A kind of electromagnetic shielding conductive foam and preparation method thereof
[technical field] the present invention relates to electromagnetic shielding material field, specifically a kind of electromagnetic shielding conductive foam and preparation method thereof.
[background technology] conductive sponge is a kind of material integrating conduction and electro-magnetic screen function, and it is a kind of tridimensional network, has the advantage of foaming uniform pore diameter, softness, high resilience, not furfur; Also there is the conductive effective phase long, shield effectiveness is good, not by the impact of temperature and humidity, sheet resistance value by features such as practical use settings, can be widely used in the packaging of computer, LCD display, LCD TV, laser printer, high speed copier, communication apparatus, mobile phone, satellite communication, Medical Devices, high-pressure unit test, instrument, pad/dividing plate, plate electronic product, shockproof conduction.At present, conductive sponge mainly adopts three-dimensional porous polyurethane sponge to be base material, this base material is three-dimensional porous structure, there is larger specific area, performance for electromagnetic shielding is very excellent, but along with the fast development of electronic technology, to the requirement of electromagnetic shielding material ultrathin and the requirement of electromagnetic shielding material sheet resistance and vertical resistor characteristic more and more higher.Now commercially conductive sponge cannot meet the growth requirement of modern electronic technology far away, and existing technique cannot produce the porous matrix that thickness is less than 0.8mm.Therefore, developing ultra-high conductivity and ultra-thin conductive sponge, is the active demand of electromagnetic shielding material technical development.
Application number is the invention of 201310126285.9, disclose a kind of preparation method (hereinafter referred to as carbon coating sponge preparation method) of conductive sponge, it is not more than the polyester sponge of 10 millimeters or the coiled material of polyethers sponge or sheet material for base material with thickness, concrete steps comprise Chemical Pretreatment, to the coated substrate carbonaceous conductive layer after Chemical Pretreatment, then carry out gas phase physics plated metal nickel or metallic copper, to the base material electronickelling of gas phase physics nickel deposited or copper, after washing and drying, obtain conductive sponge; Or to the first electro-coppering of the base material of gas phase physics nickel deposited or copper, re-plating nickel, obtains conductive sponge after washing and drying.There is following problem in the method: 1, with carbon coating conductive layer and the mode with gas phase physical deposition, can only produce lower than the thick polyester of 5mm or polyethers sponge, higher thickness cannot be produced, because sponge itself presents three-dimensional structure loose structure, be coated with carbon paste and gas-phase deposition cannot effectively by metal dust or colloid uniform filling in pore structure, therefore only the two sides of sponge can be caused to conduct electricity, and the non-conductive phenomenon of mid portion; Problem 2: carbon coating conductive layer can have a strong impact on the monolithic conductive of conductive sponge, because the conductance of carbon itself is less, mix rear with latex and be coated on sponge, again through physical vapour deposition (PVD), rubber layer itself can not be dissolved, and is wrapped up by metal powder layer, one is the sheet resistance having a strong impact on conductive sponge, two is that carbon dust is easy to come off when the conductive sponge made this technique carries out cutting processing, affects downstream and produces.
Application number is the patent of invention of 201310054649.7, disclose a kind of conductive sponge preparation method (hereinafter referred to as immersion sponge preparation method), in the preparation process of conductive sponge, take different compression stirring means to carry out respectively compressing, stirring in conducting solution and glue solution, make the conductive sponge of preparation better adsorb conductive particle, glue and better adhere to conductive particle and sponge, ensure that the sheet resistance of conductive sponge is less, volume resistance is more evenly distributed, make process after sponge firmness change less.The method also also exists following problem: 1, this invention does not clearly propose to adopt what conducting solution, how to make the situation that sponge is conducted electricity; 2, adopt conducting solution preimpregnation, and repeatedly soak with latex solution, compress, this technique can cause the adhesion of coating very poor, and slightly by under the effect of external force, coating is understood sponge matrix and come off.
[summary of the invention] the present invention is directed to the problems referred to above, provides a kind of ultra-thin and possess electromagnetic shielding conductive foam and the preparation method of good electric conductivity.
