CN100405886C - Polyethylene composite film for shielding wideband electromagnetic wave and its preparing method - Google Patents
Polyethylene composite film for shielding wideband electromagnetic wave and its preparing method Download PDFInfo
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- CN100405886C CN100405886C CNB2007100994661A CN200710099466A CN100405886C CN 100405886 C CN100405886 C CN 100405886C CN B2007100994661 A CNB2007100994661 A CN B2007100994661A CN 200710099466 A CN200710099466 A CN 200710099466A CN 100405886 C CN100405886 C CN 100405886C
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Abstract
The composite membrane of polythene (CMP) includes basal body membrane (BBM) and surface coating for BBM. BBM is polyvinyl resin membrane of containing additive for shielding electromagnetic wave. The weight of additive is 10-100 weight portions if the said polyvinyl resin is in 100 weight portions. The additive includes two kinds: (1) one is admixture of metal fibers and metal conduction powder; the metal fibers are admixtures of polycrystal iron fiber and stainless steel fiber; the metal conduction powders include nickel powder, copper powder, iron powder, or aluminum powder; (2) the other is admixture of metal fibers and carbon fibers; the metal fibers are polycrystal iron fiber or stainless steel fiber; carbon fibers are nicarbazin fiber or nickel plated graphite fiber. Surface coating of BBM is metallic coating with average thickness being as 1-20 micros. CMP provides effect for shielding electromagnetic wave reaching about 45dB in range 50MHz-20GHz.
Description
Technical field
The present invention relates to a kind of polyvinyl resin film, say further, relate to polyethylene film that can be wide band electromagnetic wave-shielded and preparation method thereof.
Background technology:
In the society of electronics, electric, communication and information industry high speed development, Electromagnetic Interference, electromagnetic wave information are divulged a secret and electromagnetic wave environmental pollution etc. has become serious social concern day by day.Electromagnetic wave is a kind of transmittance process of electromagnetic energy, is a kind of shear wave, and its mode of propagation and light are similar.According to schelkunoff electromagnetic shielding theory, the shielding attenuation of electromagnetic wave energy has reflection loss, absorption loss and three kinds of forms of internal reflection loss, under normal conditions, mainly is subjected to the influence of reflection loss and absorption loss.The electromagnetic protection material is exactly utilization reaches shielding electromagnetic wave to electromagnetic reflection and absorption a effect.The wave impedance of conductive material and the wave impedance of air dielectric differ bigger, mainly come shielding electromagnetic wave by reflection loss, and magnetic material are mainly by loss shields to absorption of electromagnetic wave.Two kinds of compound uses of screen method can remedy the shielding defective mutually, significantly improve the capability of electromagnetic shielding of packaging material.
The electromagnetic wave shielding material kind is more, mainly contains filled-type composite material and surface-coated (coating and plating) material two big classes.The filled-type composite material has that barrier propterty is stable, cost is low, processing technology is easy, be fit to advantages such as production in enormous quantities, but it is subjected to preparation technology's influence, when addition is excessive, compatibility between matrix and additive is poor, influence the mechanical property of material, this phenomenon is the most general in thin-film material; The shield effectiveness of surface-coated material is good, applied range, but the easy oxidation of its top layer coating material, come off, thereby cause the shield effectiveness instability.Therefore need a kind of filled-type composite membrane of research and development with overlay coating, overlay coating can reflect the electromagnetic wave of higher-frequency, and can add the magnetic additive in the film of filled-type, it can be absorbed fail the low-frequency electromagnetic wave that reflected away by coating, thereby widen the electromagnetic shielding scope of film.
Vinyon is present the most frequently used packaging material, it is one of the world's five big general-purpose plastics, has light weight, nontoxic, machine-shaping is convenient, and is cheap, advantages such as resistance to chemical attack, especially its pliability and curtain coating are good, suitable blown film is widely used in electrical equipment, chemical industry, military affairs, fields such as packaging for foodstuff.But the polyethylene electrical insulating property is good, and itself does not possess the function of shielding electromagnetic wave, can't directly prevent the electromagnetism packing, need carry out certain electromagnetism modification to it.
