CN108102483A - A kind of waterborne antibacterial electrically-conducting paint and preparation method thereof - Google Patents
A kind of waterborne antibacterial electrically-conducting paint and preparation method thereof Download PDFInfo
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- CN108102483A CN108102483A CN201810010499.2A CN201810010499A CN108102483A CN 108102483 A CN108102483 A CN 108102483A CN 201810010499 A CN201810010499 A CN 201810010499A CN 108102483 A CN108102483 A CN 108102483A
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- waterborne antibacterial
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of waterborne antibacterial electrically-conducting paints, are made of the raw material of following parts by weight：50 80 parts of film forming matter, 15 35 parts of amine-modified epoxy resin curing agent, 10 20 parts of modified graphene, 20 30 parts of color stuffing, 24 parts of coalescents, 0.5 1 parts of antiseptic, 24 parts of other auxiliary agents, appropriate deionized water；Coating of the present invention has shown good performance, and wherein specific volume resistance reaches 107Rank, electric conductivity are very excellent；And antibiotic rate reaches more than 90%, has fine antibiotic property to Escherichia coli and staphylococcus aureus.
Description
Technical field
The invention belongs to paint fields, and in particular to a kind of waterborne antibacterial electrically-conducting paint and preparation method thereof.
Background technology
Coating, in the entitled paint of Chinese tradition.So-called coating is to be coated in the body surface protected or decorated, and
The continuous film of firm attachment can be formed with coated article, typically based on resin or oil or lotion, adds or does not add face
Material, filler add corresponding additive, the thick liquid being formulated with organic solvent or water.Chinese coating circle is more authoritative《It applies
Material technique》What one book was defined as：Coating is a kind of material, and this material can be coated in object with different construction technologies
Surface forms and adheres to securely, with some strength, continuous solid film.So formed film common name film, also known as paint film or
Coating.With the continuous development of science and technology, coating progressively becomes that a kind of specificity is strong, strong functional fine chemistry product.
Electrically-conducting paint is widely used in the multiple fields such as electric system, petroleum refining industry, aerospace and electronics,
Its demand is in gradual increased trend.According to conductive mechanism, electrically-conducting paint can be divided into two kinds of structural type and admixing type.Knot
Configuration electrically-conducting paint because there are complex process, it is expensive the problems such as, admixing type electrically-conducting paint is caused to become electrically-conducting paint and being ground
Study carefully exploitation and industrialized emphasis, however the problems such as admixing type electrically-conducting paint is of high cost, density is big, seriously polluted still up for into
One step solves.In order to improve conductive anti-corrosion coating technique, its cost and density are reduced, reduces pollution, it is necessary to find a kind of new
Admixing type electrically-conducting paint.Patent (CN101108947A, CN1221768A, CN 101935489A) is successively described with inorganic
Coating of the conductive filler as conductive filler, to reach its conductive standard, these coating, which need to add substantial amounts of inorganic conductive, to be filled out
Material, and the compatibility poor of inorganic filler and resin so that the mechanical properties decrease of paint film；Patent (CN102070960A,
CN101368058A, CN 101418122A) coating of the conducting polymer as conductive filler is successively described, though this kind of coating
So there is preferable compatibility, but the cost is relatively high.Patent (CN1704191A, CN1013122179A,
CN103205174A) using conductive filler of the metal powder as coating, this kind of coating is with excellent electric conductivity, but cost also phase
To higher, and corrosion resistance is bad, and metallic pollution is serious.Therefore it is good to develop a kind of stability, the novel conductive that conducts electricity very well applies
Material becomes the important research direction of electrically-conducting paint.
In addition, as the improvement of people's living standards, the requirement to decorative product is also higher and higher, in order to be reduced or avoided
The pollution that bacterium brings, more and more urgent to the demand of antimicrobial form coating therewith, corresponding research is also more and more.
