• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:

    公开号:BE1020350A3
    申请号:E2011/0325
    申请日:2011-05-26
    公开日:2013-08-06
    发明作者:Rik Dewitte；Wim Verbrugghe
    申请人:Bekaert Sa Nv；
    IPC主号:
    专利说明:

    Use of a foaming agent to improve electromagnetic shielding
    Description
    Technical Area
    The invention relates to an object made of plastic via injection molding. The object is suitable for a housing with better protection against electromagnetic interference (EMI) and / or with better electrostatic discharge properties (ESD). The invention also relates to an assembly with two or more such articles made of plastic. The invention further relates to a method for making such objects from plastic.
    PRIOR ART U.S.-A-4,664,971 describes a plastic article containing electrically conductive fibers. The article has shielding properties against electromagnetic interference and against radio frequency. To obtain such an object, plastic granules containing electrically conductive fibers are used as an intermediate product. These granules are mixed with a predetermined amount of pure plastic material and this mixture is introduced into the hopper of, for example, an extruder. The material is then heated to soften the plastic and processed to distribute the fibers in the plastic to obtain an object in plastic with good shielding properties. US-A-4,664,971 points out that foaming agents can be used to make such articles from thermoplastic or thermosetting foam material.
    US-A-5,399,295 describes a composite plate consisting of a continuous matrix of a synthetic material with conductive fibers with random distribution therein and a particulate, conductive or semi-conductive filler. Injection molding is a possible production technique and foaming agents can be used in the production of such a composite plate.
    Plastic articles obtained according to US-A-4,664,971 have acceptable shielding properties in their central parts. However, the peripheral zones (which are close to the surface of the object made of plastic) are rich in pure plastic material and poor in fiber material. Moreover, fibers have a strong tendency to assume a direction parallel to the surface, therefore there is no good electrical contact with the outside. In general, there are also almost no fibers that protrude through the surface. A housing is generally assembled from two or more parts that fit neatly together. Due to the absence of fibers on the surface of the article in plastic, the overlap or contact zone of the two parts has a poor concentration of fibers. The electromagnetic radiation seeks the weakest point. Since the degree of shielding of an entire housing is determined by the parts that are weakest, the overlap zone determines the shielding and protection of the entire housing. And since this overlap zone is poor in security and protection, the entire housing is poor in protection and security. The aforementioned problem of border areas rich in plastic has been noted previously, e.g. in EP 0,674,326 which describes an electrical conductor containing an insulation of plastic. An integral body is made from a mixture of plastic material and metal fibers. The fibers have a small cross-sectional dimension with respect to the length. The body is produced via extrusion or injection molding, such that during the production process the metal fibers concentrate substantially in the central parts of the body in view of the flow direction in the production process.
    WO-A-2006/128741 solves the problem by providing an extra piece outside the final surface, this extra piece is then broken down. Although this provides an adequate technical solution to the problem, this technique has a major disadvantage from the point of view of costs. Other techniques avoid the use of electrically conductive fibers and provide the surface of the plastic objects with an electrically conductive coating. These techniques can also be very efficient but require the extra step of applying a coating.
    Description of the invention
    It is an object of the invention to avoid the disadvantages of products according to the prior art. It is another object of the invention to provide a cost-effective solution for better protection and shielding against electromagnetic interference and for better electrostatic dissipation.
    According to a first aspect of the present invention, an object is provided from plastic. This object is suitable as a housing and offers better protection against electromagnetic interference and / or better electrostatic dissipation properties. The object is made by means of low pressure injection molding. The plastic object contains at least 0.25 volume percent electrically conductive additives. The plastic object has a cellular structure. The cellular structure is obtained by using a foaming agent in the low pressure injection molding process, wherein at least 0.25 weight percent foaming agent is used. The weight percentage of the blowing agent is calculated on the weight of the mixing of raw materials used in the low pressure injection molding process.
