CN103262667B - The method producing that conduct electricity and/or pressure drag trace on polymeric substrate - Google Patents
The method producing that conduct electricity and/or pressure drag trace on polymeric substrate Download PDFInfo
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- 230000005611 electricity Effects 0.000 title claims abstract description 6
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- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 14
- 239000003610 charcoal Substances 0.000 claims abstract description 9
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 9
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- KARVSHNNUWMXFO-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane;hydrate Chemical compound O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O KARVSHNNUWMXFO-UHFFFAOYSA-N 0.000 claims description 9
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Abstract
For being radiated in non-conductive polymer base material the method producing that conduct electricity and/or pressure drag trace by laser, it is characterized in that, described base material is composite polymeric materials, including the substrate of non-one-tenth charcoal polymer with comprise the dispersion phase of carbon nano-fiber and/or nanotube, wherein said composite also comprises the granule of phyllosilicate.
Description
Technical field
The present invention relates to by using laser beam to produce the side of that conduct electricity and/or pressure drag trace on polymeric substrate
Method.
Background technology
EP0230128A and WO0223962A describes for writing (writing) conductive trace on polymeric substrate
Laser means.The trace obtained includes the conduction produced by the surfacing at local laser heating thermal decomposition base material
Carbon.The material that can act as base material is the polymeric material of easy carbonization, as such as Benzaldehyde resin, polyimides, furfuryl alcohol polymerization
Thing, or easily decompose any other polymer producing high carbonization productivity；Described polymeric substrate is additionally may included in laser wave
Long lower improve the dispersion electric charge that light absorbs, as such as, carbon, Talcum, cotton or wood powder.
Summary of the invention
It is an object of the invention to provide the method being suitable for producing conductive trace on polymeric substrate, described polymeric substrate
It is not intended that the base material (" non-one-tenth charcoal polymer " (non char forming polymer)) of applicable carbonization, i.e. in thermal decomposition
After be difficult to carbonization.
It is a further object to provide in the polymer allowed in being widely used in vehicle and household electrical appliance and produce
Conduction and/or the method for pressure drag trace, as such as polypropylene and polyethylene.
In view of this kind of purpose, it is an object of the invention to as in the method defined in appended claims, it constitutes this explanation
The integral part of book.
The present invention considers to use composition polymer base material, including the polymer being filled with the dispersion phase comprising carbonization accelerator
Substrate；Due to the existence of carbonization accelerator, laser ablation the Polymer-pyrolysis mechanism caused, by volatilization, carry out conductive carbon
The formation of structure.When mixing, add the additive as accelerator in polymeric matrix to, trace conduction can be participated in, increase
Thick.
As carbonization accelerator, employ multiple silky nano structure, selected from carbon nano-fiber (CNF), single wall (SWCNT)
With the CNT (CNT) of many walls (MWCNT) type, itself and/or functionalization, and some of them atom N replaces the carbon of carbon
Nanotube (azotized carbon nano pipe or CNNT).
The CNT used in the present invention and the filament that is made up of " carbon-coating " of nanofiber, described carbon-coating be or
Many or few crystallization and be ordered into, stacking and/or winding.Nanofiber and carbon nanotube types the strictest
It is classified as follows, although it has been generally acknowledged that all carbon structures extend along the Main way of growth, form " pipe " with inner chamber, such as carbon nanometer
Pipe." graphene layer (" graphenic layer "), thus it is considered that by carbon atom C-sp for the definition of most stringent of classificating requirement2
The thin slice of composition, is ranked up and organizes (formation hexagon) having the planar fashion of honeycomb texture.For structure, described
Graphite is formed at single graphene layer (graphenic layer) at top by overlieing one another thus forms crystal.
According to the definition that this is tightened up, described CNT (CNT) has the graphite being generally parallel to filament alignment
Alkene layer (graphenic layer), thus constitute " nanotube ", internal more or less hollow and have parallel and roll
Wall.On the other hand, described carbon nano-fiber (CNF) is entirely these structures, the most orderly, and when in order, it is put down
Face is stacked, or forms wall, and these walls can be by according to the graphene film winding relative to a certain angle of filament axes/stacking
(graphenic sheet) forms (" herringbone " structure).
