CN106782757B - A kind of printable compliant conductive slurry and its conducting wire and preparation method - Google Patents
A kind of printable compliant conductive slurry and its conducting wire and preparation method Download PDFInfo
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- CN106782757B CN106782757B CN201611254140.7A CN201611254140A CN106782757B CN 106782757 B CN106782757 B CN 106782757B CN 201611254140 A CN201611254140 A CN 201611254140A CN 106782757 B CN106782757 B CN 106782757B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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Abstract
The invention discloses a kind of printable compliant conductive slurry and its conducting wires and preparation method.Specifically, compliant conductive slurry is can print to be made of complex conductive particle and polysiloxane；Wherein, the mass percent of the complex conductive particle is 40%~85%.The complex conductive particle is that nonmetallic core surface is coated with metal surface, particle of the diameter not higher than 20 μm.The present invention substitutes traditional simple metal conductive particle or carbon conductive filler using silver-plated conductive particle; with high conductivity, low-density and characteristic of low cost; the not free settling in polysiloxane flexible polymer; the compliant conductive slurry of high conductivity can be prepared, and the easy of compliant conductive circuit can be carried out by the traditional printings such as silk-screen printing mode and made.The present invention is of low cost, simple in structure, simple for production easy, is suitable for the emerging fields such as flexible print circuit, flexible display screen, flexible wearable electronics, electronic skin.
Description
Technical field
The present invention relates to a kind of printable compliant conductive slurry and its conducting wires and preparation method.
Background technology
Compliant conductive circuit in addition to the conducting function for having conventional conductive circuit, also have mechanical flexibility, be suitable for stretch,
The various mechanical deformations such as bending, winding, folding, distortion, in flexible print circuit, flexible display screen, flexible electronic skin, can wear
The emerging fields such as wearing electronic are with important application prospects.Printing technology is to realize circuit pattern large area, quickly, efficiently make
One of important method.It is hyundai electronics material to integrate conductive, flexible and impressionability electrocondution slurry and its conducting wire
The forward position direction for expecting research field, gets more and more people's extensive concerning.
The main component of electrocondution slurry is conductive filler and resin matrix.Conductive filler has the metal materials such as gold, silver, copper, nickel
The conductive filler of material, the carbon series conductives such as carbon black, graphite, carbon nanotube material and plating metal on surface, such as copper electroplate, glass
Glass bead surface plates metal and polymer microballoon plating metal on surface etc..According to filler size, but can be divided into it is spherical, random
Grain, two-dimensional sheet and one-dimensional linear filler.The type of conductive filler and the difference of shape, can to the percolation threshold of electrocondution slurry,
The performances such as electric conductivity, viscosity have an important influence on.Resin matrix then mainly provides mechanics mechanical performance and adhesive property.Tradition
Electrocondution slurry usually using micro silver powder as filler, but silver it is expensive, and amount commonly usually need to reach 75wt% or more can just obtain
Obtain stable high conduction performance.In order to reduce the percolation threshold of conductive filler in the slurry, reducing filler usage amount and then reduce
Cost, 103400637 A of patent CN are replaced traditional using the branch silver silver that microstructure is three-dimensional dendritic metal crystal structure
Electrocondution slurry is made with resin compounded in micro silver powder.A diameter of 0.5 μm~50 μm of three-dimensional dendritic metal crystal structure used, two
The length of grade dendritic morphology is 5nm~5 μm.The electrical property of made conductive silver paste is suitable with traditional silver paste, and silver-colored loading is but shown
Writing reduces, and effectively reduces cost of material.But the preparation difficulty of three-dimensional dendritic silver powder itself used in the patent is big,
Technical threshold is high, it is difficult to which mass production is to meet industrial quantization demand.
In order to reduce cost while meet electric conductivity requirement as far as possible, 101419851 A of patent CN select carbon series conductive
Material such as graphite powder, carbon fiber, expanded graphite, carbon black, coke, carbon nanotube or combinations thereof object etc. prepares composite guide as filler
Electric material, this method use hot pressing or kneaded and formed, and the process is more complicated, and made conducing composite material maximum conductivity is 150
~200S/cm, it is still relatively low.In order to solve the problems, such as that the excessive free settling of conductive filler density and gold and silver noble metal cost are higher,
By noble metal loadings such as gold, silver on low-density cheap material surface, the core-shell structural conductive filler of plating metal on surface is formed, both may be used
The cost of filler can be reduced again by reducing the density of filler, at the same time can also largely retain the high conductance of the metals such as gold and silver
Rate characteristic.105225768 A of patent CN are conductive filler using silver-plated glass beads and silvered glass fiber, and diluted
PDMS is uniformly mixed and cures to obtain the flexible conductive film of sandwich structure.The patent of invention is exactly the material using plating metal on surface
Material is that conductive filler reaches the purpose for reducing cost, while improving conductivity, but the flexible conductive film of the sandwich structure without
Method makes compliant conductive circuit as electrocondution slurry by mode of printing.
