CN109627829A - A kind of liquid metal conductive coating and its preparation method and application - Google Patents
A kind of liquid metal conductive coating and its preparation method and application Download PDFInfo
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- CN109627829A CN109627829A CN201811360920.9A CN201811360920A CN109627829A CN 109627829 A CN109627829 A CN 109627829A CN 201811360920 A CN201811360920 A CN 201811360920A CN 109627829 A CN109627829 A CN 109627829A
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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
-
- 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
-
- 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
- C09D5/004—Reflecting paints; Signal 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
- C08K2003/085—Copper
Abstract
The present invention relates to a kind of liquid metal conductive coatings, component including following parts by weight: the liquid metal conductive coating includes the component of following parts by weight: 18-22 parts of liquid metal, 28-32 parts of matrix resin, 10-14 parts of conductive filler, 23-27 parts of solvent, 3.5-4.5 parts of coupling agent, 0.1-0.3 parts of dispersing agent, 0.1-0.3 parts of defoaming agent, 0.1-0.2 parts of levelling agent.Conductive coating proposed by the present invention is prepared using liquid metal fusing point is low, electric conductivity is high and safe and non-toxic characteristic with stable high-performance conductive coating；With respect to the advantages that for conventional conductive coating, with good dispersion, electric conductivity is excellent, and safety and environmental protection is unlikely to deteriorate, and wearability is good.
Description
Technical field
The present invention provides a kind of conductive coating based on liquid metal, belongs to conductive coating field, and in particular to a kind of liquid
State metallic conduction coating and its preparation method and application.
Background technique
Traditional spraying process must be by oil removing, roughening, sensitization, activation, reduction, electroless copper etc., gigantic project, processing
Subsequent trouble.And conductive coating is sprayed on non-metallic products surface that other metals can be electroplated, that is, has saved cost and operation
Simplicity can also reduce environmental pollution, so that polymer surface achievees the purpose that antistatic or shielding electromagnetic wave, therefore lead
Electrocoating paint serves as electrode and reflecting coating, heating coating, antistatic aspect in electronic circuit industry important application.But at present
Conductive coating has that dispersibility is poor, preparation process is complicated, stability is low, not wear-resisting and environmentally friendly etc. in practical applications
Problem.
Summary of the invention
In order to overcome the above technical problems, the present invention provides a kind of liquid metal conductive coating, overcomes existing conductive painting
Expect preparation process is complicated, stability is low, not environmentally the disadvantages of.Conductive coating proposed by the present invention utilizes liquid metal fusing point
The high and safe and non-toxic characteristic of low, electric conductivity, it is prepared with stable high-performance conductive coating；Opposite conventional conductive applies
For material, the advantages that with good dispersion, electric conductivity is excellent, and safety and environmental protection is unlikely to deteriorate, and wearability is good.
Technical scheme is as follows:
A kind of liquid metal conductive coating, the component including following parts by weight: the liquid metal conductive coating includes such as
The component of lower parts by weight: 18-22 parts of liquid metal, 28-32 parts of matrix resin, 10-14 parts of conductive filler, 23-27 parts of solvent, idol
Join agent 3.5-4.5 parts, 0.1-0.3 parts of dispersing agent, 0.1-0.3 parts of defoaming agent, 0.1-0.2 parts of levelling agent.
Further, the liquid metal be one of gallium-base alloy, bismuth-base alloy, indium-base alloy or kamash alloy or
It is a variety of, and the liquid metal is in 5 DEG C~232 DEG C metals being in a liquid state.Preferably, the liquid metal be gallium indium, gallium tin,
One of gallium zinc, bismuth indium bianry alloy are a variety of；Or it is closed for gallium indium tin, gallium indium zinc, indium tin zinc, bismuth indium tin, bismuth indium-zinc ternary
One of gold is a variety of；It or is gallium indium tin zinc and/or bismuth indium tin zinc quaternary alloy；Or for by lead, silver, copper, aluminium or chromium
One or more elements and one of above-mentioned binary, ternary, quaternary alloy or a variety of middle low temperature multicomponent alloys being formulated；
The temperature of the middle low temperature multicomponent alloy is within the scope of RT~200 DEG C；Further preferably in BiInSn, InSn or GaInSnZn
It is one or more.