    The production process used is low pressure injection molding. This means that during injection of the molten material, the mold is not completely filled with molten material: for example, the injected volume of raw material is more than 5% lower than the volume of the mold, preferably more than 10% lower than the volume of the mold; more preferably, more than 12% lower than the volume of the mold. With this low pressure injection molding, the emphasis, this is the pressure against the screw that is used after the injection of the molten material, is low (lower than 70 bar). Preferably there is no emphasis to use. In a specific embodiment, the valve is closed after the injection phase, which means that the mold and feed are physically separated from each other, so that no pressure can be applied to the injected polymer in the mold.
    The preferred minimum volume percentages of electrically conductive additives in the object are 0.5, 0.6, 0.75, 1.0, 1.5, 2.0, 2.5 and 3.0; e.g. when using stainless steel fibers as electrically conductive additives. For additives with a smaller specific length (length over diameter ratio) and a low specific density, the volume percentages can be much higher and can go up to 50-60 volume%. Preferably, the conductive object is produced from plastic by using between 0.25 and 10 weight percent foaming agents, more preferably between 1 and 3 weight percent. The weight percentage of foaming agent is calculated based on the weight of the mixing of raw materials used in the low pressure injection molding process.
    The cellular structure is the result of the use of a foaming agent that is mixed together with the plastic granulates and the additives. During the homogenization process, the foaming agent is kept sufficiently under pressure so that the gas cannot escape. Thereafter, when the mixture of the plastic material with the additives is injected into the mold, the conductive additives will - thanks to the low pressure injection molding process - be driven more towards the surface of the molded object through the gas released from the foaming agent. , then in prior art products (eg compared to high pressure injection molding).
    When using low pressure injection molding, the result is a higher proportion of conductive additives in the border zones and a more random arrangement of the conductive additives in comparison with prior art articles. Typically the invention also results in conductive additives protruding through the surface of the object made of plastic, this is very important for a good result (shielding, protection) (preferably at least 30 electrically conductive additives per square centimeter protrude through the surface ). The combination of a sufficiently high concentration in the boundary zones, a more random distribution of the additives in the boundary zones and a sufficiently high amount of additives that protrude through the surface will result in a relatively low surface resistance or in a high surface conduction. This will ultimately result in a surface conduction that is almost as good as the bulk conductivity of the article.
    The use of the foaming agent results in a foam morphology of the plastic-closed cellular structure, i.e., a closed-cell structure. The number and dimensions of the cells are determined by the injection rate and the manner of injection (i.e. the type of pouring, the diameter of the nozzle, the shape of the pouring / nozzle ...). Sometimes it is not desirable for additives to protrude through the surface of the object. In this case, these protruding additives can be removed by planing or polishing the surface. The additives are then present on the surface but no longer protrude through the surface. The distribution of pores can be seen over the entire object from plastic or over a part of the object.
    The electrically conductive additives can be: metal fibers, stainless steel fibers, titanium fibers, carbon fibers covered with a nickel layer, carbon fibers, carbon black, carbon nano tubes, glass beads coated with a silver layer, coated glass fibers ...
    In a preferred embodiment, the plastic object is in the form of a two-dimensional or three-dimensional plate with a thickness between 1.0 mm to 10 mm, e.g. from 3.0 mm or 4.0 mm to 10.0 mm. However, thicker objects are also possible. The thickness can be up to 50.0 mm and even more. The term "thickness" refers to the minimum cross-sectional dimension of the 2-D or 3D plate. Foaming can be done by means of a physical foaming agent, often nitrogen or with a chemical foaming agent. Chemical foaming agents are agents that decompose and release a gas under injection molding conditions. Examples of chemical foaming agents are ADC (azodiacarbonamide), OBSH (oxybis benzene sulfonyl hydrazide), TSH (p-toluene sulfonyl hydrazide), BSH, 5PT, DNPT (dinitroso pentamethylene tetramine), SBCCA ... e.g. CO 2, H 2 O, NH 3 or N 2. Two types of chemical foaming agents can be used: exothermic and endothermic foaming agents. Exothermic foaming agents are normally based on azodiacarbonamide (ADC) and other hydrazine derivatives, contained in different matrices. Exothermic foaming agents have a high yield of gas, a homogeneous gas distribution. Exothermic foaming agents are not very abrasive for the molds. Exothermic foaming agents have almost no tendency to "blooming". Exothermic foaming agents are not approved for food applications. In general, the cycle times are longer with exothermic foaming agents than with endothermic. The endothermic foaming agents are based on bicarbonates and citric acid compositions. The endothermic foaming agents have a rather limited gas yield and sometimes have a tendency to "bloom" and produce a fine microcellular structure. The mold will often have to be covered with a chromium layer to prevent corrosion by citric acid. The endothermic foaming agents are approved for food applications. Typically, the endothermic foaming agents have shorter cycle times since they absorb energy for the decomposition of the gases.