In more detail, described CNT (CNT) is divided into:
-SWCN (SWCNT), when they are made up of list " Graphene " layer being wrapped in the most with it, thus shape
Become tubular structure (because it is surrounded by wall)；
-multi-walled carbon nano-tubes (MWCNT), when they are by coaxial many " Graphene " slice-shaped being wound around on top each other
Cheng Shi, simplest MWCNT are " double-walled carbon nano-tube " or DWCNT, and its wall is by two graphene planes one another around curling
Composition.
The mode that " Graphene wall (the graphenic wall) " of nanotube is wound around or winds is by two instructions (m, n) tables
Show, which define and determine the different types of chiral vector of SWCNT.During as m=0 or as m=n, described nanotube is called " saw
Profile of tooth " or " armchair shape ", it is otherwise " chirality " (m ≠ n, m > 0).SWCN (SWCNT) and double-walled carbon nano-tube
(DWCNT) this " finely " divides for proving that different electrical characteristics are necessary: according to different " chiralitys ", described CNT
There are different electrical characteristics and can be quasiconductor (band gap is up to ≈ 2eV) or metal (band gap=0eV).For many walls carbon
Nanotube (n > 2), electrical property is metal (Eg=0eV), is given because it is the summation contributed by single wall.
For given CNT (n, m), if n=m(armchair shape) described nanotube is metallic, if n-m
Being the multiple of 3, described nanotube is the quasiconductor with very spatia zonularis, and the most described nanotube is gentle quasiconductor.So
And, this general rule has exception, owing to more or less significant curvature can affect electrical characteristics.
In theory, described metal nano-tube can support the highest electric current density ≈ 109A/cm2, it is non-compared with copper
The biggest value.Electric conductivity (low-resistivity) is the highest.
From scientific literature, carbon nano-fiber (CNF), the electricity of the CNF/CNT system of CNT (CNT) and/or mixing
Performance is the most various, and is difficult to define, because it depends on several factors, in particular how carries out electrical measurement and (measures ginseng
Number), if measure on single filament and depend on nano-filaments itself characteristic (synthesis temperature, use carbon before
The type of body, the existence of " coating ", catalyst residual, impurity and/or " adulterant ", the diameter of nano-filaments and length, depend on
In thing followed crystalline order degree, depend on that sample is at CNT when measuring in the system including more than one filament
And/or uniformity in terms of the distribution of diameter/length/phase place present in CNF.Further, since existing defects, diameter, spiral
Property, the finite size of nanotube, temperature, there is magnetic field, etc., experiment value be less than theoretical value.Such as, following table shows pin
Some electric current density measured and resistivity values to CNT.Those values of described herein value and other types material are entered
Go and compared:
It is believed that described CNT (CNT) is similar to use the nitridation of CNT structure (armchair shape, zigzag)
CNT (CNNT), some of them atom N replaces carbon.
With a certain amount of, described CNF and/or CNT is attached in polymeric matrix, the nano composite material obtained with holding
Less than conductivity threshold, typically with (weight of the most described nano composite material) 0.1 to 10% by weight, and preferably by weight
The amount of gauge 1 to 3%.
It is proved the existence disperseing above-mentioned silky nano structure in the composite the formation of conductive trace is had
Essence ground importance.It is true that with the amount similar to CNT, from the comparative experiments only using carbon black to carry out, send out
The most only create more weak conductive trace, this purpose being not suitable for finding application.As a non-limiting example, can recognize
Selective surface's ablation of the local heating induction polymeric matrix for being produced by laser beam so that go out to be now dispersed in substrate
Nanotube or carbon nano-fiber.Additionally, the interaction of laser beam and polymeric matrix promotes its thermal decomposition, and carbon subsequently
Formed.The carbon formed by this way, as the bridge between the nanotube highlighted by ablation process or nanofiber
Work, so that trace conduction.
In one preferred embodiment, likely it is used in combination with above-mentioned CNT as carbonization accelerator and belongs to
Phyllosilicate family preferably has average thickness < 5nm and the maximum gauge < phyllosilicate of 10nm；Preferably belong to smectic glue
The phyllosilicate of Tujia, especially montmorillonite, Strese Hofmann's hectorite., fluoro hectorite, pyrophyllite.