Further, described matrix resin is epoxy resin, phenolic resin, alkyd resin, acrylic resin, polyurethane tree
One of rouge is a variety of；Preferred acrylic resins.
Further, the conductive filler is carbon black, carbon fiber, graphite, silver powder, copper powder, silver-plated copper powder, metal oxidation
One of object, sheet metal, metallized glass fiber, metallic fiber, glass microballoon, mica are a variety of；It is preferred that silver-plated copper powder.
The partial size of the conductive filler is at 1 μm -100 μm, and preferably 1 μm -40 μm.
Further, the solvent be water, it is ethyl acetate, ethyl alcohol, ketone, one or more of in aromatic hydrocarbons；It is preferred that acetic acid
Ethyl ester.
Further, the levelling agent be one of BYK-3550, diacetone alcohol, dimethyl silicone polymer or a variety of,
Preferably BYK-3550.
The coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, (the β alkene methoxyl group of vinyl three
Ethyoxyl) silane, titanate esters, Aluminate, tri- mercaptopropyltriethoxysilane of γ, one of 3- aminopropyl triethoxysilane
Or it is a variety of；Preferably silane coupling agent.
The defoaming agent be silicone emulsion, the fatty acid ester compounded object of higher alcohols, polyoxyethylene polyoxypropylene pentaerythrite ether,
Polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxyethylene polyoxypropylene glycerin ether, BYK-094, phosphate disappear
One of infusion is a variety of, preferably BYK-094.
The dispersing agent is waterglass, sodium tripolyphosphate, calgon, sodium pyrophosphate, polyethylene glycol type polyalcohol, gathers
One of ethylenimine derivatives, BYK-193 or a variety of；Preferably BYK-193.
One of as a preferred embodiment of the present invention, the liquid metal conductive coating includes the group of following parts by weight
Point: it is 18-22 parts of liquid metal, 28-32 parts of acrylic resin, 10-14 parts of silver-plated copper powder, 23-27 parts of ethyl acetate, silane coupled
3.5-4.5 parts of agent, 0.1-0.3 parts of BYK-193,0.1-0.3 parts of BYK-094,0.1-0.2 parts of BYK-3550.
The present invention also provides a kind of preparation methods of liquid metal conductive coating, comprising:
1) coupling agent, defoaming agent, dispersing agent, levelling agent are sequentially added in matrix resin, is stirred while adding, added
Solvent obtains uniform organic carrier, stands at room temperature；
2) liquid metal being in a liquid state is added in organic carrier obtained by step 1), high-speed stirred makes its dispersion, obtains liquid
State metallic conduction coating.
Wherein, in step 1), the agitating mode is that hand operated mixing and magnetic agitation successively carry out, as long as can make each group
Divide uniformly mixed agitating mode；The magnetic agitation rotating speed is the rising of the interval 500rad/min-1500rad/min, often
5min increases by 200 turns；The mixing time is 0.5-2h.
In this method, if the liquid metal fusing point is higher than room temperature, the liquid metal that the fusing point is higher than room temperature is placed in
Make constant temperature processing in air or in vacuum；The constant temperature processing time, treatment temperature are changed into liquid for liquid metal alloy
State is advisable；Preferably, the constant temperature processing time is 0.5-2h；Preferably, the treatment temperature is closed greater than or equal to low melting point
The fusing point of gold, it is further preferable that the treatment temperature is higher than 1-10 DEG C of the low-melting alloy fusing point.
The present invention also protects above-mentioned liquid metal conductive coating to be used as electrode and reflecting coating in electronic circuit industry, add
Application in hot coating, antistatic coating.
