阅读说明：本技术 一种基于一维、二维材料的力致导电胶的制备与应用 (A kind of preparation and application causing conducting resinl based on one-dimensional, two-dimensional material power ) 是由 张久洋 楼洋 于 2019-08-15 设计创作，主要内容包括：本发明公开了一种基于一维、二维材料的力致导电粘合剂的制备与应用,在一维、二维材料的表面涂覆液态金属层作为导电填料的力致响应导电膜,形成力致导电材料,其制备方法是将液态金属以超声的方式分散于易挥发溶剂中形成液态金属悬浊液,再将该液态金属悬浊液喷洒与于一维、二维基质表面,制备出基于一维、二维材料表面涂覆液态金属层作为导电填料的力致导电材料。本导电胶的应用包括(1)各类设备的力感应部件,例如柔性触摸屏,智能布料,机器人的触觉交互部件等。(2)用作各种电路的导电粘合剂。(The invention discloses a kind of preparation and application that electroconductive binder is caused based on one-dimensional, two-dimensional material power, on one-dimensional, two-dimensional material surface, coating liquid-metal layer causes response conductive film as the power of conductive filler, it forms power and causes conductive material, preparation method is to disperse liquid metal in a manner of ultrasound formation liquid metal suspension in easy volatile solvent, again by the liquid metal turbid liquid spraying and Yu Yiwei, two-dimentional stromal surface, the power cause conductive material based on one-dimensional, two-dimensional material surface coating liquid-metal layer as conductive filler is prepared.The application of this conducting resinl includes that the power of (1) various kinds of equipment incudes component, such as flexible touch screen, intelligent cloth, haptic interaction component of robot etc..(2) it is used as the electroconductive binder of various circuits.)

1. a kind of preparation method for causing conducting resinl based on one-dimensional, two-dimensional material power, which is characterized in that in one-dimensional, two-dimensional material Surface coating liquid-metal layer as conductive filler power cause response conductive film, formed power cause conductive material, preparation method It is to disperse liquid metal in a manner of ultrasound formation liquid metal suspension in easy volatile solvent, then the liquid metal is hanged Turbid sprinkling and Yu Yiwei, two-dimentional stromal surface, prepare and are used as and are led based on one-dimensional, two-dimensional material surface coating liquid-metal layer The power of electric filler causes conductive material.

2. the preparation method according to claim 1 for causing conducting resinl based on one-dimensional, two-dimensional material power, which is characterized in that It is described to cause response conductive film as the power of conductive filler in one-dimensional, two-dimensional material surface coating liquid-metal layer, it forms power and causes Conductive material, preparation method also: liquid metal is coated on mechanical stirring or the mode of infiltration one-dimensional, two-dimensional material Conductive filler is mixed into adhesive by stromal surface by churned mechanically method, solidified with high-temperature heating, chemistry initiation, Liquid metal is coated on one-dimensional, two-dimensional material stromal surface by the method for solvent volatilization.

3. the preparation method according to claim 1 or 2 for being caused conducting resinl based on one-dimensional, two-dimensional material power, feature are existed In the mixture of the conductive filler and adhesive is laid in one piece of surface of circuit substrate, then another piece is had the electricity of electrode Base board is placed on the mixture, and upper layer and lower layer substrate needs to be aligned, and forms sandwich；Pass through hot pressing, chemistry initiation solidification Method make power cause conducting resinl upper and lower base plate bonding, the mixture film of the conductive filler and adhesive is in upper and lower two electrode at this time Between have good electric conductivity and horizontal direction is in state of insulation.

4. the liquid-metal layer according to claim 1 or 2 coated based on one-dimensional, two-dimensional material surface, which is characterized in that The liquid metal layer material is Metallic Gallium and the eutectic containing indium, zinc, bismuth, cadmium, tin, lead, dysprosium or indium as auxiliary element Type low-melting alloy, fusing point are below 150 degrees Celsius.

5. the liquid-metal layer according to claim 1 or 2 coated based on one-dimensional, two-dimensional material surface, which is characterized in that One-dimensional, the two-dimensional material, including macromolecular fibre, inorganic material, oxide nano thread；Material morphology includes different sizes Nanometer rods, nanotube, nano wire, nanofiber or nano thin-film.