Aspect filled-type electromagnetic shielding polyethylene composite material, the main both at home and abroad at present additive that uses has metallic fiber and metal powder, the electro-conductive glass microballon etc. of nanometer carbon black, CNT (carbon nano-tube), conductivity.Change into industrial group as FDAC and fill material that the AAS matrix the makes screening effectiveness when the 100-1000MHz more than 30dB with brass fiber; The carbon fiber of Beijing University of Chemical Technology macromolecular material blending and modifying research department development/PVC paste composite material is 35dB to the electromagnetic shielding effect of 1000MHz.
Stainless steel fibre is the material that is usually used in anti-electromagnetism field, but its quality softness, the compatibility of fiber and organic resin is very poor, is difficult for adding in the resin matrix, and therefore, general addition is all little, and is maximum about 8%.The screening effectiveness of the LDPE/ stainless steel fibre electromagnetic shielding material of Beijing Institute of Technology's blast science and technology laboratory development is 22dB, the maximum addition of stainless steel fibre is about 10%, when maximum addition, the mechanics tensile property of material is 9MPa, and elongation at break is 50%.The adding that is stainless steel fibre is very big to the mechanical property influence.Thereby mechanical property, electromagnetism and electric conductivity to flexible packing material all have decisive influence.
Coating material commonly used is a good conductivity, is difficult for the metal material of oxidation, mainly contains aluminium powder, nickel powder, copper powder etc.Advantages such as wherein aluminium powder has good conductivity, is difficult for oxidation, and coating temperature is low are materials commonly used in the plated film.The Wang Ronghua of Aerospace Material ﹠ Technology Inst. etc. has compared the shield effectiveness of different coating, and wherein the vacuum aluminium coated layer of 1.3 μ m reaches 30dB at the screening effectiveness of 30-1000MHz.
Summary of the invention:
The present invention is directed to the shortcoming that polyethylene can't shielding electromagnetic wave, adopt the electromagnetic wave shielding additive of magnetic to add in the polyvinyl resin, make base film, make it absorb the electromagnetic wave of low-frequency range; And, make it can reflect the electromagnetic wave of higher frequency band at base film surface plating layer of metal layer.Thereby by the method that adopts plated film and filled-type screened film to combine,, make its wideband section electromagnetic wave that can shield the height frequency range at filled-type polyethylene screened film outside plating layer of metal layer, from and have that packing intercepts, anti-static function.
The purpose of this invention is to provide a kind of polyethylene composite film for shielding wideband electromagnetic wave, it can be mainly used in the electromagnetic protection inner packaging material field of military products and electronic product.Another object of the present invention provides the preparation method of described polyethylene composite film for shielding wideband electromagnetic wave.
Polyethylene composite film for shielding wideband electromagnetic wave of the present invention comprises base film and base film overlay coating, and wherein base film is the polyethylene resin film that contains the electromagnetic wave shielding additive.In described polyvinyl resin 100 parts by weight, it is 10～100 parts by weight that electromagnetic wave shielding contains agent, is preferably 30～70 parts by weight.Described electromagnetic wave shielding additive is mainly two kinds, and a kind of is the mixture of metal species conductive fiber and metal conductive powder, and another kind is the mixture of metal species conductive fiber and carbon element fibrid.Wherein the base film overlay coating is the coat of metal, is preferably aluminium coat or nickel coating.The coating average thickness is 1～20 μ m.Thickness of coating is preferably 5～20 μ m, more preferably 10～20 μ m.
Polyethylene composite film of the present invention, wherein said polyvinyl resin are that the prior art kind can be used for the polyvinyl resin that blowfilm shaping prepares membrane product usually.
Polyethylene composite film of the present invention, when wherein the contained electromagnetic wave shielding additive of base film was metal species conductive fiber and metal conductive powder, the metal species conductive fiber was the mixture of polycrystalline iron fiber and stainless steel fibre.Metal species conductive fiber diameter range is 1～30 μ m, is preferably 1～20 μ m, 5～20 μ m more preferably, and fiber length ranges is 0.5～50mm, is preferably 1～30mm, more preferably 1～20mm.Described metal conductive powder is one of following material: nickel powder, copper powder, iron powder, aluminium powder are preferably nickel powder.The average grain diameter of metal conductive powder is 1～3 μ m.Wherein the weight ratio of metal conductive powder, polycrystalline iron fiber and stainless steel fibre is 1: 1: 1～1: 1: 4.