The beneficial effects of the present invention are:
(1) organic carrier that liquid metal and matrix resin and other functional reagents form forms homogeneous phase, without preparation
Alloying pellet reduces cost；
(2) defoaming agent, dispersing agent, levelling agent etc. are added in organic carrier, reduce the surface tension of liquid metal, raising is led
The adhesiveness of electrocoating paint and matrix；
(3) use flake silver-plated copper powder for basic filler, improve using electrolytic copper powder be filler bring resistivity not
Stable disadvantage, while also overcoming and being easy to produce the bad existing of Ion transfer using the conductive coating that fine silver powder is filler production
As.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
In following embodiments, the test method of conductive coating performance and mechanical property are as follows: GB/T 5210, GB/T 6739-
2006、GB/T 1732-1993、GB/T 1517-1973、GB/T 1410-2006。
Embodiment 1
The present embodiment provides a kind of liquid metals conductive coating, each component and according to the mass fraction as shown in table 1:
Table 1
By way of stirring, acrylic resin, silver-plated copper powder, silane coupling agent, BYK-094, BYK-193, BYK-
3550 sequentially add and are mixed into uniform organic carrier, then carry out magnetic agitation (revolving speed from 500rad/min to 1500rad/min,
Every 5 minutes increase by 200 turns), be added solvent, to above-mentioned solution be stirred 0.5h form it into mixing be sufficiently formed it is airborne
Body；
The GaInSnZn alloy being in a liquid state at room temperature is stirred into 30min in homogenizer, after making liquid metal viscosity increase,
It mixes with above-mentioned organic carrier, is mixed into after magnetic agitation (revolving speed 1500rad/min) 0.5h is carried out after hand operated mixing again
Even phase can be made into liquid metal conductive coating.
After tested, conductive coating performance and mechanical property are as follows: volume resistivity can achieve 7.95 × 106 Ω cm,
Adhesive force can achieve 0 grade, surface drying time 7min, and hardness of paint film can achieve 6H, impact resistant strength 69kgcm.
Embodiment 2:
The present embodiment provides a kind of liquid metals conductive coating, each component and according to the mass fraction as shown in table 2:
Table 2
By way of stirring, acrylic resin, silver-plated copper powder, silane coupling agent, BYK-094, BYK-193, BYK-
3550 sequentially add and are mixed into uniform organic carrier, then carry out magnetic agitation (revolving speed from 500rad/min to 1500rad/min,
Every 5 minutes increase by 200 turns), be added solvent, to above-mentioned solution be stirred 0.5h form it into mixing be sufficiently formed it is airborne
Body；
After weighing proportionally by the liquid metal raw material (indium and tin) of simple substance, be put into vacuum high-frequency induction melting furnace by its
Dissolution, by the InSn alloy of liquid after homogenizer 30 minutes, after making liquid metal viscosity increase, then with it is above-mentioned have it is airborne
Body mixes, and is uniformly mixed after carrying out magnetic agitation (revolving speed 1500rad/min) 0.5h after hand operated mixing again, that is, can be made into liquid
Metallic conduction coating.
After tested, conductive coating performance and mechanical performance are as follows: volume resistivity can achieve 8.10 × 106 Ω cm,
Adhesive force can achieve 0 grade, surface drying time 10min, and hardness of paint film can achieve 4H, impact resistant strength 73kgcm.
Embodiment 3
The present embodiment provides a kind of liquid metals conductive coating, each component and according to the mass fraction as shown in table 3:
Table 3
By way of stirring, acrylic resin, silver-plated copper powder, silane coupling agent, BYK-094, BYK-193, BYK-
3550 sequentially add and are mixed into uniform organic carrier, then carry out magnetic agitation (revolving speed from 500rad/min to 1500rad/min,
Every 5 minutes increase by 200 turns), be added solvent, to above-mentioned solution be stirred 0.5h form it into mixing be sufficiently formed it is airborne
Body；
After weighing proportionally by the liquid metal raw material (bismuth, indium and tin) of simple substance, it is put into vacuum high-frequency induction melting furnace
It after being dissolved, is put into homogenizer and stirs 30min, after making liquid metal viscosity increase, then mix with above-mentioned organic carrier, hand
It is mixed into homogeneous phase after carrying out magnetic agitation (revolving speed 1500rad/min) 0.5h again after dynamic stirring, that is, can be made into liquid metal
Conductive coating.
After tested, conductive coating performance and mechanical performance are as follows: volume resistivity can achieve 7.50 × 106 Ω cm,
Adhesive force can achieve 0 grade, surface drying time 8min, and hardness of paint film can achieve 4H, impact resistant strength 61kgcm.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of liquid metal conductive coating, which is characterized in that the component including following parts by weight: the liquid metal conduction applies
Material includes the component of following parts by weight: 18-22 parts of liquid metal, 28-32 parts of matrix resin, 10-14 parts of conductive filler, solvent
23-27 parts, 3.5-4.5 parts of coupling agent, 0.1-0.3 parts of dispersing agent, 0.1-0.3 parts of defoaming agent, 0.1-0.2 parts of levelling agent.