    According to a second aspect of the invention, an assembly is developed suitable for a housing that offers better protection against electromagnetic interference and / or better electrostatic dissipation properties. The assembly consists of two plastic articles according to the first aspect of the invention. The objects are placed close to each other with a flexible electrically conductive seal in intimate contact with both plastic objects. Examples of such a seal can be e.g. nickel or copper coated woven polyester, silver or Monel coated woven nylon, electrically conductive rubber components. The following references may be mentioned as examples: Schlegel EMI E81 5 3; Schlegel EMI E77 5 3; Schlegel EMI E08 5 3; Laird 4096 AB 51K; Laird 4357 ab 51K. Other seals such as metal mesh, conductive rubbers or conductive foams or flexible metal ... are also possible.
    In a test with a sheet thickness of 5.0 mm and with 2.5 volume percent stainless steel fibers, almost the same shielding effect was achieved for an assembly with connection (39.5 dB) as for the plate itself (without connection) (41.8 dB) where the protection by the central zone in the plastic object.
    According to a third aspect of the present invention, a method is being developed to make a plastic object according to the first aspect of the invention. The method consists of the following steps: (a) providing a plastic material; (b) providing a foaming agent; (c) provide electrically conductive additives; (d) bringing the plastic material, foaming agents and electrically conductive additives together under temperature and pressure and producing the object from plastic through low pressure.
    In this process, the foaming agent drives the electrically conductive additives over the entire volume of the article from plastic and creates a cellular structure in the article from plastic. Additives will even protrude through the external surface of the object from plastic, caused by the driving force (this compared to high pressure injection molding where almost no additives protrude through the surface).
    More than 0.25 weight% foaming agent is preferably used. Preferably between 0.25 and 10 weight% foaming agent. Most preferred, between 1 and 3 weight% foaming agent is used. The weight percentage of foaming agent is calculated on the weight of the raw material mix used in the low pressure injection molding process.
    It should be noted that the invention requires low pressure injection molding. In high pressure injection molding, a foaming agent can be mixed together with the plastic granulate or the polymer in the hopper of the machine. During the melting and compacting of the material in the screw of the injection molding machine, the product is kept under pressure so that the foaming agent cannot escape. Once the melting and compacting has been carried out, the material is injected into the mold. With high pressure injection molding, an emphasis is used to avoid shrink marks in the final product even after the material has been injected into the mold. This focus prevents the gas from pushing the electrically conductive additives to the surface of the object from plastic. The additives in the boundary zones are oriented parallel to the surface of the object. Thus, high pressure injection molding with foaming agents does not result in the advantages of the invention. Sometimes high pressure injection molding foaming agents are used as an aid or to achieve shorter cycle times.
    Brief description of the figures
    Figure 1 shows a composite granulate with electrically conductive fibers Figure 2 shows a low-pressure injection molding machine Figure 3 shows an assembly of two plates
    Figure 4 shows the fiber orientation in the cross-section of a plastic conductive object according to the state of the art Figure 5 shows the fiber orientation in the cross-section of a plastic conductive object according to the invention
    Description of embodiments
    Stainless steel fibers are a suitable choice as electrically conductive additives to calculate the required electromagnetic shielding. Fiber from stainless steel can be obtained by the technique of bundling. This technique is described e.g. in US-A-2 050 298, US-A-3 277 564 and in US-A-3 394 213. The starting material is wire rod with a suitable stainless steel composition.