In order to disperse in the polymer matrix (peel off and/or insert) with promoting the lamella nanoscale of phyllosilicate, can
To use organically-modified smectic clays (organic clay).By being present in the inorganic cation between these lamellas (typically
It is alkali and alkaline earth metal ions ion) and the ion exchange this modification of acquisition of organic ion.
Such as, as modified cation, it is possible to use ammonium Or
If you are using, it is possible to the amount between by weight 0.1 to 20%, and preferably 0.5 to 10%, (these values are
Refer to the weight of composite) layered silicate is introduced in polymeric matrix.
It finds particular application in formed or including the base material of the most non-one-tenth charcoal polymer produces conductive trace, should
Term refers to specify the polymerization that its thermal decomposition (at a temperature of usually above 500 DEG C) causes polymer to volatilize the most completely
Thing.
Nonetheless, it is intended that be also applied for " becoming charcoal polymer " according to method of the present invention, i.e. its structure is in thermal decomposition
Rear generation volatiling reaction and the polymer of carburizing reagent.
It is therefore preferred that described matrix material can be well-known with poor efficiency in producing material with carbon element
Thermoplastic polymer；In particular, preferred polyolefin polymers and copolymer, including polyethylene (include, UHMWPE, HMWPE,
HDPE, MDPE, MLDPE, LDPE), polypropylene, ethylene-propylene copolymer, styrene polymer (PS), ethylene copolymer include
Polyethylene vinyl acetate (EVA) and acrylic polymer, especially include polyacrylate, polymethacrylates and gather
Methyl methacrylate.
Described polymeric material can also include the mixture of two or more above-mentioned polymer.
Present invention also contemplates that the use of polymeric material, polymer as escribed above and copolymer, including compatibilization copolymer,
Compatibilization copolymer especially for the phyllosilicate likely added.As the bulking agent (alkene for phyllosilicate
Hydrocarbon polymer) we list such as maleic polyvinyl ester (maleate grafted polyethylene, MA-g-PE) and maleic acid poly-third
The copolymer of alkene ester (maleate graft polypropylene, MA-g-PP), and poly-(ethylene-co-vinyl acetate).
For by laser inscription trace, it is possible to use in a continuous manner, regulative mode or pulsed operation and
There is any lasing light emitter (its condition is that it has mainly thermal interaction) of certain wavelength, thus with polymeric matrix and/
Or the additive as the interpolation of carbonization accelerator interacts.
The light source launched in near-infrared or visible ray, and the lasing light emitter of transmitting is suitable for this purpose in far infrared.
But, second is directly and interpolymer interaction, cracks this polymer, and therefore induces carbonization, decomposes this polymer, and first
Individual directly do not interact with polymeric matrix, but with nanotube interaction, give off heat to polymer by heating, thus
Decompose.In both cases, the effect of laser is converted into the increase of nanotube local density in laser treated regions, and this leads
Cause to increase electrical conductivity by exceeding permeation limit.This effect increased by nanotube local density, is characterized exactly
Laser treatment in object, and not there is the negative effect damaged or damage nanotube itself (due to the peak power used
The highest (typically, the lasing light emitter of such as Q-switch)).
The lasing light emitter that can use in the process is preferably:
-laser instrument Nd:YAG(is also referred to as disc laser) or Nd:YLF or Nd:YVO4 or Nd: have about 1 at near-infrared
Micron launches the glass of wavelength, and mean power is between 5 to 500W, under the conditions of continuous or pulse operation.It should be noted that
Use Q-switching light sources (pulse persistance 5-500ns), although the negative change of resistivity can be provided, right rather than most suitable,
Because the high-peak power reached causes nanotube damaged.On the other hand, it is optimum for using the laser instrument with transmitting continuously
, because this interaction causes the pyrolysis of polymeric material not damage nanotube；But, even with based on neodymium
Laser instrument (pulse under the conditions of free-running operation, or regulation, or under altofrequency (f > 20kHz) under Q-Switching Condition) lead
The electrical conductivity causing processing region significantly increases.