Above-mentioned will be as the metal species fiber of bat wool with compound as the electromagnetic shielding additive as the metal conductive powder of ball filler, the conductance of its conductance when using spherical or bat wool separately.Because the shape of filler has considerable influence to conductance, generally speaking, various fillers and time spent are favourable to improving conductance, two kinds of fillers and time spent, exist between particle by point-to-point, by putting line, by line to point, to four kinds of ways of contact of line, interparticle contact area is big by line, and contact probability is big, it is intensive relatively, complete to form conductive network, electric conductivity is also higher, widens the electromagnetic wave shielding scope simultaneously, can work in coordination with the electromagnetic shielding effectiveness that improves polyethylene film.
Polyethylene composite film of the present invention, when wherein the contained electromagnetic wave shielding additive of base film was the mixture of metal species conductive fiber and carbon element fibrid, described metal species conductive fiber was any or its mixture in above-mentioned polycrystalline iron fiber and the above-mentioned stainless steel fibre.
The above carbon element fibrid is one of following material: nickel-coated carbon fibers, nickel plating graphite fibre.The diameter range of carbon element fibrid is 1～30 μ m, is preferably 1～20 μ m, 5～20 μ m more preferably, and fiber length ranges is 0.5～50mm, is preferably 1～30mm, more preferably 1～20mm.
The weight ratio of metal species conductive fiber and carbon element fibrid is 1: 4～4: 1 in the described electromagnetic wave shielding additive, is preferably 1: 2～2: 1.
The compatibility of above-mentioned carbon element fibrid and matrix resin is better than the metal species conductive fiber, and it can be combined closely with matrix resin, and evenly disperses in matrix resin, therefore can reduce the electromagnetic shielding content of additive relatively; Add the carbon element fibrid in addition and can also improve the mechanical property of matrix, when being subjected to external force, particle is in a lot of little deformed area of the inner generation of matrix, absorb big energy, can transmit the stress that is born preferably, can cause the matrix surrender again, consume a large amount of impact energys, play enhancing and toughness reinforcing effect; The carbon element fibrid can also improve the antistatic behaviour of composition in addition, plays synergy with the metal species conductive fiber aspect electromagnetic shielding.
Polyethylene composite film of the present invention can also include in the wherein said base film in polyvinyl resin 100 parts by weight, the antioxidant of 0.5～1 parts by weight.Described antioxidant is phenolic antioxidant and/or monothioester kind antioxidant, and when antioxidant was the mixture of phenolic antioxidant and monothioester kind antioxidant, the weight ratio of phenolic antioxidant and monothioester kind antioxidant was 0.8: 1.2～1.2: 0.8.Wherein said phenolic antioxidant is preferably four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, and the monothioester kind antioxidant is preferably dilauryl thiodipropionate.
For described metal species fiber and metal conductive powder are disperseed in polyvinyl resin better, polyethylene composite film of the present invention in polyvinyl resin 100 parts by weight, also can include the atoleine of 0.5～1 parts by weight in its base film.
Polyethylene composite film of the present invention can also include additive commonly used in the polyethylene film in the wherein said base film, as plasticizer, bulking agent, coupling agent etc., use amount is common consumption.
The preparation method of polyethylene composite film for shielding wideband electromagnetic wave of the present invention is as described below:
Comprise described each component is fully mixed by described amount, make the pellet of filled-type polyethylene matrix film through the melt-mixing method of common polyvinyl resin, this pellet is joined blown film in the inflation film manufacturing machine, to plate one deck aluminium lamination on the film that make again, thereby obtain described polyethylene composite film for shielding wideband electromagnetic wave.
Specifically can be: above-mentioned each component is passed through high-speed mixer by described consumption, it is mixed, wherein blender blend rotating speed is 800～1000 commentaries on classics/min.Through double-screw melt blending, blending temperature is the typical temperature of the common melt blending technology of polyethylene with described mixture, preferably can be 150～170 ℃.Cooling afterwards, pelletizing, make electromagnetic wave shielding material grain.Pellet is blown film on inflation film manufacturing machine, and the blown film temperature adopts the typical temperature of polyethylene blown film, preferably can be 158～166 ℃.On the film that makes, plate layer of metal film then, preferred aluminium film of metal film or nickel film.The coating average thickness is 1～20 μ m, is preferably 5～20 μ m, more preferably 10～20 μ m.Aluminize or the vacuum degree 20-8Pa of Ni-Speed middle bell jar bombarding current 100mA.The aluminium powder that aluminium coated is selected for use is a powdery, content 〉=99.5%, commercially available aluminium powder average particle diameter≤200 orders (≤100 μ m), relative conductivity 0.61, relative permeability 1.The nickel powder that nickel coating is selected for use is a powdery, and commercially available nickel powder average particle diameter is 1.50～3 μ m.