A kind of electromagnetic shielding conductive foam, comprises film matrix, it is characterized in that, the thickness of described film matrix is 0.1-5.0mm, mass density is 10-100g/ ㎡; Film matrix has several holes by porous mold punching, and its mesoporous lateral separation that to be the fore-and-aft distance between 0.1-2.0mm, Kong Yukong be between 0.5-2.0mm, Kong Yukong is 0.5-2.0mm, and percent opening is 10-90%; Film matrix surface and hole wall are coated with Nanometer Copper bisque, and the thickness of Nanometer Copper bisque is 0.1-500 μm; The surface electrical of Nanometer Copper bisque is coated with double-level-metal conductive layer, and described double-level-metal conductive layer is copper conductive layer and nickel overcoat, and the thickness of copper conductive layer and nickel overcoat is 1-100 μm; The thickness of the double-level-metal conductive layer of film matrix positive and negative becomes gradient sex differernce to distribute, and wherein the double-level-metal conductive layer thickness in front is 3-200 μm, and the double-level-metal conductive layer thickness of reverse side is 2-100 μm.
Described film matrix adopts the one in polyurethane, polyethers or PE.
The coating method of described Nanometer Copper bisque is cold spraying mode, or copper nanoparticle furnishing slurry is coated to matrix surface again.
Described copper nanoparticle is spherical copper powder, and average grain diameter is 10-1000nm.
The preparation method of this electromagnetic shielding conductive foam, it is characterized in that, first use porous mold in several holes of film matrix upper punch, then coated with nano copper powder layer on film matrix surface and hole wall, electro-coppering and the electronickelling of common process is carried out again on the matrix surface after coating and hole wall, subsequently by clean for the material washed with de-ionized water after plating and be placed in drying oven high temperature nitrogen and dry up, bake out temperature is 80-300 DEG C, obtains this product.
Compared with prior art, advantage applies of the present invention in: 1, adopts film to be that matrix carries out punching, thinner or thicker conductive foam can not only be processed, and aperture on conductive foam is very even.2, conductive sponge has high strength, high antifatigue.3, the mode of cold spraying or coated copper conductive paste is adopted to carry out applying spherical copper powder layer, can effectively by copper powder uniform filling in pore structure, make the sheet resistance of conductive sponge less, volume resistance is more evenly distributed, conduct electricity very well, and the difficult problem of conductive foam at die cutting process dry linting can be solved preferably.4, metal coating has gradient distribution, the common material of relatively single thickness coatings, can effectively to successively decrease loss to electromagnetic wave, electromagnetic wave absorption in more wide frequency ranges.5, the inventive method changes the traditional handicrafts such as existing painting conducting resinl, chemical plating, PVD, and operation is simpler, has unrivaled technical advance for the conductive foam product obtaining high conductivity.
[accompanying drawing explanation]
Fig. 1 is the structure cutaway view of electromagnetic shielding conductive foam of the present invention
Fig. 2 is the vertical, horizontal pitch-row display schematic diagram of A portion matrix endoporus in Fig. 1
Wherein, 1, film matrix, 2, hole, 3, Nanometer Copper bisque, 4, copper conductive layer, 5, nickel overcoat.
[embodiment] is described below enforcement of the present invention below in conjunction with accompanying drawing:
Embodiment one:
Product structure: see Fig. 1, Fig. 2 is 0.1mm at thickness, and mass density is 90g/m
2pE film matrix 1 on by porous mold punching have some holes 2, aperture is 0.1mm, and the fore-and-aft distance between hole 2 and hole 2 is 0.5mm, and the lateral separation between hole 2 and hole 2 is 0.5mm, and percent opening is 10%.The wall in film matrix 1 surface, hole 2 is coated with the ball shaped nano copper powder layer 3 that average grain diameter is 10nm, and the thickness of Nanometer Copper bisque 3 is 0.1 μm, and the coating method of Nanometer Copper bisque 3 is cold spraying.The surface electrical of Nanometer Copper bisque 3 is coated with double-level-metal conductive layer, and the copper conductive layer 4 being positioned at the inside in double-level-metal conductive layer is 2um at the thickness in film matrix 1 front, is 1 μm at the thickness of film matrix 1 reverse side.The nickel overcoat 5 being positioned at outside is 1 μm at the thickness in film matrix 1 front, it is 1 μm at the thickness of film matrix 1 reverse side, namely the conductive layer thickness of film matrix positive and negative becomes gradient sex differernce to distribute, and front side conductive layer thickness is 3um, and reverse side conductive layer thickness is 2um.