-CO2Laser instrument, has the wavelength between 9 to 11 microns, and mean power is between 5 to 1000W, at continuous print, arteries and veins
Under operating condition that is that rush or that regulate.
-diode laser, wavelength is between 0.5 to 3 micron, and mean power is between 5 to 1000W, at continuous print, arteries and veins
Under operating condition that is that rush or that regulate.
-fibre laser, ytterbium fibre laser type, to launch and be about 1 micron, mean power is between 5 to 1000W, even
That continue, pulse or regulation operating condition under.For the light-pulse generator under Q-Switching Condition, apply and swash for Nd:YAG
The identical observation that light device is carried out.
In a preferred embodiment, by applying 0.1 to 10 joule/mm3Between per unit length specific energy (
Corresponding to the energy of per unit volume in size) carry out laser illumination laser and (be applicable to the wavelength (UV-of all considerations
FIR)).
In the case of impulsive condition laser operations, the peak power of application (is expressed as pulsed laser energy, refers to every list
Plane amasss the pulse duration) it is preferably no greater than 15 megawatts/cm2。
In the case of continuous laser operates, peak power is corresponding to the mean power of application, preferably at 5 watts/cm2To 10
Megawatt/cm2Between.
With from 5mm/s until the speed of 20m/s, polymeric substrate is write trace.This speed depends on being used
The power of laser instrument: power is the biggest, it is possible to use speed the biggest.Commercially available light source easily reaches hundreds of watts of merits in principle
Rate, thus allow to carry out described method with the speed of tens of meters per minute.
Laser spot can be configured to circle, or elongated such as blade-shaped.
Single channel (it uses the diameter (or width) laser spot equal to track width) can be used, or use mutually
Many passages (being used for producing relative to the broader trace of laser spot diameter) side by side, or use being permitted on top each other
Multichannel writes trace.By using scanning system, it is thus also possible to use " waving " function, screw is placed on straight line by this
On the top of motion (for this reason, the track width of generation depends on the diameter of spiral).
The air that is positioned in interaction zone or inert gas flow can be there is (typically at atmosheric pressure
For nitrogen, it is also possible to be argon and helium) in the case of write, thus limit and can promote what polymeric substrate burnt
The existence of oxygen.Cover with noble gas and improve the method, but this is optional.Further possibility be use have lazy
The sealing treatment room of property atmosphere, pressure is between 0.1atm to 5atm.
Accompanying drawing explanation
In conjunction with accompanying drawing, from following description and from embodiment, according to the other feature of the method for the invention and
Advantage will become clearer from, wherein:
-Fig. 1 is a schematic diagram, it is shown that three kinds of possible Direct Laser write configurations, including:
1) movement of sample；
2a) the movement of head；
2b) by having the movement of the laser beam of the probe of galvanometer mirror；
-Fig. 2 is the schematic diagram of laser scanning head；
-Fig. 3 a, 3b and 3c are the electron micrographs of the conductive trace obtained；
-Fig. 4 shows resistivity map, for the function of writing speed of the CNT of various concentration.
Referring to the drawings, in order to detect trace, no matter use which kind of light source, it is anticipated that configuration below:
1. sample is moved (Fig. 1-1) by motorized shaft, and described laser beam, suitably focus on, keep fixing: according to axle
Configuration and the type of motor, it is possible to realize moving in the space with up to 5 degree of freedom (thus also manufactured three-dimensional mark
Line, speed is up to 500m/min)；
2. the movement of laser beam:
A) by the system (Fig. 1-2 a) of the mobile motorized shaft focusing on laser head, therefore mobile laser on sample surfaces
Bundle；System and performance are similar to situation during mobile example；
B) by having the probe (Fig. 1-2 b) of galvanometer mirror: (use and be equipped with regular F-θ lens in the plane
Or the probe of telecentric lens) or (use Z dynamic scan head) mobile laser beam in space, speed can reach 50m/min.
3. mobile beam and sample, has the mixed configuration between 1 and 2a, first and second are dispensed from by
Degree, most conveniently based on geometry.
The trace formed has and allows generally for, with the highest, being directly proportional to the length of conductive trace, and therefore with its
The frequency that impedance is directly proportional is to launch the feature of signal.Additionally, they can support the power supply with finite size circuit.