CN100352872A discloses a kind of antibiotic mildew-resistant algae-resistant anticorrosion paint, which includes host agent and curing agent, and host agent includes ring
Oxygen resin, nanometer color stuffing, the agent of nano inorganic antibiotic mildew-resistant algae-resistant and organic solvent；Curing agent for polyamide curing agent 650 or
The mixture of modified amine curing agent T31 or the two；The nano inorganic antibacterial and mouldproof algicide resists for nano composite inorganic
Bacterium algicide and nano inorganic carrying silver antimicrobials；The coating of the invention is more than the antibiotic rate of Escherichia coli and Staphylococcus aureus
99%, mould proof, anti-algae grade is 0 grade, can prevent drinking water " secondary pollution ".
But it is not much in the prior art on the research for being provided simultaneously with antibacterial and conductive two kinds of functional character coating, and with
The development of economic society, increasing to the demand that is provided simultaneously with above two performance coating, therefore, development one kind is provided simultaneously with
The coating of electric conductivity and anti-microbial property has a very important significance.
The content of the invention
The object of the present invention is to provide the very excellent comprehensive environmental protection coating material of a kind of anti-microbial property and conductive capability with
And the preparation method of the coating.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of waterborne antibacterial electrically-conducting paint, is made of the raw material of following parts by weight：50-80 parts of film forming matter, amine are modified
15-35 parts of epoxy curing agent, 10-20 parts of modified graphene, 20-30 parts of color stuffing, 2-4 parts of coalescents, antiseptic
0.5-1 parts, 2-4 parts of other auxiliary agents, appropriate deionized water.
Wherein, the film forming matter is Germany's Lu Borun CARBOSET PL-958 acrylate copolymer emulsions.
The amine-modified epoxy resin curing agent is polyamide modified epoxy curing agent.
The preparation method of the modified graphene is：First, graphene oxide powder 0.4-1g is taken, in the condition of ultrasonic wave
The lower n,N-Dimethylformamide for adding in 100-200mL forms uniform dispersion liquid, adds in suitable two hexamethylene of catalyst afterwards
Base carbodiimide, is warming up to 55-75 DEG C, and the isopropanolamine of 2~6g is slowly added under continuous stirring, when reaction 6-10 is small,
Obtain product modification graphene oxide, product is washed, dry after it is spare；Then products therefrom modified graphene oxide is continued
It is scattered under ultrasound condition in a certain amount of deionized water and forms dispersion liquid, and add in appropriate hydrazine hydrate, the reductase 12 4h at 100 DEG C,
Last reduzate washing is drying to obtain the modified graphene.
Pigment is rutile titanium dioxide in the color stuffing, and filler is mica powder, talcum powder, one kind in calcium carbonate or several
Kind.
The coalescents are propylene-glycol diacetate.
The antiseptic is montmorillonite load copper silver antibacterial agent, and its preparation method is：(1) copper acetate and acetic acid are prepared respectively
Silver-colored solution, and above two solution is added drop-wise to simultaneously in a certain amount of montmorillonite under continuous stirring；(2) by step (1)
Mixed liquor 45min is stirred to react at 45 DEG C, be cooled to 25 DEG C or so afterwards, and add in reducing agent continue to stir 45min it is left
The right side is then centrifuged for, washs and is drying to obtain the antiseptic；The load capacity of Ag is 0.5-1wt%, Cu in wherein described antiseptic
Load capacity be 2-3wt%.
Other described auxiliary agents include 0.01-0.05 parts of 1-3 parts of thickener, 0.2-0.5 parts of preservative and pH adjusting agent.
The present invention also provides the preparation methods of the waterborne antibacterial electrically-conducting paint, specifically comprise the following steps：First will
The film forming matter of parts by weight is added in reaction vessel with modified graphene, suitable deionized water and heats up under continuous stirring
To 70~90 DEG C of 2~4h of reaction；System is cooled to 30~40 DEG C after having reacted, under 600~800 revs/min of speed stirring
It is slowly added to amine-modified epoxy resin curing agent, color stuffing, coalescents, antiseptic and thickening into reaction kettle respectively successively
Agent, preservative are eventually adding pH adjusting agent and pH value are adjusted to 8-10, and add in water and adjust viscosity, obtain coating composition,
In the above-mentioned time interval sequentially added be 5-10min.
Heretofore described auxiliary agent thickener, preservative and pH adjusting agent are not specifically limited, as long as not to the present invention
Goal of the invention generate limitation.