Product preparation method: first use porous mold in several holes of PE film matrix upper punch, then the mode of cold spraying is adopted directly to be coated to by copper nanoparticle particle on film matrix surface and hole wall, electro-coppering and the electronickelling of common process is carried out again on the matrix surface after coating and hole wall, subsequently by clean for the material washed with de-ionized water after plating and be placed in drying oven high temperature nitrogen and dry up, bake out temperature is 80 DEG C, obtains this product.
The product prepared by said method and existing conductive sponge are cut into the print of same volume, and the contrast carrying out the performances such as thickness, electric conductivity, dry linting rate respectively detects, and testing result as shown in Table 1.
Detected by contrast, the thickness integral thinned of porous composite material of the present invention, average conductivity can improve 82%, average dry linting rate reduces by 99%.
Table one:
|
Sponge thickness |
Resistivity |
Dry linting rate |
Carbon coating sponge preparation method |
≤5mm |
1.5 |
73% |
Soak sponge preparation method |
≥0.8mm |
1.0 |
30% |
The present embodiment |
0.106mm |
0.22 |
0.6% |
Embodiment two:
Product structure: see Fig. 1, Fig. 2 is 0.5mm at thickness, and mass density is 70g/m
2polyurethane film matrix 1 on by porous mold punching have some holes 2, aperture is 0.5mm, and the fore-and-aft distance between hole 2 and hole 2 is 0.8mm, and the lateral separation between hole 2 and hole 2 is 1.0mm, and percent opening is 35%.The wall in film matrix 1 surface, hole 2 is coated with the ball shaped nano copper powder layer 3 that average grain diameter is 100nm, and the thickness of Nanometer Copper bisque 3 is 10 μm, and the coating method of Nanometer Copper bisque 3 copper nanoparticle furnishing slurry is coated to again matrix 1 surface.The surface electrical of Nanometer Copper bisque 3 is coated with double-level-metal conductive layer, and the copper conductive layer 4 being positioned at the inside in double-level-metal conductive layer is 20um at the thickness in film matrix 1 front, is 10 μm at the thickness of film matrix 1 reverse side.The nickel overcoat 5 being positioned at outside is 20 μm at the thickness in film matrix 1 front, it is 10 μm at the thickness of film matrix 1 reverse side, namely the conductive layer thickness of film matrix positive and negative becomes gradient sex differernce to distribute, and front side conductive layer thickness is 40um, and reverse side conductive layer thickness is 20um.
Product preparation method: first use porous mold in several holes of polyurethane film matrix upper punch, then copper nanoparticle particle furnishing slurry is coated to again on film matrix surface and hole wall, electro-coppering and the electronickelling of common process is carried out again on the matrix surface after coating and hole wall, subsequently by clean for the material washed with de-ionized water after plating and be placed in drying oven high temperature nitrogen and dry up, bake out temperature is 120 DEG C, obtains this product.
The product prepared by said method and existing conductive sponge are cut into the print of same volume, and the contrast carrying out the performances such as thickness, electric conductivity, dry linting rate respectively detects, and testing result as shown in Table 2.
Detected by contrast, the thickness integral thinned of porous composite material of the present invention, average conductivity can improve 85%, average dry linting rate reduces about 98%.
Table two:
|
Sponge thickness |
Resistivity |
Dry linting rate |
Carbon coating sponge preparation method |
≤5mm |
1.5 |
73% |
Soak sponge preparation method |
≥1.0mm |
1.0 |
30% |
The present embodiment |
0.56mm |
0.18 |
0.8% |
Embodiment three:
Product structure: see Fig. 1, Fig. 2 is 0.7mm at thickness, and mass density is 10g/m
2polyurethane film matrix 1 on by porous mold punching have some holes 2, aperture is 1.0mm, and the fore-and-aft distance between hole 2 and hole 2 is 1.0mm, and the lateral separation between hole 2 and hole 2 is 1.2mm, and percent opening is 70%.The wall in film matrix 1 surface, hole 2 is coated with the ball shaped nano copper powder layer 3 that average grain diameter is 500nm, and the thickness of Nanometer Copper bisque 3 is 100 μm, and the coating method of Nanometer Copper bisque 3 copper nanoparticle furnishing slurry is coated to again matrix 1 surface.The surface electrical of Nanometer Copper bisque 3 is coated with double-level-metal conductive layer, and the copper conductive layer 4 being positioned at the inside in double-level-metal conductive layer is 50um at the thickness in film matrix 1 front, is 25 μm at the thickness of film matrix 1 reverse side.The nickel overcoat 5 being positioned at outside is 50 μm at the thickness in film matrix 1 front, it is 30 μm at the thickness of film matrix 1 reverse side, namely the conductive layer thickness of film matrix positive and negative becomes gradient sex differernce to distribute, and front side conductive layer thickness is 100um, and reverse side conductive layer thickness is 80um.