6. one-dimensional, two-dimensional material surface coating liquid-metal layer conductive filler according to claim 5, feature exist In the material of the macromolecular fibre includes nylon, polyurethane, polycarbonate, polypropylene, polyethylene；Inorganic material includes Graphene sheet layer, carbon nanotube, silicon, nanometer silica line, metal nanometer line or nanometer sheet；Oxidate nano wire material includes Copper oxide, zinc oxide, calcium oxide.

7. one-dimensional, two-dimensional material surface coating liquid-metal layer conductive filler according to claim 2, feature exist In the adhesive is made of host agent and auxiliary agent；The host agent of adhesive includes:

Hot setting adhesive: epoxy resin tackifier, phenolic resin class adhesive, unsaturated polyester (UP) class adhesive, polyurethane Class adhesive, polyimide adhesive, allyl resin class adhesive, alkyd resin class adhesive；

Thermoplastic adhesive: polyethylene kind adhesive, PP type adhesive, polyvinyl chloride adhesive, crylic acid resin Adhesive, polycarbonate-based adhesive；

Modified multicomponent adhesive: phenolic aldehyde-epoxy type adhesive, phenolic aldehyde-polyurethane-type adhesive, phenolic aldehyde-nitrile rubber type Adhesive, phenolic aldehyde-Pioloform, polyvinyl acetal type adhesive, epoxy-polyamide type adhesive；

The auxiliary agent of adhesive is curing agent, initiator, catalyst, promotor, crosslinking agent, diluent, plasticizer, toughener, increasing Thick dose or stabilizer.

8. a kind of application that conductive material is caused based on one-dimensional, two-dimensional material power of method preparation as claimed in claim 1 or 2, It is characterized by: the power that power cause conductive material is used for various kinds of equipment is incuded component.

9. the application according to claim 8 for causing conductive material based on one-dimensional, two-dimensional material power, it is characterised in that: institute The power induction component stated includes the haptic interaction component of flexible touch screen, intelligent cloth, robot.

10. the application according to claim 9 for causing conducting resinl based on one-dimensional, two-dimensional material power, it is characterised in that: described Power incude component, caused power incudes the external force of component materials conductive access, including pressure, shearing force or folding force, with Under upper external force, the resistance of material is strongly reduced in the direction of the force, and circuit is connected.

Technical field

The present invention is a kind of preparation and application that conducting resinl is caused based on one-dimensional, two-dimensional material power, belongs to power and causes conduction material Expect the technical field of preparation.

Background technique

Power sends a telegraph response flexible encapsulant material in biomedical engineering, robot, flexible electronic device, conductive 3D printing The fields such as material are widely used.The electric conductivity of most of conductive flexible material is from conductive filler, and flexibility is from gluing Agent.In the case where being subject to external force, the movement of inner conductive filler may be implemented in the flexibility of adhesive, leads to changing for electric conductivity Become, to realize that power sends a telegraph response.The intensity of the electric conductivity of conductive filler, size, shape and adhesive and flexible all pole The earth influence power sends a telegraph the electric conductivity and mechanical strength of response flexible material.

The emergence trend of Electronic Packaging industry becomes clear day by day, display, and the products such as sensor move towards city from laboratory , therefore novel easy processing is developed, high performance power sends a telegraph response encapsulating material and is of great significance.

Summary of the invention

Technical problem: conductive packaging material is caused based on one-dimensional, two-dimensional material power the purpose of the present invention is to provide a kind of The preparation method of (glue).Another object is a kind of application that conductive packaging material (glue) is caused based on one-dimensional, two-dimensional material power Method.The control to liquid-metal layer thickness may be implemented by adjusting liquid metal and one-dimensional, two-dimensional material ratio, in turn The electric conductivity of control force cause conductive material.

Technical solution: a kind of preparation method that conducting resinl is caused based on one-dimensional, two-dimensional material power of the invention be it is one-dimensional, The surface coating liquid-metal layer of two-dimensional material causes response conductive film as the power of conductive filler, forms power and causes conductive material, Preparation method is to disperse liquid metal in easy volatile solvent in a manner of ultrasound formation liquid metal suspension, then by the liquid State metal turbid liquid spraying and Yu Yiwei, two-dimentional stromal surface are prepared based on one-dimensional, two-dimensional material surface coating liquid metal Layer causes conducting resinl as the power of conductive filler.

