, calcining again, by nano-metal-oxide fiber, silane coupled
Agent is added in organic solvent, and 2~12h is stirred at 40~60 DEG C, through cooling, is filtered, washed, dries and obtain modified Nano metal
Oxide fibre.
3. addition type conductive coating according to claim 2, which is characterized in that the soluble metallic salt is selected from four chlorinations
One of titanium, butyl titanate, isopropyl titanate are a variety of.
4. addition type conductive coating according to claim 2, which is characterized in that the polymer is selected from polyvinyl alcohol, gathers
One of vinylpyrrolidone, polyethylene glycol oxide are a variety of.
5. addition type conductive coating according to claim 2, which is characterized in that the soluble metallic salt polymerize with described
The weight ratio of object is 2~8:1.
6. addition type conductive coating according to claim 1, which is characterized in that the modified graphene is to use following sides
Method is made: graphene is added in organic solvent, after ultrasonic wave disperses, adds silane coupling agent, it is ground, filter,
Spray drying obtains modified graphene.
7. addition type conductive coating according to claim 1, which is characterized in that the coalescing agent is selected from dipropylene glycol list
One of methyl ether, Dipropylene glycol mono-n-butyl Ether, neopentyl glycol are a variety of.
8. addition type conductive coating according to claim 1, which is characterized in that the defoaming agent is organic silicon defoaming
Agent.
9. addition type conductive coating according to claim 1, which is characterized in that the addition type conductive coating, by weight
Percentages, including the following raw material: aqueous epoxy resin emulsion 50~60%, is modified aqueous alkide resin emulsion 15~23%
Nano-metal-oxide fiber 2~5%, modified graphene 2~3.5%, coalescing agent 2~4%, defoaming agent 0.1~0.5%,
Water surplus.
10. a kind of preparation method of such as addition type conductive coating according to any one of claims 1 to 9, which is characterized in that packet
Include following steps:
(1) by nano-metal-oxide fiber, modified graphene, coalescing agent, water, formula ratio 30~50% water-base epoxy tree
Fat liquor, formula ratio 30~50% aqueous alkide resin emulsion mixing after carry out ultrasonic disperse, the ultrasonic disperse time is 10~
60min obtains dispersion liquid；
(2) by the dispersion liquid warming-in-water of step (1) to 60~80 DEG C, remaining aqueous epoxy resin emulsion, remaining is added
Aqueous alkide resin emulsion, defoaming agent, after being stirred, cooling obtains addition type conductive coating.
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| CN114121384A (en) * | 2022-01-29 | 2022-03-01 | 深圳市明盛威先导科技有限公司 | Water-based conductive slurry and preparation method and application thereof |
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