In order to obtain the compliant conductive slurry for adapting to mechanically deform, 105702323 A of patent of invention CN are with nano silver wire
For conductive material, with hydroxyethyl meth acrylate phosphate, polyurethane resin, polyvinyl butyral, solvent, antifoaming agent,
Curing agent etc. is compound to prepare the compliant conductive silver paste with excellent adhesion and buckle resistance.But nano silver wire used in the invention
Price is far above the conventional conductive filler such as silver powder, and usage amount is up to 30%~60% in the system, and it is soft will to significantly increase this
The cost of property conductive silver paste.At the same time, in the compliant conductive silver paste organic solvent use, it will be limited in certain matrix materials
Use on material, such as organic solvent may dissolve or corrode fiber paper base matrix.
Invention content
In view of this, in order to overcome the problems, such as drawbacks described above and, the present invention provide it is a kind of it is of low cost, simple in structure, make
It is convenient, solvent-free, printable, matrix is applied widely, the compliant conductive slurry of low-temperature curable and its printed wire and preparation
Method.It is core that the present invention, which selects lightweight polymeric microballoon, and silver-plated in its surface chemistry, the low-density conduction for preparing nucleocapsid is filled out
Material.By being simply mixed with PDMS prepolymers and its curing agent, compliant conductive slurry can be prepared, which is passed through into screen printing
Brush, blade coating printing, the printing technologies such as mask version printing can with the various patterns such as printed film, back-shaped circuit, then cured technique,
Compliant conductive circuit can be made.
One aspect of the invention provides a kind of printable compliant conductive slurry, which is characterized in that it is by composite conducting
Grain and polysiloxane are made；The complex conductive particle be nonmetallic core surface be coated with metal surface, diameter it is not high
In 20 μm of particle；
Preferably, organic solvent or inorganic solvent are free of in the electrocondution slurry；
It is highly preferred that organic solvent be selected from acetone, butanone, ethyl alcohol, methanol, isopropanol, benzene, toluene, styrene, just oneself
It is one or more in alkane, hexamethylene, dichloromethane, chloroform, ether, glycol monoethyl ether, acetonitrile, pyridine etc.；
Inorganic solvent is one or more in water, liquefied ammonia, sulfuric acid, nitric acid etc..
In specific embodiments of the present invention, the mass percent of the complex conductive particle is 40%~85%.
In specific embodiments of the present invention, the nonmetallic kernel of the complex conductive particle is selected from glass, ceramics, inertia
The microballoon that polymer is formed；
It is highly preferred that the microballoon is selected from polystyrene microsphere (PS), polyacrylic acid microballoon (PAA), polymethylacrylic acid
One in methyl esters microballoon (PMMA), poly- phenolic resin microspheres (PF), polydivinylbenezene microballoon (PDVB) or its copolymer microsphere
Kind or it is a variety of, grain size be 200nm~10 μm (200nm, 400nm, 600nm, 800nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm,
7μm、8μm、9μm、10μm)；
It is highly preferred that the density of the nonmetallic kernel is 0.6-1.5g/cm3(preferably 0.8-1.2g/cm3, more preferably
For 0.9-1.1g/cm3, 1.0g/cm3)；
It is highly preferred that the content of the nonmetallic core surface metal surface account for complex conductive particle quality 30%~
80%.
In specific embodiments of the present invention, metal in the metal surface be selected from gold, silver, copper, nickel, aluminium, tungsten, iron,
It is one or more in titanium, palladium, platinum；
Preferably, the metal surface is by being chemically or physically plated on nonmetallic core surface；
It is highly preferred that the metal surface is at least coated with 1 layer of metal；More preferably 1 layer or 2 layers.
In specific embodiments of the present invention, polysiloxane is by polysiloxane prepolymer and its curing agent system
At；
Preferably, the mass ratio of polysiloxane prepolymer and curing agent is 5:1~15:1；
It is highly preferred that the polysiloxane be selected from dimethyl silicone polymer, cyclomethicone, amino silicone,
It is one or more in polymethylphenylsiloxane, polysiloxane polyether copolymer；
It is highly preferred that the polysiloxane prepolymer is selected from dimethyl silicone polymer (PDMS)；
It is highly preferred that the curing agent is selected from small molecule silane, preferably the small molecule silicon with silicone hydroxyl, siloxy
Alkane.