It is described to cause response conductive film as the power of conductive filler in one-dimensional, two-dimensional material surface coating liquid-metal layer, Form power and cause conductive material, preparation method also: with mechanical stirring or the mode of infiltration by liquid metal be coated on it is one-dimensional, two Conductive filler, i.e., be mixed into adhesive by the stromal surface for tieing up material by churned mechanically method, is solidified with high-temperature heating, is changed It learns and causes, liquid metal is coated on one-dimensional, two-dimensional material stromal surface by the method for solvent volatilization.

The mixture of the conductive filler and adhesive is laid in one piece of surface of circuit substrate, then has electrode for another piece Circuit substrate be placed on the mixture, upper layer and lower layer substrate needs to be aligned, formed sandwich；Pass through hot pressing, chemistry initiation Cured method makes power cause conducting resinl upper and lower base plate bonding, and the mixture film of the conductive filler and adhesive is upper and lower two at this time There is good electric conductivity between electrode and horizontal direction is in state of insulation.

The liquid metal layer material be Metallic Gallium and containing indium, zinc, bismuth, cadmium, tin, lead, dysprosium or indium as auxiliary at The cocrystallizing type low-melting alloy divided, fusing point are below 150 degrees Celsius.

One-dimensional, the two-dimensional material, including macromolecular fibre, inorganic material, oxide nano thread；Material morphology includes Various sizes of nanometer rods, nanotube, nano wire, nanofiber or nano thin-film.

The material of the macromolecular fibre includes nylon, polyurethane, polycarbonate, polypropylene, polyethylene；Inorganic material Including graphene sheet layer, carbon nanotube, silicon, nanometer silica line, metal nanometer line or nanometer sheet；Oxidate nano wire material Including copper oxide, zinc oxide, calcium oxide.

The adhesive is made of host agent and auxiliary agent；The host agent of adhesive includes:

Hot setting adhesive: epoxy resin tackifier, unsaturated polyester (UP) class adhesive, gathers phenolic resin class adhesive Ammonia ester adhesive, polyimide adhesive, allyl resin class adhesive, alkyd resin class adhesive；

Thermoplastic adhesive: polyethylene kind adhesive, PP type adhesive, polyvinyl chloride adhesive, acrylic acid tree Lipid adhesive, polycarbonate-based adhesive；

Modified multicomponent adhesive: phenolic aldehyde-epoxy type adhesive, phenolic aldehyde-polyurethane-type adhesive, the fine rubber of phenolic aldehyde-fourth Glue-type adhesive, phenolic aldehyde-Pioloform, polyvinyl acetal type adhesive, epoxy-polyamide type adhesive；

The auxiliary agent of adhesive is curing agent, initiator, catalyst, promotor, crosslinking agent, diluent, plasticizer, toughening Agent, thickener or stabilizer.

The application based on one-dimensional, two-dimensional material power cause conducting resinl of the method for the invention preparation is: power cause is led Power of the electric glue for various kinds of equipment incudes component.

The power induction component includes the haptic interaction component of flexible touch screen, intelligent cloth, robot.

The power incudes component, and caused power incudes the external force of component materials conductive access, including pressure, shearing force or Folding force, under the above external force, the resistance of material is strongly reduced in the direction of the force, and circuit is connected.

Surface is coated with the one-dimensional of liquid-metal layer, two-dimensional material matrix as conductive filler and adhesive raw materials knot It closes, power is made and causes conductive material, under external force, the electric conductivity of force part can change material obtained.

The utility model has the advantages that

Compared with power of the tradition containing conductive filler causes conducting resinl, the present invention has the following advantages:

(1) conductive filler declared in this patent is one-dimensional, the two-dimensional material that surface is coated with liquid metal, passes through adjusting The control to liquid-metal layer thickness may be implemented in liquid metal and one-dimensional, two-dimensional material ratio, and then control force causes conduction The electric conductivity of material.