When containing stainless steel fibre in the electromagnetic wave shielding agent of polyethylene composite film of the present invention, stainless steel fibre is more easily reunited in preparation process, influence addition, and easily disperse inhomogeneous in material content, for the dispersiveness of improving stainless steel fibre to obtain the better mixing effect, after stainless steel fibre can being carried out preliminary treatment, again each component is fully mixed, promptly preferably includes the preparation method of following steps:
1. handle with after an amount of fusion in the described polyvinyl resin long stainless steel fibre being carried out surface solidification, be about to evenly apply on the long stainless fiber beam surface polyethylene of skim fusion; Herein be meant in right amount long stainless steel fibre to be wrapped after the used polyethylene fusion gets final product, be generally 1/2～1 times of stainless steel fibre weight to be processed.
2. after treating that polyethylene on the stainless steel fibre solidifies, long stainless steel fibre is cut into the short fiber of described length;
3. same each component that remains polyvinyl resin that comprises of above-mentioned stainless steel fibre is after treatment fully mixed by described amount;
4. above-mentioned compound is made the pellet of described polyethylene matrix film through melt blending;
5. again this pellet is obtained described polyethylene matrix film through blowfilm shaping;
6. afterwards metal powder is plated on the above-mentioned polyethylene matrix film and forms the coat of metal, the coating average thickness is 1～20 μ m, is preferably 5～20 μ m, more preferably 10～20 μ m.The vacuum degree 20-8Pa of vacuum plating process middle bell jar, bombarding current 100mA.Preferred aluminium coated of the described coat of metal or nickel coating.Thereby obtain described polyethylene composite film for shielding wideband electromagnetic wave.
The base film of polyethylene composite film of the present invention is the polyethylene film that contains the electromagnetic shielding additive, wherein the electromagnetic shielding additive is compound, because the synergy of the compound interpolation of multiple screener can improve the screening effectiveness of material, widen the electromagnetic wave shielding scope.Base film mainly reflects and absorbs the electromagnetic wave of low-frequency range thus.Coating on the polyethylene composite film of the present invention is the coat of metal, can well be used to reflect frequency electromagnetic waves.Thus, the electromagnetic wave shielding performance of polyethylene composite film for shielding wideband electromagnetic wave of the present invention in the 50MHz-20GHz scope is all better, and its electromagnetic shielding effect can be up to about 45dB.
Embodiment:
Below in conjunction with embodiment, further specify the present invention.
Raw material:
Polyethylene: low density polyethylene (LDPE) (LDPE), the Beijing Yanshan Petrochemical Company chemical plant provides, trade mark AC-100, density 0.9225g/cm
3, melt flow rate (MFR) 2.0g/10min, granular.
Antioxidant: the weight ratio of four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol esters and dilauryl thiodipropionate is 1: 1 a mixture, and Beijing Olympic Competition is insulted scientific ﹠ trading Co., Ltd. and sold.
The stainless steel long fibre: fibre diameter is about 6.5 μ m, relative conductivity 0.1, and relative permeability 〉=1000, Hunan Correspondent new material Co., Ltd provides.
Polycrystalline iron fiber: the river precious nano material of oil nuclear Co., Ltd provides, and black short fiber, diameter range are 6.5～9 μ m, and length range is 0.5～2mm, relative conductivity 0.17, relative permeability 〉=1000.
Nickel powder: the Wuxi provides along reaching metal dust Co., Ltd, dark-grey black bead chain shape powder, and particle size range is 1.5～3 μ m, resistance 1～3 Ω/cm, relative permeability 1.
Aluminium powder: Beijing chemical reagents corporation provides, content 〉=99.5%, particle diameter≤200 orders, relative conductivity 0.61, relative permeability 1.
Nickel-coated carbon fibers: fibre diameter is about 20 μ m, and length is about 3mm.Shanghai Ka Ji specialization industry science skill company provides;
Electromagnetic performance and Mechanics Performance Testing:
According to " method of measurement of SJ20524-95 material screening effectiveness " standard testing electromagnet shield effect; By " GB1401-89 solid insulating material specific insulation and surface resistivity test method " standard testing surface resistivity; According to " GB 13022-91 stretched plastic film method for testing performance " test tensile property.