Another aspect of the invention provides a kind of printable compliant conductive paste compound, which is characterized in that it includes
Complex conductive particle, polysiloxane prepolymer and its curing agent；
The complex conductive particle is that nonmetallic core surface is coated with metal surface, particle of the diameter not higher than 20 μm；
Preferably, organic solvent or inorganic solvent are free of in the electrocondution slurry；
It is highly preferred that organic solvent be selected from acetone, butanone, ethyl alcohol, methanol, isopropanol, benzene, toluene, styrene, just oneself
It is one or more in alkane, hexamethylene, dichloromethane, chloroform, ether, glycol monoethyl ether, acetonitrile, pyridine etc.；
Inorganic solvent is one or more in water, liquefied ammonia, sulfuric acid, nitric acid etc..
In specific embodiments of the present invention, the complex conductive particle accounts for the matter of printable compliant conductive paste compound
It is 40%~85% (preferably 40%-80%, more preferably 50%-65%) to measure percentage.
In specific embodiments of the present invention, the nonmetallic kernel of the complex conductive particle is selected from glass, ceramics, inertia
The microballoon that polymer is formed；
In specific embodiments of the present invention, the microballoon is selected from polystyrene microsphere (PS), polyacrylic acid microballoon
(PAA), poly (methyl methacrylate) micro-sphere (PMMA), poly- phenolic resin microspheres (PF), polydivinylbenezene microballoon (PDVB) or
One or more in its copolymer microsphere, grain size is 200nm~10 μm；
In specific embodiments of the present invention, the density of the nonmetallic kernel is 0.6-1.5g/cm3(preferably 0.8~
1.2g/cm3, more preferably 0.9-1.1g/cm3, more preferably 1.0g/cm3)；
In specific embodiments of the present invention, the content of the nonmetallic core surface metal surface accounts for complex conductive particle
The 30%~80% of quality.
In specific embodiments of the present invention, metal in the metal surface be selected from gold, silver, copper, nickel, aluminium, tungsten, iron,
It is one or more in titanium, palladium, platinum；
Preferably, the metal surface is by being chemically or physically plated on nonmetallic core surface；
Preferably, at least it is coated with 1 layer of metal surface；More preferably 1 layer or 2 layers.
In specific embodiments of the present invention, the mass ratio of polysiloxane prepolymer and curing agent is 5:1~15:1；
It is highly preferred that the polysiloxane prepolymer is selected from dimethyl silicone polymer (PDMS)；
It is highly preferred that the curing agent is selected from small molecule silane, preferably the small molecule silicon with silicone hydroxyl, siloxy
Alkane.
The grain size of complex conductive particle used in the present invention is 1~11 μm.
Another aspect of the invention provides a kind of preparation method of printable compliant conductive slurry or combinations thereof object, system
Include for step：
(1) complex conductive particle is synthesized
Using nonmetallic kernel as matrix, on its plating metal on surface surface layer；
(2) mixed slurry of silver-plated conductive particle and polysiloxane is prepared
Weigh the complex conductive particle obtained by polysiloxane prepolymer and its curing agent and step 1)；
Optionally, each ingredient mechanical agitation that step 2) weighs is mixed or high speed rotation is mixed to form uniformly.
Preferably, it is made in the following manner in the step of metallized surfaces on nonmetallic kernel：
I) it is roughened
Roughening treatment is carried out on nonmetallic kernel with strong acid；
Ii it) is sensitized
To carry out sensitized treatment on nonmetallic kernel to being obtained obtained by step i) in stannous chloride aqueous solution；At room temperature at sensitization
Manage 30min~3h；
Iii) chemical plating
Prepare silver ammino solution, and by step ii) the nonmetallic kernel after gained sensitization is added in silver ammino solution, then plus
Enter go back original reagent, the reaction was complete obtains complex conductive particle.
Another aspect of the present invention provides a kind of compliant conductive medium, is passed through on substrate by electrocondution slurry above-mentioned
Printing gained；
Preferably, the printing is selected from silk-screen printing, blade coating printing, mask version printing.
Another aspect of the present invention provides a kind of compliant conductive circuit plate, which is characterized in that is printed on substrate aforementioned
Compliant conductive medium,
Preferably, the substrate is selected from hard material plank, flexible flexible material plank or elastic material plank；
It is highly preferred that hard material plank is selected from silicon chip, sheet glass, metallic plate, plastic plate, plank；
Flexible flexible material plank is selected from the fabric etc. of plastic film, paper, natural fiber or synthetic fibers；
Elastic material plank is selected from silicon rubber film, polyurethane film, ethylene-vinyl acetate copolymer film, polyethylene
Film, polyvinyl chloride film, polybutadiene membrane, polystyrene thermoplastic film.
Substrate of the present invention can carry out mechanically deform, specifically include flexibility, Rigid bending, torsion, stretching.