(2) conductive filler declared in this patent is the particle that surface is coated with liquid-metal layer, and wherein liquid metal applies Layer be Metallic Gallium and the cocrystallizing type low-melting alloy containing elements such as indium, zinc, bismuth, cadmium, tin, lead, dysprosium, indiums as auxiliary element, Its fusing point is below 150 degrees Celsius, has stronger mobility compared to solid-state conductive filler.

(3) conductive filler declared in this patent is one-dimensional, the two-dimensional material that surface is coated with liquid-metal layer, passes through machine The modes such as tool cutting or chemical attack can control the size of matrix.

(4) matrix declared in this patent is the materials such as nanometer rods, nanotube, nano wire, nanofiber and nano flake, Larger to density, the liquid metal for being easy aggregation plays good peptizaiton, and making material after processing is not in that conduction is filled out The case where material deposition, electric conductivity stable homogeneous.

(5) based on one-dimensional, two-dimensional materials such as nanometer rods, nanotube, nano wire, nanofiber and nano thin-films in this patent Surface coats liquid-metal layer as the power of conductive filler and causes the resistance range of conductive film big, can by increasing the size of external force Resistance of the conductive film on external force direction is down to 1 ohm or less from tens of megaohms.

(6) power in this patent causes conductive film to be suitable for many kinds of force, such as pressure for the electroresponse of external force, shearing force, Folding force etc., resistance sharply declines on Impact direction, and circuit is connected.

Detailed description of the invention

Fig. 1 is the polyester fiber of uncoated liquid-metal layer,

Fig. 2 is the polyester fiber coated with liquid-metal layer.

Specific embodiment

The present invention can be achieved through the following technical solutions:

A kind of preparation and application causing conducting resinl based on one-dimensional, two-dimensional material power comprising the steps of:

Step (1) preparation is caused based on one-dimensional, two-dimensional material surface coating liquid-metal layer as the power of conductive filler conductive Material: by liquid metal by ultrasound in a manner of be scattered in easy volatile solvent, then by liquid metal droplet turbid liquid spraying in (one-dimensional, two-dimentional matrix includes various sizes of nanometer rods, nanotube, nano wire, nanofiber and nanometer to one-dimensional, two-dimentional matrix Film etc.) surface, or with mechanical stirring, the modes such as infiltration are by liquid metal coating and one-dimensional, two-dimentional stromal surface, then by surface The conductive filler for being coated with liquid metal is mixed into adhesive by churned mechanically method, is solidified with high-temperature heating, chemistry initiation, The methods of solvent volatilization forms material, stores for future use；

Step (2) causes conducting resinl as the power of conductive filler based on one-dimensional, two-dimensional material surface coating liquid-metal layer Application method: incuding component for the power that power cause conductive material is installed on various kinds of equipment, such as flexible touch screen, intelligent cloth, Haptic interaction component of robot etc. connects circuit and data sink, that is, collects the electric signal that external force generates, and external force can wrap Include pressure, shearing force, folding force etc..In addition to this, the mixture of conductive filler and adhesive is laid in surface of circuit substrate, Another piece of substrate with electrode, which is placed in upper layer and lower layer substrate on mixture, again needs to be aligned, and forms sandwich.By hot pressing, The methods of chemistry initiation solidification makes power that conducting resinl be caused to be bonded upper and lower base plate, and the film has good between upper and lower two electrode at this time Electric conductivity and horizontal direction is in state of insulation.

In order to better illustrate the present invention, it is further elaborated below with reference to example, but the contents of the present invention are not only It is confined to following example.

Preparation process example (for using pet fiber as the matrix of conductive filler)

The polyester fiber that step (1) prepares surface coating liquid-metal layer causes the conductive filler of conductive film as power

The mode of the spraying of a certain amount of liquid metal, mechanical stirring or solvent volatilization is coated on polyester fiber, is obtained To using polyester fiber as core, liquid metal coating is the skin-core structure of skin, and storage at room temperature is spare.

Step (2) prepares the polyester fiber of surface coating liquid-metal layer and the mixture of epoxy resin

The polyester fiber of a certain amount of surface coating liquid-metal layer is added in a certain amount of epoxy resin, mechanical stirring is The polyester fiber of uniform surface coating liquid-metal layer and the mixture of epoxy resin are obtained, storage at room temperature is spare.