Use these conductive traces, such as, it is therefore possible to send signal effective for remote control sensor.Separately
On the one hand, for power supply, in the case of circuit is lower powered, they can be conveyed through several square centimeters of grades circuit or
Larger area.
The resistivity value of the conductive trace that can be obtained by the method according to the invention depends on different factor, including base
Matter polymer and the character of additive, the content of carbonization accelerator, the condition of laser irradiation and application parameter, depositing of inert atmosphere
, air or other.
Detailed description of the invention
Embodiment 1
Material
In this embodiment, the granule of polyethylene (PE) or polypropylene (PP) nano composite material is prepared, at height
Under temperature, the CNT(of the industrial source (MITSUI) of certain percentage by weight is from 1 to 3%) mixed.Load the polyvinyl of CNT
Matter also added with 5% organically-modified sodium montmorillonite (Na-OMMT) and 5% poly-(ethylene-co-vinyl acetate) (EVA), comprises 19%
The vinyl acetate (EVA) of weight.On the other hand, based on polyacrylic substrate added with the maleated polypropylene ester (MA-of 5% weight
G-PP), the maleic anhydride of 1% weight is comprised.EVA and MA-g-PP is used as the bulking agent of montmorillonite.In order to mix, use melt
Blender (Brabender).Temperature in mixing chamber is maintained at 170-180 DEG C, and incorporation time is limited to 5min, thus keeps away
Exempt from the oxidation of the nano composite material prepared, from mixing chamber, take out this nano composite material and reduce to thin slice thick for about 1mm
(using pressure heating to 175-195 DEG C and the load of about 20bar).
Laser treatment
The lasing light emitter used is (model Extreme of the Q-switch with 1.06 micron wave lengths and 0-170W power
E200Quanta System) Nd:YAG.The repetition rate of described light source, otherwise can be to launch continuously between 7-60kHz
(cw) form operates.It is made up of the probe with aperture 15mm for moving the system of laser beam, wherein amasthenic lens
There is the flat field of 250mm focal length.
In this embodiment, lasing light emitter, under the power of 11 watts, operates with continuous radiation pattern.Described laser treatment exists
Nitrogen flows down and carries out.Under the different scanning speed of laser beam and use two different in width: 0.6 and 1.2mm to manufacture mark
Line, 10mm length spaced apart 1.5mm.
Result
In order to carry out impedance measurement, employ two instruments: electric impedance analyzer HP4192A(has high full scale 2M Ω)
For frequency analysis and Tektronix multimeter(Tyke circuit tester) DM5120(has high full scale 300M Ω)
For analyzing continuously.
As the electrode for measuring, employing two kinds of tungsten filaments, they suitably bend to allow and have mark to be analyzed
The contact that line is good.By micromanipulator by the positioning of electrode that so formed on sample, and the distance between contacting is about
For 9mm.
Resistivity along with the reduction of writing speed (i.e. irradiation time) and reduces along with the increase of track width.Conductance
Rate is also directly proportional to the percentage ratio of nanotube, but the process show the saturation of concentration more than 2%, this represent polyethylene and
Polyacrylic percolation threshold.
Nano composite material based on polyethylene:
Use said method, the resistivity that the end points at the trace obtained is measured, for 0.6mm width and write with 25mm/s
Trace in the nano composite material comprising 1%CNT, about 100-200k Ω cm, for 2-3% concentrations of nanotubes, then under
It is down to 10-20k Ω cm.
For 1.2mm width and with 8mm/s write trace, for 1%CNT concentration, it is thus achieved that lowest resistivity value be
11k Ω cm, and be 0.6-0.7k Ω cm for 2-3% concentration.
Based on polyacrylic nano composite material:
Use said method, the resistivity measured at the end points of the trace obtained, comprise 1% for writing on 13mm/s
Trace in the nano composite material of CNT, about 3k Ω cm, for the concentrations of nanotubes of 2-3%, then drop to 0.5-0.9k
Ω·cm.The trace wide for 0.6mm and wide those traces of 1.2mm, conductivity value is similar.
Embodiment 2:CO
2
Lasing light emitter
Material
Described nano composite material and preparation method are similar to embodiment 1.