In addition, the present invention is also protected by the preparation-obtained waterborne antibacterial electrically-conducting paint of the preparation method.
The present invention technique effect be：(1) present invention utilizes the electric property of graphene uniqueness, electronics is in graphene layer
The interference very little being subject in piece during transmission, is not susceptible to scatter, mobility is up to 2 × 105cm2/ (Vs), resistivity are about
10-6' Ω cm, electric property are splendid；Graphene is applied in coating by the present invention, is prepared for the electrically-conducting paint haveing excellent performance,
Wherein, modification has been carried out to graphene first, the grafting hydrophilic group on graphene so that graphene can be follow-up anti-
Process is answered to penetrate into well in film forming matter, so as to play good electric action.
(2) antiseptic that uses of the present invention is carries the silver-colored antiseptic with copper simultaneously, and montmorillonite is as carrier, can be abundant
Larger diffusional area can be provided for silver and copper using montmorillonite, it is silver-colored scattered with copper beneficial to Antibacterial Constituents, it improves anti-
Bacterium effect；
(3) present invention is a kind of water paint, has the good feature of environmental protection, and the present invention is made using various components matching
With obtained coating has excellent adhesion, mechanical property, filming performance, is a kind of coating of excellent quality.
Specific embodiment
Technical scheme is further elaborated with reference to embodiment：
Embodiment 1
A kind of waterborne antibacterial electrically-conducting paint, is made of the raw material of following parts by weight：Film forming matter Germany Lu Borun
70 parts of CARBOSET PL-958 acrylate copolymer emulsions, polyamide modified 25 parts of epoxy curing agent, modified graphene 15
Part, 25 parts of color stuffing, 3 parts of coalescents propylene-glycol diacetate, 0.6 part of montmorillonite load copper silver antibacterial agent, AT-70 thickeners
2 parts, auspicious RAYB0600.3 parts of the treasured of preservative, 0.03 part of pH adjusting agent ammonium hydroxide, appropriate deionized water；Ag in wherein described antiseptic
Load capacity for 0.6wt%, the load capacity of Cu is 2.5wt%, and pigment is rutile titanium dioxide in the color stuffing, and filler is cloud
Female powder.
Embodiment 2
A kind of waterborne antibacterial electrically-conducting paint, is made of the raw material of following parts by weight：Film forming matter Germany Lu Borun
50 parts of CARBOSET PL-958 acrylate copolymer emulsions, polyamide modified 15 parts of epoxy curing agent, modified graphene 10
Part, 20 parts of color stuffing, 2 parts of coalescents propylene-glycol diacetate, 0.5 part of montmorillonite load copper silver antibacterial agent, AT-70 thickeners
1 part, auspicious RAYB0600.2 parts of the treasured of preservative, 0.01 part of pH adjusting agent ammonium hydroxide, appropriate deionized water；Ag in wherein described antiseptic
Load capacity for 0.5wt%, the load capacity of Cu is 2wt%, and pigment is rutile titanium dioxide in the color stuffing, and filler is talcum
Powder.
Embodiment 3
A kind of waterborne antibacterial electrically-conducting paint, is made of the raw material of following parts by weight：Film forming matter Germany Lu Borun
80 parts of CARBOSET PL-958 acrylate copolymer emulsions, polyamide modified 35 parts of epoxy curing agent, modified graphene 20
Part, 30 parts of color stuffing, 4 parts of coalescents propylene-glycol diacetate, 1 part of montmorillonite load copper silver antibacterial agent, AT-70 thickeners 3
Part, auspicious RAYB0600.5 parts of the treasured of preservative, 0.05 part of pH adjusting agent ammonium hydroxide, appropriate deionized water；Ag in wherein described antiseptic
Load capacity for 1wt%, the load capacity of Cu is 3wt%, and pigment is rutile titanium dioxide in the color stuffing, and filler is carbonic acid
Calcium.