Another aspect of the present invention provides a kind of preparation method of compliant conductive circuit plate comprising following steps：
The printable compliant conductive slurry of the present invention is patterned by printing technology, and compliant conductive is made in curing molding
Wiring board；
Preferably, the condition of curing molding is solidification 10min~for 24 hours at 20~150 DEG C.
In a particular embodiment, printable compliant conductive slurry provided by the invention and its conducting wire comprising (1)
Silver-plated conductive particle；(2) PDMS flexible polymers.Mass percent shared by silver-plated conductive particle is 40%-85%.
Preferably, the silver-plated conductive particle is the core-shell structural conductive particle of electroplate using polymer microballoon as core,
Surface silver content accounts for the 30%~80% of silver-plated conductive particle quality.
Preferably, the polymer microballoon is polystyrene, polymethyl methacrylate, polyacrylic acid, poly- divinyl
One or more in benzene or its copolymer, grain size is 200nm~10 μm.
Preferably, the PDMS flexible polymers include PDMS prepolymers and its curing agent, and the two mass ratio is 10:1, Gu
Change temperature be room temperature~150 DEG C, hardening time for 24 hours~10min.
In addition, the present invention also provides a kind of printable compliant conductive slurry and its preparation methods of conducting wire, including
Following step：
(1) silver-plated conductive particle is synthesized
With polystyrene (PS), polymethyl methacrylate (PMMA), polyacrylic acid (PAA), poly- phenolic resin (PF), gather
The low-density such as divinylbenzene (PDVB) or its copolymer microsphere (about 1.0g/cm3) spherical polymer particles be matrix, pass through
Chemical plating method deposits Argent grain on its surface, and the conductive particle of electroplate is prepared.
(2) mixed slurry of silver-plated conductive particle and PDMS flexible polymers is prepared
Silver-plated conductive particle is directly added into the mixture of PDMS prepolymers and its curing agent, mechanical agitation mixing or high
Speed rotation is mixed to form uniform mixed slurry.
(3) mixed slurry is patterned by printing technology, and compliant conductive circuit is made in curing molding.
Mixed slurry prepared by step (2) is existed by printing technologies such as silk-screen printing, blade coating printing, mask version printings
The pattern of setting is printed as on substrate, curing for 24 hours~10min at room temperature~150 DEG C obtains conducting wire pattern.Substrate can be
The hard materials such as silicon chip, sheet glass, metallic plate can also be the flexible flexible material such as plastic film, paper, fabric, also
Can be the highly elastic materials such as silicon rubber film, polyurethane film.
On the one hand the centre of sphere present invention employs polymer microballoon as complex conductive particle only carries out gold with particle surface
Belong to plated film, reduces the cost of conductive particle；The density of the density ratio coat of metal of another aspect polymer microballoon is low, to subtract
The light density of filler, slows down sedimentation tendency of the filler in PDMS；Furthermore the filler of spherical structure advantageously reduces PDMS
The viscosity of mixed slurry, to increase printing effect, simultaneously because the evenly dispersed of complex conductive particle also correspondingly reduces
The dosage of complex conductive particle, and increase electrical efficiency.
Printable compliant conductive slurry provided by the invention and its conducting wire and preparation method, advantage are as follows：
1, the present invention has density low using the core that polymer microballoon is silver-plated conductive particle, made silver-plated conductive particle,
The characteristics of being not easy to deposit in PDMS flexible polymer solution, while there is higher conductivity, made compliant conductive slurry knot
Structure is uniform, performance is stable, electric conductivity is good；
2, the present invention is easy using the core that spherical polymer is silver-plated conductive particle, grain size, and preferred 200nm~
10 μ m in size size appropriateness, made slurry viscosity is moderate, it can be achieved that the large area printing of fining compliant conductive circuit makes；
3, electrocondution slurry of the invention does not use any solvent, be advantageously implemented electrocondution slurry in not organic solvent-resistant or
It is printed on the strong basis material of hygroscopicity；
4, conductive circuit of the invention shows good tensility and flexibility, can bear significantly deformation, such as
Stretch, bending, fold, winding with distortion etc..
5, preparation method is simple by the present invention, of low cost.
Description of the drawings
Fig. 1 schemes for silver-plated conductive particle SEM.
Fig. 2 is silver-plated conductive particle SEM partial enlarged views.
Fig. 3 is the conducting wire section SEM being printed on paper.
Fig. 4 is the conducting wire section SEM figures being printed on PI films.
Fig. 5 is the demonstrating conductive property figure for being printed on conducting wire on silicon chip.
Fig. 6 is to be printed on the demonstrating conductive property figure of conducting wire in the bent state on PI films.
Fig. 7 is to be printed on the demonstrating conductive property figure of conducting wire in a folded configuration on conventional A4 paper.