Step (3) prepares polyester fibre surface coating liquid-metal layer as the power of conductive filler and causes conductive film

The mixture of the polyester fiber of surface coating liquid-metal layer and epoxy resin is heated at high temperature and is solidified, room is cooled to Warm standby is used.The resistance in z-axis direction can be down to 50m Ω from 50M Ω hereinafter, and protecting always with the increase of the size of the power of application The all directions held perpendicular to external force are in state of insulation.

Application example (for using polyester fiber as the application of the conductive material of conductive filler)

It is applied to the substrate surface with electrode to coat polyester fiber and the adhesive mixture of liquid metal, then will be another Block is placed on mixture that (upper layer and lower layer substrate needs precise alignment, it is ensured that the electrode energy of upper layer and lower layer substrate with the substrate of electrode Enough precise alignments, to guarantee the anisotropy of conducting resinl), form sandwich sandwich.It forms, is cooled to by hot setting Room temperature is spare.Processing temperature (temperature is generally greater than 30 DEG C of glass transition temperature) is set according to the glass transition temperature of adhesive, herein The pressure perpendicular to sample direction is applied to sample under temperature environment, it is cooling in the case where keeping pressure to restore to room temperature, it obtains To anisotropy conductiving glue.Conducting resinl has good electric conductivity on the direction along external force at this time, and remains perpendicular to external force All directions be in state of insulation (conduction resistance value be lower than 100m Ω).

In addition to this, by the way that in conjunction with the adhesive of different mechanical properties, can prepare has different response sensitivities to mechanics Power cause conducting resinl, for example conductive filler mix with silicon rubber, high-temperature heating cure under pressure, the conductive material softness after solidification It is flexible, the tactile inductor of available machines used people.

Although general explanation and specific example above has done detailed description to the present invention, in the present invention On the basis of the present invention can be realized to bound, the section value of cited raw material and response parameter, just do not do here Additionally repeat.

Performance test:

Tensile property test: it is carried out by CB/T 1040.3-2006, using SANS E42.503 type microcomputer controlled electronic ten thousand Energy testing machine is tested in room temperature, and rate of extension 5mm/min, every kind of sample need to test 5 battens, as a result average.It stretches Toughness can be by carrying out integral acquisition to tensile stress-strain curve.

Compression performance test: it is carried out by CB/T 1040.3-2006, using SANS E42.503 type microcomputer controlled electronic ten thousand Energy testing machine is tested in room temperature, and compression speed 1mm/min, every kind of sample need to test 5 battens, as a result average.

Impact strength: being tested with shock machine, is carried out according to GB/T 1843-2008, and simply supported beam mode, test are selected Temperature is room temperature.

Hardness performance analysis: it is tested with Shore durometer, test temperature is room temperature.

Differential scanning calorimeter: it is tested using DSC25 TA differential scanning calorimeter.Sample is carried out in nitrogen protection Test, heating rate are 5 DEG C/min, and temperature scanning range is 20-300 DEG C.

Dynamic thermo-mechanical property test: being tested using Q800 type dynamic thermo-mechanical analsis instrument, and test pattern is double outstanding Arm, for sample having a size of 80mm × 10mm × 4mm, heating rate is 3 DEG C/min, frequency 1Hz, Range of measuring temp 0-200 ℃。

Thermogravimetric analysis: being tested using TG 209F1 type thermogravimetric analyzer, and sample is tested in nitrogen protection, heating Rate is 10 DEG C/min, and temperature scanning range is 25-800 DEG C.

Scanning electron microscope characterization: sample extension test plane of disruption surface topography can pass through FEI Nova Nano SEM 450 scanning electron microscope are tested.

Electric conductivity test: Keysight 34461A uses bifilar mode monitored resistance to change over time at room temperature.Power supply Line periodicity (NPLC) and measurement range are 0.02 and automatic mode, and measuring option is resistance 2W.Electric wire is by rectangle sample Two sides are connected to Keysight 34461A.In the above process, all conducting wires are all firmly fixed by insulating tape.