Embodiment 4
The preparation method of modified graphene is described in embodiment 1-3：First, graphene oxide powder 0.7g is taken, in ultrasound
The n,N-Dimethylformamide that 120mL is added under conditions of ripple forms uniform dispersion liquid, adds in suitable catalyst two afterwards
Carbodicyclo hexylimide is warming up to 60 DEG C, and the isopropanolamine of 4g is slowly added under continuous stirring, when reaction 8 is small, is produced
Object modified graphene oxide, product is washed, dry after it is spare；Then products therefrom modified graphene oxide is continued into ultrasonic item
It is scattered under part in a certain amount of deionized water and forms dispersion liquid, and add in appropriate hydrazine hydrate, the reductase 12 4h at 100 DEG C, also finally
It originates in object washing, be drying to obtain the modified graphene.
Embodiment 5
The preparation method of waterborne antibacterial electrically-conducting paint described in embodiment 1-3, includes the following steps：First by parts by weight
Film forming matter is added in reaction vessel with modified graphene, suitable deionized water and is warming up to 80 DEG C instead under continuous stirring
Answer 3h；System is cooled to 35 DEG C after having reacted, slowly to add into reaction kettle respectively successively under 700 revs/min of speed stirring
Enter amine-modified epoxy resin curing agent, color stuffing, coalescents, antiseptic and thickener, preservative, be eventually adding pH adjustings
PH value is adjusted to 9 by agent, and is added in water and adjusted viscosity, obtains coating composition, wherein the above-mentioned time interval that sequentially adds is
8min。
Comparative example 1
With embodiment 1, uniquely difference lies in do not add in modified graphene.
Comparative example 2
With embodiment 1, uniquely difference lies in do not add in antiseptic.
The coating of 1-3 of the embodiment of the present invention and comparative example 1-2 are tested for the property, the result is shown in the following table 1：
As can be seen from Table 1, each coating of the embodiment of the present invention has shown good performance, wherein embodiment 1-3 coating
Specific volume resistance reach 107Rank, more much smaller than 1 specific volume resistance of comparative example, electric conductivity is very excellent；And resist
In terms of bacterium rate, the antibiotic rate of embodiment 1-3 addition antiseptics is much better than the antibiotic rate of comparative example 2.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, still may be used
To modify to the technical solution recorded in foregoing embodiments or carry out equivalent substitution to which part technical characteristic.
Within the spirit and principles of the invention, any modifications, equivalent replacements and improvements are made should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of waterborne antibacterial electrically-conducting paint, which is characterized in that be made of the raw material of following parts by weight：Film forming matter 50-80
Part, 15-35 parts of amine-modified epoxy resin curing agent, 10-20 parts of modified graphene, 20-30 parts of color stuffing, 2-4 parts of coalescents,
0.5-1 parts of antiseptic, 2-4 parts of other auxiliary agents, appropriate deionized water.
2. waterborne antibacterial electrically-conducting paint according to claim 1, which is characterized in that the film forming matter is Germany Lu Borun
CARBOSET PL-958 acrylate copolymer emulsions.
3. waterborne antibacterial electrically-conducting paint according to claim 2, which is characterized in that the amine-modified epoxy resin curing agent
For polyamide modified epoxy curing agent.
4. according to claim 1-3 any one of them waterborne antibacterial electrically-conducting paints, which is characterized in that the modified graphene
Preparation method is：First, graphene oxide powder 0.4-1g is taken, the N, N- bis- of 100-200mL are added under conditions of ultrasonic wave
Methylformamide forms uniform dispersion liquid, adds in suitable catalyst dicyclohexylcarbodiimide afterwards, is warming up to 55-75
DEG C, the isopropanolamine of 2~6g is slowly added under continuous stirring, when reaction 6-10 is small, obtains product modification graphene oxide,
Product is washed, dry after it is spare；Then products therefrom modified graphene oxide is continued to be scattered under ultrasound condition a certain amount of
Dispersion liquid is formed in deionized water, and adds in appropriate hydrazine hydrate, the reductase 12 4h at 100 DEG C, last reduzate washing, drying
Up to the modified graphene.
5. according to claim 1-4 any one of them waterborne antibacterial electrically-conducting paints, which is characterized in that face is filled out described in coalescents
Pigment is rutile titanium dioxide in material, and filler is one or more of mica powder, talcum powder, calcium carbonate.
6. according to claim 1-5 any one of them waterborne antibacterial electrically-conducting paints, which is characterized in that the coalescents are third
Glycol diacetate.