Fig. 8 is to be printed on demonstrating conductive property figure of the conducting wire under reeling condition on non-dust cloth.
Fig. 9 is the grain size distribution of silver-plated conductive particle.
Figure 10 is the viscosity test results of the printable compliant conductive slurry of the present invention.
Specific implementation mode
Embodiment 1：
(1) complex conductive particle is synthesized
The polystyrene microsphere for being about 5.5 μm using average grain diameter, by chemical plating process in its electroplate, is obtained as core
Silver-plated conductive particle (as shown in Figures 1 and 2).The preparation process of silver-plated conductive particle is as follows：I) it is roughened：1 gram of styrene is micro-
Ball powder is added in beaker, and 20 milliliters a concentration of 98% of the concentrated sulfuric acid is added into beaker, beaker is placed in Vltrasonic device and is surpassed
Sound makes Polystyrene powder be uniformly dispersed in concentrated sulfuric acid, is then transferred to beaker in 50 DEG C of water-bath, in magnetic agitation
Lower reaction 4h is made into the aqueous dispersions of 200mL 5mg/mL after being washed with deionized totally；II) sensitization：By 200mL 5mg/
ML roughening polystyrene microsphere aqueous dispersions are added in the stannous chloride solution of 200mL 10mg/mL, and 30 DEG C are stirred 1h
So that polystyrene microsphere is fully sensitized, the aqueous dispersions of 200mL 5mg/mL are made into after being washed with deionized totally；III) chemistry
Plating：The 200mL 15mg/mL silver ammonia that 200mL 5mg/mL tin polystyrene microsphere aqueous dispersions are added to Fresh is molten
Liquid is stirred to react 2h at 30 DEG C, is washed with deionized dry with the mixed solution of 200mL 20mg/mL potassium sodium tartrate solutions
Only, silver-plated polystyrene conductive particle is obtained after drying.
(2) mixed slurry of silver-plated conductive particle and PDMS flexible polymers is prepared
Silver-plated polystyrene conductive particle is added in the mixture of PDMS prepolymers and its curing agent (conductive particle matter
Amount is 3 with PDMS mass ratioes:2), high speed rotation vacuumizes de-bubbled 30min after mixing at room temperature, and compliant conductive slurry is made
Material.Above-mentioned slurry is respectively printed at silicon chip, polyimide (PI) film, A4 paper, non-dust cloth etc. no by screen printing technique
In the substrate of same material, and 30min is heated by printing slurry curing molding at 120 DEG C, obtain compliant conductive circuit.
The internal microstructure of conductive circuit is as shown in Figure 3 and Figure 4, it can be seen that silver-plated conductive micro-balloons are in PDMS matrixes
In it is evenly dispersed.Fig. 3 is also seen that there is printed wire high resolution ratio, line width respectively may be about 100 μm with line-spacing.After tested with
It calculates, the conductivity of made conducting wire is 3.85 × 104S/m.In order to visually demonstrate the electric conductivity of the conductive circuit with
Printed wire is connect by flexibility with external circuit and LED bulb, under different mechanical deformations the material can lightening LED lamp bubble, such as
Shown in Fig. 5~8.
Embodiment 2：
(1) complex conductive particle is synthesized
The polystyrene microsphere for being about 1 μm using average grain diameter, by chemical plating process in its electroplate, is plated as core
Silver-colored conductive particle.
(2) mixed slurry of silver-plated conductive particle and PDMS flexible polymers is prepared
Silver-plated polystyrene conductive particle is added in the mixture of PDMS prepolymers and its curing agent (conductive particle matter
Amount is 7 with PDMS mass ratioes:3), high speed rotation vacuumizes de-bubbled 30min after mixing at room temperature, and compliant conductive slurry is made
Material.It is thin that above-mentioned slurry by metal mask version doctor blade technique is respectively printed at glass, polyethylene terephthalate (PET)
In the substrates of unlike materials such as film, A4 paper, and 4h is heated by printing slurry curing molding at 80 DEG C, obtain flexible conductive wire
Road.After tested with calculating, the conductivity of made conducting wire is 4.7 × 104S/m。
Embodiment 3：
(1) complex conductive particle is synthesized
The polystyrene microsphere for being about 1 μm using average grain diameter, by chemical plating process in its electroplate, is plated as core
Silver-colored conductive particle.