Product preparation method: first use porous mold in several holes of polyether film matrix upper punch, then copper nanoparticle particle furnishing slurry is coated to again on film matrix surface and hole wall, electro-coppering and the electronickelling of common process is carried out again on the matrix surface after coating and hole wall, subsequently by clean for the material washed with de-ionized water after plating and be placed in drying oven high temperature nitrogen and dry up, bake out temperature is 200 DEG C, obtains this product.
The product prepared by said method and existing conductive sponge are cut into the print of same volume, and the contrast carrying out the performances such as thickness, electric conductivity, dry linting rate respectively detects, and testing result as shown in Table 3.
Detected by contrast, the thickness of porous composite material of the present invention is slightly thin, average conductivity can improve about 90%, average dry linting rate reduces about 98%.
Table three:
|
Sponge thickness |
Resistivity |
Dry linting rate |
Carbon coating sponge preparation method |
≤5mm |
1.5 |
73% |
Soak sponge preparation method |
≥1.0mm |
1.0 |
30% |
The present embodiment |
0.85mm |
0.12 |
1.0% |
Embodiment four:
Product structure: see Fig. 1, Fig. 2 is 5.0mm at thickness, and mass density is 35g/m
2polyurethane film matrix 1 on by porous mold punching have some holes 2, aperture is 2.0mm, and the fore-and-aft distance between hole 2 and hole 2 is 2.0mm, and the lateral separation between hole 2 and hole 2 is 2.0mm, and percent opening is 90%.The wall in film matrix 1 surface, hole 2 is coated with the ball shaped nano copper powder layer 3 that average grain diameter is 1000nm, and the thickness of Nanometer Copper bisque 3 is 500 μm, the coating method cold spraying of Nanometer Copper bisque 3.The surface electrical of Nanometer Copper bisque 3 is coated with double-level-metal conductive layer, and the copper conductive layer 4 being positioned at the inside in double-level-metal conductive layer is 100um at the thickness in film matrix 1 front, is 50 μm at the thickness of film matrix 1 reverse side.The nickel overcoat 5 being positioned at outside is 100 μm at the thickness in film matrix 1 front, it is 50 μm at the thickness of film matrix 1 reverse side, namely the conductive layer thickness of film matrix positive and negative becomes gradient sex differernce to distribute, and front side conductive layer thickness is 200um, and reverse side conductive layer thickness is 100um.
Product preparation method: first use porous mold in several holes of PE film matrix upper punch, then the mode of cold spraying is adopted by copper nanoparticle particle coating on film matrix surface and hole wall, electro-coppering and the electronickelling of common process is carried out again on the matrix surface after coating and hole wall, subsequently by clean for the material washed with de-ionized water after plating and be placed in drying oven high temperature nitrogen and dry up, bake out temperature is 300 DEG C, obtains this product.
The product prepared by said method and existing conductive sponge are cut into the print of same volume, and the contrast carrying out the performances such as thickness, electric conductivity, dry linting rate respectively detects, and testing result as shown in Table 4.
Detected by contrast, porous composite material average conductivity of the present invention can improve 86%, average dry linting rate reduces about 97%.
Table four:
|
Sponge thickness |
Resistivity |
Dry linting rate |
Carbon coating sponge preparation method |
≤5mm |
1.5 |
73% |
Soak sponge preparation method |
≥1.0mm |
1.0 |
30% |
The present embodiment |
5.28mm |
0.17 |
1.5% |
In double-level-metal conductive layer of the present invention, the metal adopted is not limited to copper nickel dam, also can be monometallic or the alloy arbitrarily such as copper, nickel, silver.