2. liquid metal conductive coating according to claim 1, which is characterized in that the liquid metal be gallium-base alloy,
One of bismuth-base alloy, indium-base alloy or kamash alloy are a variety of, and the liquid metal is to be in a liquid state at 5 DEG C~232 DEG C
Metal.
3. liquid metal conductive coating according to claim 2, which is characterized in that the liquid metal be gallium indium, gallium tin,
One of gallium zinc, bismuth indium bianry alloy are a variety of；
It or is one of gallium indium tin, gallium indium zinc, indium tin zinc, bismuth indium tin, bismuth indium-zinc ternary alloy or a variety of；
It or is gallium indium tin zinc and/or bismuth indium tin zinc quaternary alloy；
Or for by one of lead, silver, copper, aluminium or chromium or multiple element and one of above-mentioned binary, ternary, quaternary alloy or
A variety of middle low temperature multicomponent alloys being formulated；
Preferably one of BiInSn, InSn or GaInSnZn or a variety of.
4. liquid metal conductive coating according to claim 1 to 3, which is characterized in that described matrix resin is epoxy
One of resin, phenolic resin, alkyd resin, acrylic resin, polyurethane resin are a variety of；Preferred acrylic resins.
5. liquid metal conductive coating according to claim 1 to 4, which is characterized in that the conductive filler is carbon
Black, carbon fiber, graphite, silver powder, copper powder, metal oxide, sheet metal, metallized glass fiber, metallic fiber, glass are micro-
One of pearl, mica are a variety of；It is preferred that silver-plated copper powder.
6. -5 any liquid metal conductive coating according to claim 1, which is characterized in that the partial size of the conductive filler
At 1 μm -100 μm, preferably 1 μm -40 μm.
7. -6 any liquid metal conductive coating according to claim 1, which is characterized in that the solvent is water, acetic acid
It is ethyl ester, ethyl alcohol, ketone, one or more of in aromatic hydrocarbons；Ethyl acetate；
And/or the levelling agent be one of BYK-3550, diacetone alcohol, dimethyl silicone polymer or a variety of, preferably
BYK-3550；
And/or the coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, (the β alkene methoxy of vinyl three
Base oxethyl) silane, titanate esters, Aluminate, tri- mercaptopropyltriethoxysilane of γ, one in 3- aminopropyl triethoxysilane
Kind is a variety of；Preferably silane coupling agent；
And/or the defoaming agent is silicone emulsion, the fatty acid ester compounded object of higher alcohols, polyoxyethylene polyoxypropylene pentaerythrite
Ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxyethylene polyoxypropylene glycerin ether, BYK-094, phosphate
One of defoaming agent is a variety of, preferably BYK-094；
And/or the dispersing agent be waterglass, sodium tripolyphosphate, calgon, sodium pyrophosphate, polyethylene glycol type polyalcohol,
One of polyethylenimine derivates, BYK-193 or a variety of；Preferably BYK-193.
8. liquid metal conductive coating according to claim 1, which is characterized in that the component including following parts by weight: liquid
18-22 parts of state metal, 28-32 parts of acrylic resin, 10-14 parts of silver-plated copper powder, 23-27 parts of ethyl acetate, silane coupling agent
3.5-4.5 parts, 0.1-0.3 parts of BYK-193,0.1-0.3 parts of BYK-094,0.1-0.2 parts of BYK-3550.
9. a kind of preparation method of liquid metal conductive coating characterized by comprising
1) coupling agent, defoaming agent, dispersing agent, levelling agent are sequentially added in matrix resin, is stirred while adding, added molten
Agent obtains uniform organic carrier, stands at room temperature；
2) liquid metal being in a liquid state is added in organic carrier obtained by step 1), high-speed stirred makes its dispersion, obtains liquid gold
Belong to conductive coating.