(2) mixed slurry of silver-plated conductive particle and PDMS flexible polymers is prepared
Silver-plated polystyrene conductive particle is added in the mixture of PDMS prepolymers and its curing agent (conductive particle matter
Amount is 1 with PDMS mass ratioes:1), mechanical agitation vacuumizes de-bubbled 30min after mixing at room temperature, and compliant conductive slurry is made
Material.Above-mentioned slurry is respectively printed at the unlike materials such as glass, stainless steel substrates, plastics, rubber, A4 paper by screen printing technique
Substrate on, and place printing slurry curing molding at room temperature for 24 hours, obtain compliant conductive circuit.After tested with calculating,
The conductivity of made conducting wire is 9.2 × 103S/m。
4 viscosity test of embodiment
Using polystyrene microsphere as core, by chemical plating process in its electroplate, silver-plated conductive particle is obtained.Using sharp
Light Particle Size Analyzer (Malvern, Mastersizer 3000) tests the particles size and distribution of made silver-plated conductive particle, as a result
As shown in figure 9, its particle size range is about 1~11 μm, about 5.7 μm of average grain diameter.By silver-plated conductive particle and PDMS prepolymers and
Its curing agent is uniformly mixed by different proportion, obtains compliant conductive slurry.The viscosity of the electrocondution slurry is (difficult to understand using rotational rheometer
Land productivity Anton Paar, MCR302) it is tested, a diameter of 25mm of rotary parallel plate, the gap distance of parallel-plate and test panel is 106
μm, it is 1~100s that shear rate, which tests section,-1.When being not added with silver-plated conductive particle, PDMS viscosity is 3.18Pas；It is silver-plated to lead
When electric particle additive amount is 30wt%, mixed slurry viscosity is 3.83Pas；As silver-plated conductive particle additive amount gradually increases
To 40wt%, 50wt%, 55wt% and 60wt%, mixed slurry viscosity is increased separately to 5.06,6.41,8.33 and 9.14Pa
S, and above-mentioned slurry viscosity is not substantially change with shear rate increase.Plating silver fillers additive amount is further increased to
When 65wt%, 70wt% and 75wt%, initial viscosity (the shear rate 1s of slurry-1When) significantly rise to 35.7,107 with
1090Pas, and its viscosity with the increase of shear rate is gradually decrease to 9.42,10.03 (shear rate is with 10.69Pas
100s-1When).In terms of the result actually printed, when plating Argent grain additive amount less than 50wt%, slurry viscosity is too low, is easy to lead
Cause printed wire horizontal proliferation；When plating Argent grain additive amount higher than 65wt%, slurry viscosity is excessively high, it is difficult to pass through silk-screen printing
Technique obtains fine printed wire, but can print making conducting wire by modes such as mask plate blade coatings.Silver-plated granule content
In 50wt%~65wt%, slurry viscosity is more moderate, and silk-screen printing technique has both been suitble to be also applied for the techniques such as blade coating printing,
High-resolution conductive circuit can be easy to get.
Although the present invention is disclosed above with preferred embodiment, however, it is not to limit the invention, any affiliated technology neck
Have usually intellectual in domain, without departing from the spirit and scope of the present invention, when can make some changes and embellishment, therefore this
The protection domain of invention is when subject to the claim institute defender of claims.
Claims (36)
1. a kind of printable compliant conductive slurry, which is characterized in that it is made of complex conductive particle and polysiloxane；Institute
It is particle of the diameter not higher than 20 μm that nonmetallic core surface is coated with metal surface to state complex conductive particle；The electrocondution slurry
In be free of organic solvent or inorganic solvent；
Metal in the metal surface is one or more in gold, silver, copper, nickel, aluminium, tungsten, iron, titanium, palladium, platinum；
The mass percent that the complex conductive particle accounts for printable compliant conductive slurry is 50wt%~85wt%；
The density of the nonmetallic kernel is 0.6-1.5g/cm3。
2. printable compliant conductive slurry according to claim 1, organic solvent be selected from acetone, butanone, ethyl alcohol, methanol,
Isopropanol, benzene, toluene, styrene, n-hexane, hexamethylene, dichloromethane, chloroform, ether, glycol monoethyl ether, acetonitrile,
It is one or more in pyridine；
Inorganic solvent is one or more in water, liquefied ammonia, sulfuric acid, nitric acid.
3. printable compliant conductive slurry according to claim 1 or 2, which is characterized in that complex conductive particle, which accounts for, to be printed
The mass percent of brush compliant conductive slurry is 50wt%~80wt%.
4. a kind of printable compliant conductive paste compound, which is characterized in that it includes complex conductive particle, polysiloxane
Prepolymer and its curing agent；The complex conductive particle is that nonmetallic core surface is coated with the diameter of metal surface not higher than 20 μm
Particle；Organic solvent or inorganic solvent are free of in the conductive paste composition；
Metal in the metal surface is one or more in gold, silver, copper, nickel, aluminium, tungsten, iron, titanium, palladium, platinum；
The mass percent that the complex conductive particle accounts for printable compliant conductive paste compound is 50wt%~85wt%；
The density of the nonmetallic kernel is 0.6-1.5g/cm3。
5. printable compliant conductive paste compound according to claim 4, organic solvent be selected from acetone, butanone, ethyl alcohol,
Methanol, isopropanol, benzene, toluene, styrene, n-hexane, hexamethylene, dichloromethane, chloroform, ether, glycol monoethyl ether,
It is one or more in acetonitrile, pyridine；
Inorganic solvent is one or more in water, liquefied ammonia, sulfuric acid, nitric acid.