Laser treatment
The light source used is CO2Laser instrument, has coaxial flow (model: an El-En Blade1500) wavelength of slow catalysis:
10.6 μm and power are between 100 to 1500 watts.Light source can be operated in the way of regulation or continuous transmitting.
In this embodiment, to launch operating condition continuously, with the actual power of on sample 32 watts, manufacture these marks
Line.Motor system is made up of the chuck (chuck) rotated together with the flat board fixed thereon with described sample；Square-shaped metal is covered
Mould (mask) and amasthenic lens likely select the size of speckle and clash into the laser power of sample.Obtain with nozzle and nitrogen stream
Obtained more inert atmosphere.
Result
Conductivity measurement has been carried out in the way of being similar to embodiment 1.
Nano composite material based on polyethylene:
Using said method, the resistivity value measured at the end points of the trace obtained, for 1.2mm width and with 9mm/
S writes on the trace in the nano composite material comprising 1%CNT, about 1.6k Ω cm, for the concentrations of nanotubes of 2-3%, then under
It is down to 1.3-0.9k Ω cm.
Based on polyacrylic nano composite material:
For the trace write with 9mm/s, described resistivity value reaches about 0.15k Ω cm.
Fig. 4 shows resistivity curve figure, for the function of the writing speed of various concentration C NT of reference example 2.
Have been carried out test, wherein compare the composite polymeric materials having He not there is montmorillonite.Lower table report
Passing through CO2Laser treatment (have slower, the coaxial flow of catalysis, 10.6 mum wavelengths, 50W laser power on sample, with
Continuously scheme, the writing speed with different) the most significant resistivity measurement that carries out on the conductive trace that obtains.
In the table,
∞ refers to the most reach instrument calibration end；
PP represents the polypropylene added with 2.5% weight CNT；
PE represents the polyethylene added with 2.5% weight CNT；
PP+MT represents added with 2.5% weight CNT and the polypropylene of 10% weight montmorillonite；
PE+MT represents added with 2.5% weight CNT and the polyethylene of 10% weight montmorillonite.
The resistivity measured from upper table it is inferred that in the sample have montmorillonite is substantially less than does not has montmorillonite
The resistivity of sample, every other condition is identical.
The base material being all made up of composite polymeric materials can be applied to according to the method for the invention, and be applied to
There is the base material of the surface layer formed by above-mentioned composite polymeric materials.
The method that the conductivity values obtained after laser ablation can apply the present invention, so that electrical connection even replaces
Copper that is expensive and that be difficult to reclaim connects.The trace generated according to path (it can change according to expectation), may be used for
The electrical equipment that is simple to manufacture (e.g., button, sensor, antenna, etc.) is combined in and is widely used in the poly-of automobile and household electrical appliance
In compound.
Owing to being equipped with the property of CNT, they are used as filler for being commonly used to manufacture assembly in automobile industry
In polymeric matrix, it is possible to obtain the particular electrical of composite.Especially, add CNT or CNF, even if with relative to
The low-down percentage ratio of conventional filler, it is provided that higher conductivity values, additionally, under doses, it is possible to for composite
There is provided piezoresistive characteristic, so that it becomes sensitive to the existence of outside degeneration and Pressure stimulation.Can know therefore, it is possible to provide
The polymer (simply touching (simple brushing), light pressure or impact) of the most dissimilar contact, the most actually makes
Make " touching sensitive integrated switch " material.
Ratio between change and the power of applying of the electrical property of composite, it is also possible to allow to manufacture distributed pressure
Sensor.Particularly, suitable laser treatment is used on the composite, it is possible to portion generates CNT(only at quilt in the substrate
The region of laser beam bombardment), it is derived from the region with high concentration CNT.It is also possible to directly manufacture on polymeric matrix
Different conductive traces and pressure drag region, so that surface is furnished with the internal circuit carried for signal and has push button function
Sensitive active region.