10. application of any liquid metal conductive coating of claim 1-9 in electronic circuit industry.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373590A (en) * | 2019-07-16 | 2019-10-25 | 中国科学院理化技术研究所 | A kind of liquid conduction insulating materials and the preparation method and application thereof |
| CN110605400A (en) * | 2019-09-25 | 2019-12-24 | 苏州大学 | Large-scale preparation method of liquid metal nano liquid drops |
| CN110713742A (en) * | 2019-09-26 | 2020-01-21 | 扬州富威尔复合材料有限公司 | Preparation and application method of intelligent conductive paint based on liquid metal-polymer |
| CN110828029A (en) * | 2019-11-06 | 2020-02-21 | 浙江清华柔性电子技术研究院 | Conductive material and preparation method thereof |
| CN110819138A (en) * | 2019-09-29 | 2020-02-21 | 浙江安力能源有限公司 | Method for manufacturing surface coating of sodium-nickel battery ceramic tube |
| CN111093331A (en) * | 2020-01-09 | 2020-05-01 | 北京梦之墨科技有限公司 | Surface treatment method of liquid metal conductive pattern and conductive pattern |
| CN111128440A (en) * | 2020-01-07 | 2020-05-08 | 北京梦之墨科技有限公司 | Liquid metal conductive slurry, preparation method thereof and electronic device |
| CN111128441A (en) * | 2020-01-07 | 2020-05-08 | 北京梦之墨科技有限公司 | Liquid metal conductive paste and electronic device |
| CN111192705A (en) * | 2020-01-07 | 2020-05-22 | 北京梦之墨科技有限公司 | Liquid metal conductive paste, electronic device and manufacturing method thereof |
| CN111863308A (en) * | 2019-04-30 | 2020-10-30 | 北京梦之墨科技有限公司 | Colored conductive paste, preparation method thereof and electronic device |
| CN112592607A (en) * | 2020-12-29 | 2021-04-02 | 成都芙涵麟涂料科技有限公司 | Preparation method of filler for conductive coating |
| WO2021121278A1 (en) * | 2019-12-19 | 2021-06-24 | 北京梦之墨科技有限公司 | Liquid metal conductive slurry and electronic device |
| CN115011221A (en) * | 2022-07-19 | 2022-09-06 | 青岛德冠超导材料制造有限公司 | Antistatic, mildew-proof and antibacterial coating composition, and preparation method and application thereof |
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| CN110605400A (en) * | 2019-09-25 | 2019-12-24 | 苏州大学 | Large-scale preparation method of liquid metal nano liquid drops |
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| CN110819138A (en) * | 2019-09-29 | 2020-02-21 | 浙江安力能源有限公司 | Method for manufacturing surface coating of sodium-nickel battery ceramic tube |
| CN110828029A (en) * | 2019-11-06 | 2020-02-21 | 浙江清华柔性电子技术研究院 | Conductive material and preparation method thereof |
| US11776708B2 (en) | 2019-12-19 | 2023-10-03 | Beijing Dream Ink Technologies Co., Ltd. | Liquid metal conductive paste and electronic device |
| WO2021121278A1 (en) * | 2019-12-19 | 2021-06-24 | 北京梦之墨科技有限公司 | Liquid metal conductive slurry and electronic device |
| CN111192705A (en) * | 2020-01-07 | 2020-05-22 | 北京梦之墨科技有限公司 | Liquid metal conductive paste, electronic device and manufacturing method thereof |
| CN111128441A (en) * | 2020-01-07 | 2020-05-08 | 北京梦之墨科技有限公司 | Liquid metal conductive paste and electronic device |
| CN111192705B (en) * | 2020-01-07 | 2021-07-02 | 北京梦之墨科技有限公司 | Liquid metal conductive paste, electronic device and manufacturing method thereof |
| CN111128440A (en) * | 2020-01-07 | 2020-05-08 | 北京梦之墨科技有限公司 | Liquid metal conductive slurry, preparation method thereof and electronic device |
| CN111093331A (en) * | 2020-01-09 | 2020-05-01 | 北京梦之墨科技有限公司 | Surface treatment method of liquid metal conductive pattern and conductive pattern |
| CN112592607B (en) * | 2020-12-29 | 2022-01-11 | 惠州市七点光电科技有限公司 | Preparation method of filler for conductive coating |
| CN112592607A (en) * | 2020-12-29 | 2021-04-02 | 成都芙涵麟涂料科技有限公司 | Preparation method of filler for conductive coating |
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Application publication date: 20190416 |