6. printable compliant conductive paste compound according to claim 4 or 5, which is characterized in that the composite conducting
The mass percent that particle accounts for printable compliant conductive paste compound is 50wt%~80wt%.
7. can print compliant conductive slurry or claim 4-5 any one of them according to claim 1-2 any one of them
Printable compliant conductive paste compound, wherein the nonmetallic kernel of the complex conductive particle is selected from glass, ceramics, inertia
The microballoon that polymer is formed.
8. can print compliant conductive slurry or claim 4-5 any one of them according to claim 1-2 any one of them
Printable compliant conductive paste compound, wherein the nonmetallic kernel of the complex conductive particle is selected from glass, ceramics, inertia
The microballoon that polymer is formed, the microballoon are selected from polystyrene microsphere (PS), polyacrylic acid microballoon (PAA), polymethylacrylic acid
One in methyl esters microballoon (PMMA), poly- phenolic resin microspheres (PF), polydivinylbenezene microballoon (PDVB) or its copolymer microsphere
Kind is a variety of, and grain size is 200nm~10 μm.
9. can print compliant conductive slurry or claim 4-5 any one of them according to claim 1-2 any one of them
The density of printable compliant conductive paste compound, the nonmetallic kernel is 0.8-1.2g/cm3。
10. printable compliant conductive slurry according to claim 9 or printable compliant conductive paste compound, described non-
The density of metal inner core is 1.0g/cm3。
11. printable compliant conductive slurry according to claim 10 or printable compliant conductive paste compound, described
The content of nonmetallic core surface metal surface accounts for the 30%~80% of complex conductive particle quality.
12. can print compliant conductive slurry or claim 4-5 any one of them according to claim 1-2 any one of them
Printable compliant conductive paste compound, wherein the metal surface is by being chemically or physically plated in nonmetallic
On core surface.
13. printable compliant conductive slurry according to claim 12 or printable compliant conductive paste compound, wherein
The metal surface is at least coated with 1 layer.
14. printable compliant conductive slurry according to claim 13 or printable compliant conductive paste compound, metal
Surface layer is coated with 1 layer or 2 layers.
15. claim 1-2 any one of them can print compliant conductive slurry, wherein polysiloxane is by poly-organosilicon
Oxygen alkane prepolymer and its curing agent are made.
16. printable compliant conductive slurry according to claim 15, wherein polysiloxane prepolymer and curing agent
Mass ratio be 5:1~15:1.
17. printable compliant conductive slurry according to claim 15, the polysiloxane is selected from poly dimethyl silicon
One kind or more in oxygen alkane, cyclomethicone, amino silicone, polymethylphenylsiloxane, polysiloxane polyether copolymer
Kind.
18. printable compliant conductive slurry according to claim 15, the polysiloxane prepolymer is selected from poly- two
Methylsiloxane (PDMS).
19. printable compliant conductive slurry according to claim 15, the curing agent is selected from small molecule silane.
20. printable compliant conductive slurry according to claim 15, the curing agent is with silicone hydroxyl, siloxy
Small molecule silane.
21. claim 4-5 any one of them can print compliant conductive paste compound, wherein pre- by polysiloxane
Polysiloxane has been made in polymers and its curing agent.
22. printable compliant conductive paste compound according to claim 21, wherein polysiloxane prepolymer with
The mass ratio of curing agent is 5:1~15:1.
23. printable compliant conductive paste compound according to claim 21, the polysiloxane is selected from poly- two
One in methylsiloxane, cyclomethicone, amino silicone, polymethylphenylsiloxane, polysiloxane polyether copolymer
Kind is a variety of.
24. printable compliant conductive paste compound according to claim 21, the polysiloxane prepolymer choosing
From dimethyl silicone polymer (PDMS).
25. printable compliant conductive paste compound according to claim 21, the curing agent is selected from small molecule silane.
26. printable compliant conductive paste compound according to claim 21, the curing agent is band silicone hydroxyl, silane
The small molecule silane of oxygroup.
27. can print compliant conductive slurry or claim 4-5 any one of them according to claim 1-2 any one of them
Printable compliant conductive paste compound, the complex conductive particle account for printable compliant conductive slurry or printable compliant conductive
The mass percent of paste compound is 50wt%~65wt%.