7. according to claim 1-5 any one of them waterborne antibacterial electrically-conducting paints, which is characterized in that the antiseptic is de- to cover
Native supported copper silver antibacterial agent, its preparation method are：(1) copper acetate and silver acetate solution are prepared respectively, and under continuous stirring
Above two solution is added drop-wise to simultaneously in a certain amount of montmorillonite；(2) mixed liquor of step (1) is stirred to react at 45 DEG C
45min is cooled to 25 DEG C or so afterwards, and adds in reducing agent and continue to stir 45min or so, is then centrifuged for, washs and dries i.e.
Obtain the antiseptic；The load capacity of Ag is 0.5-1wt% in wherein described antiseptic, and the load capacity of Cu is 2-3wt%.
8. according to claim 1-5 any one of them waterborne antibacterial electrically-conducting paints, which is characterized in that other described auxiliary agents include
0.01-0.05 parts of 1-3 parts of thickener, 0.2-0.5 parts of preservative and pH adjusting agent.
9. according to the preparation method of claim 8 any one of them waterborne antibacterial electrically-conducting paint, which is characterized in that including as follows
Step：The film forming matter of parts by weight and modified graphene, suitable deionized water are added in reaction vessel continuous first
Stirring under be warming up to 70~90 DEG C reaction 2~4h；System is cooled to 30~40 DEG C after having reacted, with 600~800 revs/min
Speed stirring under be slowly added to amine-modified epoxy resin curing agent, color stuffing, coalescents, anti-into reaction kettle respectively successively
Microbial inoculum and thickener, preservative are eventually adding pH adjusting agent and pH value are adjusted to 8-10, and add in water and adjust viscosity, obtain
Coating composition, wherein the above-mentioned time interval sequentially added is 5-10min.
10. a kind of waterborne antibacterial electrically-conducting paint that preparation method according to claim 9 is prepared.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810010499.2A CN108102483A (en) | 2018-01-02 | 2018-01-02 | A kind of waterborne antibacterial electrically-conducting paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810010499.2A CN108102483A (en) | 2018-01-02 | 2018-01-02 | A kind of waterborne antibacterial electrically-conducting paint and preparation method thereof |
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| CN108102483A true CN108102483A (en) | 2018-06-01 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336716A (en) * | 2015-07-10 | 2017-01-18 | 深圳光启高等理工研究院 | Conductive coating paint preparation method |
| CN106995580A (en) * | 2017-03-27 | 2017-08-01 | 佛山汇沐化学科技有限公司 | A kind of high Antibacterial flame retardant plastic its preparation method |
| CN106995631A (en) * | 2017-05-11 | 2017-08-01 | 佛山实瑞先导材料研究院（普通合伙） | A kind of waterborne antibacterial electrically-conducting paint |
| CN107011756A (en) * | 2017-05-12 | 2017-08-04 | 段宝荣 | The preparation method of environment-friendly type graphene modified water-soluble styrene-acrylic resin antifouling conductive coating |
| CN107216745A (en) * | 2017-07-15 | 2017-09-29 | 佛山实瑞先导材料研究院（普通合伙） | A kind of waterborne flame retardant antibiotic conductive coating |
-
2018
- 2018-01-02 CN CN201810010499.2A patent/CN108102483A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336716A (en) * | 2015-07-10 | 2017-01-18 | 深圳光启高等理工研究院 | Conductive coating paint preparation method |
| CN106995580A (en) * | 2017-03-27 | 2017-08-01 | 佛山汇沐化学科技有限公司 | A kind of high Antibacterial flame retardant plastic its preparation method |
| CN106995631A (en) * | 2017-05-11 | 2017-08-01 | 佛山实瑞先导材料研究院（普通合伙） | A kind of waterborne antibacterial electrically-conducting paint |
| CN107011756A (en) * | 2017-05-12 | 2017-08-04 | 段宝荣 | The preparation method of environment-friendly type graphene modified water-soluble styrene-acrylic resin antifouling conductive coating |
| CN107216745A (en) * | 2017-07-15 | 2017-09-29 | 佛山实瑞先导材料研究院（普通合伙） | A kind of waterborne flame retardant antibiotic conductive coating |
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Application publication date: 20180601 |