Claims (13)
1. for being radiated in non-conductive polymer base material the method producing that conduct electricity and/or pressure drag trace by laser, its
Being characterised by, described base material is composite polymeric materials, including the substrate comprising non-one-tenth charcoal polymer and comprise carbon or carbonitride
Nanotube or carbon nano-fiber are as the dispersion phase of the carbonization accelerator of described non-one-tenth charcoal polymer, wherein said composition polymer
Material also includes by weight, the weight of the most described composite polymeric materials, the free montmorillonite of choosing of the amount of 0.1% to 20%,
The granule of the phyllosilicate of the group of Strese Hofmann's hectorite., fluoro hectorite and pyrophyllite composition.
Method the most according to claim 1, it is characterised in that the described non-one-tenth charcoal polymer of described substrate includes that alkene gathers
Compound, acrylic polymer or their mixture.
Method the most according to claim 2, it is characterised in that the described non-one-tenth charcoal polymer of described substrate includes poly-second
Alkene, polypropylene, polystyrene, ethylene-propylene copolymer, polyethylene vinyl acetate, polymethyl methacrylate and they
Mixture.
The most according to the method in any one of claims 1 to 3, it is characterised in that described composite polymeric materials include by
Weight meter, the weight of the most described composite polymeric materials, the carbon nano-fiber of the amount of 0.1% to 10% and/or CNT.
Method the most according to claim 1, it is characterised in that layered silicate is by organophilic functional group official
Energyization.
Method the most according to claim 1, it is characterised in that include by weight, the most described composite polymeric materials
Weight, the phyllosilicate of the amount of 0.5% to 10%.
7. according to the method described in claim 5 or 6, it is characterised in that the described non-one-tenth charcoal polymer of described substrate includes choosing
From maleic polyvinyl ester, maleated polypropylene ester and the compatibilization polymer of poly-(ethylene-co-vinyl acetate).
The most according to the method in any one of claims 1 to 3, it is characterised in that by Nd:YAG, Nd:YLF, Nd:
YVO4, Nd: glass laser source, CO2Laser instrument, diode laser source and fibre laser carry out laser irradiation.
The most according to the method in any one of claims 1 to 3, it is characterised in that by applying 0.1 to 10J/mm3Between
Specific energy carries out described laser irradiation.
The most according to the method in any one of claims 1 to 3, it is characterised in that use specific power more than 5W/cm2Company
Continuous Laser emission carries out described laser irradiation.
11. according to the method in any one of claims 1 to 3, it is characterised in that uses specific power less than 15MW/cm2
Impulse ejection carry out described laser irradiation.
12. methods according to claim 2, it is characterised in that described olefin polymer is olefin copolymer.
13. methods according to claim 2, it is characterised in that described olefin polymer is the copolymer of ethylene.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10425339.8 | 2010-10-26 | ||
| EP10425339 | 2010-10-26 | ||
| EP10425349.7A EP2448383B1 (en) | 2010-10-26 | 2010-11-11 | Process for producing conductive and/or piezoresistive traces on a polymeric substrate |
| EP10425349.7 | 2010-11-11 | ||
| PCT/EP2011/068798 WO2012055934A1 (en) | 2010-10-26 | 2011-10-26 | Process for producing conductive and/or piezoresistive traces on a polymeric substrate |
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| Publication Number | Publication Date |
|---|---|
| CN103262667A CN103262667A (en) | 2013-08-21 |
| CN103262667B true CN103262667B (en) | 2016-11-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860625A (en) * | 2003-02-24 | 2006-11-08 | 麦克德米德有限公司 | Method of fabricating electronic interconnect devices using direct imaging of dielectric composite material |
| DE102008048459A1 (en) * | 2008-09-23 | 2010-03-25 | Pp-Mid Gmbh | Producing conductive structures on surface of polymer molded bodies, comprises providing polymer molded body from a polymer phase containing carbon nanotubes and thermally treating a surface of the polymer molded body |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860625A (en) * | 2003-02-24 | 2006-11-08 | 麦克德米德有限公司 | Method of fabricating electronic interconnect devices using direct imaging of dielectric composite material |
| DE102008048459A1 (en) * | 2008-09-23 | 2010-03-25 | Pp-Mid Gmbh | Producing conductive structures on surface of polymer molded bodies, comprises providing polymer molded body from a polymer phase containing carbon nanotubes and thermally treating a surface of the polymer molded body |
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