    An example of such a composition is iron and the following components expressed in weight percent: C <0.05%, Mn <5%, Si <2%, 8 <Ni <12%, 15% <Cr <20%, Mo <3% , Cu <4%, N <0.05%, S <0.03% and P <0.05%. Another example of a suitable stainless steel type is: C <0.03%, 16% <Cr <18.5%, 10% <Ni <14, 2% <Mo <3%, Mn <2%, Si <1%, P < 0.045%, S <0.03%, with iron as a balance. Yet another example is: C <0.15%, 17% <Cr <19%, Mn <2.0%, 8.0% <Ni <10.0%, P <0.045%, Si <1.0%, S <0.03%.
    After a drawing process, the wire is covered with a coating such as iron or copper. A bundle of these covered wires is assembled in a metal tube. Thereafter, the tube thus formed is reduced in diameter via further wire drawing steps to obtain a composite bundle with a smaller diameter. The further wire drawing steps are alternated with or without a suitable heat treatment to allow further drawing. Within the composite bundle, the original threads are transformed into thin fibers that are individually embedded in an envelope. Such a bundle preferably consists of no more than 2000 fibers, e.g. between 500 and 1500 fibers. The suitable diameters of the fibers for electromagnetic interference applications are between 4 µm and 16 µm, e.g. between 8 pm and 12 pm. Once the desired final diameter has been obtained, the envelope can e.g. be removed by dissolving in an appropriate solvent. The end result is the bare fiber bundle. The bundle of stainless steel fibers can be provided with a glue and is then coated with a layer of plastic that is compatible with the raw material that will be used in injection molding, e.g. the plastic material is of the same polymer type but with a slightly lower melting temperature to facilitate mixing of the fibers together with the plastic material. The coated bundle of fibers is then cut into granules (composite granules) with a length between 4 mm and 10 mm, e.g. from 4 mm to 6 mm. Figure 1 shows such a composite granulate grain 10 with stainless steel fibers 12 and with a plastic coating 14.
    Figure 2 illustrates the process of low pressure injection molding for making an object from plastic with electrically conductive additives, such as stainless steel fibers. Injection molding apparatus 20 has an inlet opening 21 to the hopper 22 for feeding plastic powder or plastic granules together with composite granules 10 and foaming agent. Hopper 22 stores the plastic material until needed in the production process. Hopper 22 is connected to a tube 24 in which a screw 25 is installed. A heating element 26 heats tube 24. As soon as a predetermined temperature is reached, a motor 27 turns the screw 25. The raw materials are pushed by the screw 25 through the tube 24 along heating section 26 where the plastic is brought to the front of the screw in a viscous state. The viscous mass is then injected by screw 25 into a mold 28 where the material cools in the definite desired shape. In this example, the mold is filled to only 90 volume% and the back pressure is 0 bar in the low pressure injection molding process.
    In order to prevent the fibers from breaking too much and to ensure that fibers are longer than 3.5 mm (or higher than 2 mm), the shear load on fibers must be kept to a minimum. This can be achieved, among other things, by adjusting the viscosity of the polymers and by providing low shear stresses when homogenizing the raw materials and during the injection of the melt into the mold.
    Figure 3 shows a cross-section of an assembly 30 consisting of two plates 31, 32 with a seal 33 between them. The cross-section of each of plates 31, 32 can be divided into a central zone 34 and into two peripheral zones 35, 36. The foaming agent has a cellular structure 37 created over the volume of plates 31, 32. The foaming agent has also driven the stainless steel fibers 38 close to the surface of the plates 31.32. Fiber even protrudes through the surface, achieving substantially improved shielding. Moreover, the fibers will also be more randomly distributed in orientation in the edge zones under the influence of the foaming agent. Seal 33 between the two plates further improves shielding properties and avoids leaks due to a lack of contact points or dimensional problems that could result in interruptions of contact between the two plates.
    Tests were performed in which the following parameters were varied: - sealing whether or not present between the two plates; - plate thicknesses between 5.0 mm and 10.0 mm; - quantity of stainless steel fibers ranging between 1.5 and 2.5 volume percent; - amount of foaming agent varying between 1.0 and 2.5 weight percent.