28. claim 1-3,7-20,27 any one of them can print compliant conductive slurry or claim 4-14,21-27
Any one of them can print the preparation method of compliant conductive paste compound, and preparation process includes：
(1) complex conductive particle is synthesized
Using nonmetallic kernel as matrix, on its plating metal on surface surface layer；
(2) mixed slurry of silver-plated conductive particle and polysiloxane is prepared
Weigh the complex conductive particle obtained by polysiloxane prepolymer and its curing agent and step 1)；
Each ingredient mechanical agitation that step 2) weighs is mixed or high speed rotation is mixed to form uniformly.
29. preparation method according to claim 28, in the step of plating metal surface on nonmetallic kernel by with lower section
Formula is made：
I) it is roughened
Roughening treatment is carried out on nonmetallic kernel with strong acid；
Ii it) is sensitized
With in stannous chloride aqueous solution to carrying out sensitized treatment on the nonmetallic kernel obtained by step i)；Sensitized treatment at room temperature
30min~3h；
Iii) chemical plating
Silver ammino solution is prepared, and by step ii) the nonmetallic kernel after gained sensitization is added in silver ammino solution, is then added also
Original reagent, the reaction was complete obtains complex conductive particle.
30. a kind of compliant conductive medium can print compliant conductive slurry by claim 1-3,7-20,27 any one of them
Or claim 4-14,21-27 any one of them can print compliant conductive paste compound as obtained by the printing on substrate.
31. compliant conductive medium according to claim 30, the printing is selected from silk-screen printing, blade coating printing, mask plate
Printing.
32. a kind of compliant conductive circuit plate, which is characterized in that it is soft to be printed with claim 30-31 any one of them on substrate
Property conducting medium.
33. compliant conductive circuit plate according to claim 32, which is characterized in that the substrate is selected from hard laminate
Material, flexible flexible material plank or elastic material plank.
34. compliant conductive circuit plate according to claim 33, hard material plank is selected from metallic plate, plastic plate, plank；
Flexible flexible material plank is selected from the fabric of plastic film, paper, natural fiber or synthetic fibers；
Elastic material plank be selected from silicon rubber film, polyurethane film, ethylene-vinyl acetate copolymer film, polyethylene film,
Polyvinyl chloride film, polybutadiene membrane, polystyrene thermoplastic film.
35. the preparation method of claim 32-34 any one of them compliant conductive circuit plates comprising following steps：
Claim 1-3,7-20,27 any one of them be can print into compliant conductive slurry or claim 4-14,21-27 appoints
Printable compliant conductive paste compound described in one is patterned by printing technology, and flexible conductive wire is made in curing molding
Road plate.
36. preparation method according to claim 35, the condition of curing molding be solidification 10min at 20~150 DEG C~
24h。
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| CN109354877A (en) * | 2018-10-29 | 2019-02-19 | 西南大学 | A kind of flexible strain-responsive material and preparation method thereof mismatching region with modulus |
| EP3654355A1 (en) * | 2018-11-14 | 2020-05-20 | Siemens Aktiengesellschaft | Electrical sheet having a structured surface for refining the domain structure |
| CN109860562A (en) * | 2019-02-15 | 2019-06-07 | 柔电（武汉）科技有限公司 | A kind of electrode slurry, flexible pole piece and preparation method thereof, flexible battery |
| US20220076858A1 (en) * | 2019-04-10 | 2022-03-10 | Shenzhen Institutes Of Advanced Technology Chinese Academy Of Sciences | Flexible conductive thin film based on silver powder and pdms, and preparation method therefor |
| CN110987288B (en) * | 2019-12-06 | 2021-07-06 | 深圳先进技术研究院 | Conductive composite microsphere, preparation method and application thereof, and flexible pressure sensor comprising conductive composite microsphere |
| CN113871094B (en) * | 2020-06-30 | 2024-04-05 | 三元科技（深圳）有限公司 | Coating method of conductive coating of circuit and cable with conductive coating |
| CN111901980A (en) * | 2020-07-13 | 2020-11-06 | 珠海杰赛科技有限公司 | Method for manufacturing flexible circuit board |
| CN113035448B (en) * | 2021-03-09 | 2022-07-12 | 西北工业大学 | Flexible conductive metal pattern, preparation method and application thereof, and conductive material |
| CN113045960B (en) * | 2021-03-12 | 2022-02-15 | 东莞市德聚胶接技术有限公司 | Epoxy electromagnetic shielding coating and preparation method thereof |
| CN113453526A (en) * | 2021-06-29 | 2021-09-28 | 深圳先进电子材料国际创新研究院 | Low-compression-stress electromagnetic shielding material and preparation method thereof |
| CN113881229A (en) * | 2021-10-27 | 2022-01-04 | 华中科技大学 | Stretchable conductive composite material and preparation method and application thereof |
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