One, the electromagnetic shielding additive is the mixture of stainless steel fibre, polycrystalline iron fiber and conduction nickel powder
The weight ratio of nickel powder, polycrystalline iron fiber and stainless steel fibre of conducting electricity among embodiment 1-1～embodiment 1-4 is 1: 1: 1; The weight ratio of nickel powder, polycrystalline iron fiber and stainless steel fibre of conducting electricity among embodiment 1-5～1-8 is 1: 1: 2.The weight ratio of nickel powder, polycrystalline iron fiber and stainless steel fibre of conducting electricity among the embodiment 1-9 is 1: 1: 4.
The experiment concrete steps are as follows:
The polyethylene that takes out weight and be used long stainless steel fibre weight 1/2 from polyethylene is heated to molten condition, and it is coated on the surface of stainless steel fibre.After treating that polyethylene on the stainless steel fibre solidifies, be cut into the short fiber of length range at 1～10mm.With above-mentioned stainless steel fibre and polycrystalline iron fiber and the conduction nickel powder handled, and remaining polyethylene, in polyvinyl resin 100 parts by weight, the described antioxidant of 1 weight portion (four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] weight ratio of pentaerythritol ester and dilauryl thiodipropionate is 1: 1 mixture), join in the high-speed mixer.The pellet that mixes is joined in the main spout of twin-screw, charging rate is 400r/min, and wherein the temperature in extruder one district to seven district is 165 ℃, 170 ℃, 170 ℃, 170 ℃, 170 ℃, 170 ℃, 165 ℃ (head), and pressure is 1.0～1.2Mpa, melt extrude granulation.Make pellet blowing in inflation film manufacturing machine, the blown film temperature in 1-6 district is 158 ℃, 158 ℃, and 160 ℃, 162 ℃, 164 ℃, 166 ℃.On the film that blows out, aluminize, in the process of aluminizing, the vacuum degree 20-8Pa of bell jar, about bombarding current 100mA, aluminum layer thickness 15 μ m.The polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 1.Raw materials used consumption is 100 parts by weight in polyethylene all.
Two,
The electromagnetic shielding additive is the mixture of nickel-coated carbon fibers and polycrystalline iron fiber, perhaps is nickel-coated carbon fibers With the mixture of stainless steel fibre, perhaps be the mixing of nickel-coated carbon fibers, polycrystalline iron fiber and stainless steel fibre Thing
(1), the electromagnetic shielding additive is the mixture of nickel-coated carbon fibers and polycrystalline iron fiber among embodiment 2-1～embodiment 2-13.The experiment concrete steps are as follows:
Nickel-coated carbon fibers and polycrystalline iron fiber are added in the polyethylene, and add in polyvinyl resin 100 parts by weight, the described antioxidant of 1 weight portion is added in the high-speed mixer together.The pellet that mixes is joined in the main spout of twin-screw, charging rate is 400r/min, and wherein the temperature in extruder one district to seven district is 165 ℃, 170 ℃, 170 ℃, 170 ℃, 170 ℃, 170 ℃, 165 ℃ (head), and pressure is 1.0～1.2Mpa, melt extrude granulation.Make pellet blowing in inflation film manufacturing machine, the blown film temperature in 1-6 district is 158 ℃, 158 ℃, and 160 ℃, 162 ℃, 164 ℃, 166 ℃.On the film that blows out, aluminize, in the process of aluminizing, the vacuum degree 20-8Pa of bell jar, about bombarding current 100mA, aluminum layer thickness 15 μ m.The polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 2.Raw materials used consumption is 100 parts by weight in polyethylene all.
(2), the electromagnetic shielding additive is the mixture of nickel-coated carbon fibers and stainless steel fibre among embodiment 3-1～embodiment 3-13.The experiment concrete steps are as follows:
The polyethylene that takes out weight and be used long stainless steel fibre weight 1/2 from polyethylene is heated to molten condition, and it is coated on the surface of stainless steel fibre.After treating that polyethylene on the stainless steel fibre solidifies, be cut into the short fiber of length range at 1～10mm.With the stainless steel fibre of above-mentioned processing and nickel-coated carbon fibers and remaining polyethylene, in polyvinyl resin 100 parts by weight, the described antioxidant of 1 weight portion is added in the high-speed mixer together.The pellet that mixes is joined in the main spout of twin-screw, charging rate is 400r/min, and wherein the temperature in extruder one district to seven district is 165 ℃, 170 ℃, 170 ℃, 170 ℃, 170 ℃, 170 ℃, 165 ℃ (head), and pressure is 1.0～1.2Mpa, melt extrude granulation.Make pellet blowing in inflation film manufacturing machine, the blown film temperature in 1-6 district is 158 ℃, 158 ℃, and 160 ℃, 162 ℃, 164 ℃, 166 ℃.On the film that blows out, aluminize, in the process of aluminizing, the vacuum degree 20-8Pa of bell jar, about bombarding current 100mA, aluminum layer thickness 15 μ m.The polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 3.Raw materials used consumption is 100 parts by weight in polyethylene all.
(3), the electromagnetic shielding additive is the mixture of nickel-coated carbon fibers and stainless steel fibre and polycrystalline iron fiber among the embodiment 4-1, three's weight ratio is 1: 1: 1.Electromagnetic shielding additive gross weight is counted 100 parts with polyvinyl resin 100 parts by weight.Test other conditions and step all with embodiment 3-1.Gained polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 4.Raw materials used consumption is 100 parts by weight in polyethylene all.
Three, comparative example
(1), the electromagnetic shielding additive is a stainless steel fibre among comparative example 1-1～comparative example 1-10, perhaps be stainless steel fibre with and the mixture of polycrystalline iron fiber, perhaps be stainless steel fibre and conduct electricity the mixture of nickel powder.
The experiment concrete steps are as follows:
The polyethylene that takes out weight and be used long stainless steel fibre weight 1/2 from polyethylene is heated to molten condition, and it is coated on the surface of stainless steel fibre.After treating that polyethylene on the stainless steel fibre solidifies, be cut into the short fiber of length range at 1～10mm.With stainless steel fibre, perhaps stainless steel fibre with and the mixture of polycrystalline iron fiber, perhaps stainless steel fibre and the mixture of conduction nickel powder and the polyethylene of remainder reach in polyvinyl resin 100 parts by weight, and the described antioxidant of 1 weight portion together adds in the high-speed mixer.All the other conditions are with embodiment 1-1.The polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 5.Raw materials used consumption is 100 parts by weight in polyethylene all.
(2), the electromagnetic shielding additive is a polycrystalline iron fiber among comparative example 2-1～comparative example 2-6, perhaps be polycrystalline iron fiber and the mixture of conduction nickel powder.The experiment concrete steps are as follows:
With polycrystalline iron fiber, the perhaps mixture of polycrystalline iron fiber and conduction nickel powder, and polyethylene, and in polyvinyl resin 100 parts by weight, the described antioxidant of 1 weight portion together adds in the high-speed mixer.All the other conditions are with embodiment 1-1.The polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 6.Raw materials used consumption is 100 parts by weight with polyethylene all.
(3), the electromagnetic shielding additive is a nickel-coated carbon fibers among comparative example 3-1～comparative example 3-4.The experiment concrete steps are as follows:
With nickel-coated carbon fibers and polyethylene, and in polyvinyl resin 100 parts by weight, the described antioxidant of 1 weight portion together adds in the high-speed mixer.All the other conditions are with embodiment 1-1.The polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 6.Raw materials used consumption is 100 parts by weight with polyethylene all.
(4), the electromagnetic shielding additive is the conduction nickel powder among comparative example 4-1～comparative example 4-4.The experiment concrete steps are as follows:
To conduct electricity nickel powder and polyethylene, and in polyvinyl resin 100 parts by weight, the described antioxidant of 1 weight portion adds in the high-speed mixer together.All the other conditions are with embodiment 1-1.The polyethylene aluminized complex film is made batten by each standard, carry out every performance test, its key component prescription and the results are shown in Table 7.Raw materials used consumption is 100 parts by weight with polyethylene all.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Claims (9)
1. polyethylene composite film for shielding wideband electromagnetic wave, it comprises base film and base film overlay coating, and wherein the base film overlay coating is the coat of metal, and the coating average thickness is 1～20 μ m; Described base film is the polyethylene resin film that contains the electromagnetic wave shielding additive; In polyvinyl resin 100 parts by weight, containing the electromagnetic wave shielding additive is 10～100 parts by weight;
Described electromagnetic wave shielding additive is the mixture of metal species conductive fiber and metal conductive powder, and wherein the metal species conductive fiber is the mixture of polycrystalline iron fiber and stainless steel fibre; Wherein metal conductive powder is one of following material: nickel powder, copper powder, iron powder, aluminium powder, particle size range are 1～3 μ m; The weight ratio of described metal conductive powder, polycrystalline iron fiber and stainless steel fibre is 1: 1: 1～1: 1: 4;
Perhaps described electromagnetic wave shielding additive is the mixture of metal species conductive fiber and carbon element fibrid, and wherein the metal species conductive fiber is any or its mixture in polycrystalline iron fiber and the stainless steel fibre; Wherein the carbon element fibrid is one of following material: nickel-coated carbon fibers, nickel plating graphite fibre; The weight ratio of described metal species conductive fiber and carbon element fibrid is 1: 4～4: 1;
The fiber diameter range of the above metal species conductive fiber and carbon element fibrid is 1～30 μ m, and fiber length ranges is 0.5～50mm.
2. polyethylene composite film according to claim 1, wherein said electromagnetic wave shielding additive are the mixture of metal species conductive fiber and carbon element fibrid, and the weight ratio of metal species conductive fiber and carbon element class conductive fiber is 1: 2～2: 1.
3. polyethylene composite film according to claim 1, the fiber diameter range of wherein said metal species conductive fiber and carbon element fibrid are 1～20 μ m, and fiber length ranges is 1～30mm.
4. polyethylene composite film according to claim 1, in polyvinyl resin 100 parts by weight, containing described electromagnetic wave shielding additive is 30～70 parts by weight in the wherein said base film.
5. polyethylene composite film according to claim 1, in the wherein said base film in polyvinyl resin 100 parts by weight, the antioxidant that contains 0.5～1 parts by weight, described antioxidant is phenolic antioxidant and/or monothioester kind antioxidant, when antioxidant was the mixture of phenolic antioxidant and monothioester kind antioxidant, the weight ratio of phenolic antioxidant and monothioester kind antioxidant was 0.8: 1.2～1.2: 0.8.
6. polyethylene composite film according to claim 5, wherein said phenolic antioxidant are four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, and the monothioester kind antioxidant is a dilauryl thiodipropionate.
7. according to each described polyethylene composite film of claim 1～6, wherein said base film overlay coating is an aluminium coat, or nickel coating; The coating average thickness is 5～20 μ m.
8. according to the preparation method of each described polyethylene composite film for shielding wideband electromagnetic wave of claim 1～7, may further comprise the steps:
1. described each component of polyvinyl resin and electromagnetic wave shielding agent that comprises is fully mixed by described amount;
2. above-mentioned compound is made the pellet of described polyethylene matrix film through melt blending;
3. again this pellet is obtained described polyethylene matrix film through blowfilm shaping;
4. after metal powder is plated in the coat of metal of the described thickness of formation on the above-mentioned polyethylene matrix film, thereby obtains described polyethylene composite film for shielding wideband electromagnetic wave.
9. the preparation method of polyethylene composite film according to claim 8, when containing stainless steel fibre in the wherein said electromagnetic wave shielding agent, the preparation method may further comprise the steps:
1. use an amount of described polyvinyl resin, after the fusion long stainless steel fibre is carried out surface solidification and handle, be cut into the stainless steel fibre of described length afterwards;
2. same each component that remains polyvinyl resin that comprises of above-mentioned stainless steel fibre is after treatment fully mixed by described amount;
3. above-mentioned compound is made the pellet of described polyethylene matrix film through melt blending;
4. again this pellet is obtained described polyethylene matrix film through blowfilm shaping;
5. after metal powder is plated in the coat of metal of the described thickness of formation on the above-mentioned polyethylene matrix film, thereby obtains described polyethylene composite film for shielding wideband electromagnetic wave.
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| WO2024069580A1 (en) | 2022-09-29 | 2024-04-04 | Graphenest S.A. | Electromagnetic wave shielding thermoplastic composition |
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| JP2001261975A (en) * | 2000-03-16 | 2001-09-26 | Daicel Chem Ind Ltd | Electroconductive thermoplastic resin composition |
| US20020037376A1 (en) * | 2000-09-08 | 2002-03-28 | Fenton Ernest R. | Heat shrinkable article shielding against EMI and RFI |
| WO2004114365A2 (en) * | 2003-06-16 | 2004-12-29 | Integral Technologies, Inc. | Lost cost chip carrier manufactured from conductive loaded resin-based material |
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