    The effectiveness of the electromagnetic shield was directly proportional to the amount of conductive fibers. The amount of foaming agent (1-2.5 weight%) had little influence on the electromagnetic shield. Seals are recommended to achieve a good electrical overlap. The higher the fiber percentage and the higher the amount of foaming agent, the better the electrical contact and the shielding at the overlap.
    In addition to the improvement of electromagnetic interference protection, the electrostatic dissipation properties are also improved. The surface resistance is reduced even at lower concentrations of fibers because the fibers are present on and even through the surface. With 1.0 volume percent fibers, it was possible to achieve a surface resistance of less than 104 ohms.
    Figure 4 shows the cross-sectional fiber orientation of a plastic conductive article 40 according to the prior art. The plastic article has a central zone 42 and two edge zones 44 (depending on the thickness of the plate or part part, the edge zones have a thickness between 1 and 20% of the thickness of the plate or part, for example between 3% and 15% of the thickness. For example, for a sheet thickness of 5.0 mm, the edge zones may have a thickness of up to 0.75 mm, while for a sheet thickness of 2.5 mm, the thickness of the edge zones may be between 200 µm and 300 µm.) .
    In the example in Figure 4, stainless steel fibers 46 are used as conductive additives. The stainless steel fibers 46 have an arbitrary orientation in the central zone 42. A lower volume percentage of stainless steel fibers is present in the edge zones 44 than in the central zone 42. The stainless steel fibers in the edge zones 44 are substantially parallel aligned with the surface 48 of the object. from plastic. There are virtually no stainless steel fibers that protrude through the surface 48 of the article of plastic.
    Figure 5 shows the cross-sectional fiber orientation of a plastic conductive article 50 according to the invention. The plastic article has a central zone 52 and two edge zones 52. In the example in Figure 5, stainless steel fibers 56 are used as conductive additives. The stainless steel fibers 56 have an arbitrary orientation in the central zone 52. A lower volume percentage of stainless steel fibers is present in border zones 54 than in the central zone 52, but the volume percentage of stainless steel fibers in the border zones 54 is higher than in a comparable plastic object according to the state of the art (see figure 4). In a plastic conductive object 50 according to the invention (Fig. 5), the stainless steel fibers in the boundary zones 54 have a more random orientation as compared to stainless steel conductive plastic fibers of the prior art. In a plastic conductive article 50 according to the invention, there is an important amount of stainless steel fibers protruding through the plastic surface 58 of the article.
    Table 1 shows test results of the number of stainless steel fibers protruding per square centimeter through the surface of a plastic article according to the invention. Both samples were produced by means of low pressure injection molding, whereby the matrix was filled for 90% and a 0 bar pressure was used. The electrically conductive additives used are stainless steel fibers (alloy 302A) with a diameter of 8 microns and a length of 5 mm (as fed into the hopper of the low pressure injection molding machine). The endothermal foaming agent Tracel TACIL IN7200 (from Tramaco) was used. The number of electrically conductive additives (in this case the number of stainless steel fibers) protruding through the surface can be counted while the sample is viewed under a microscope.
    Table 1: Number of stainless steel fibers protruding per square centimeter through the surface of a plastic object according to the invention
    List of reference marks 10 composite granules 12 stainless steel fibers 14 plastic coating 20 injection molding device 21 inlet opening 22 feed hopper 24 tube 25 screw 26 heating element 27 motor 28 mold 30 assembly with two plates 31 first plate 32 second plate 33 seal 34 central zone of the first plate 35, 36 edge zones of the first plate 37 pores, cellular structure 38 fibers 40 plastic conductive object according to the prior art 42 central zone of a plastic conductive object according to the prior art 44 peripheral zone of a plastic conductive object according to the state of the art 46 fibers from stainless steel 48 surface of a conductive object made of plastic according to the state of the art 50 conductive object made of plastic according to the invention 52 central zone of a conductive object made of plastic according to the invention 54 edge zone of a conductive plastic article according to the invention 56 fibers from r stainless steel 58 surface of a plastic conductive object according to the invention
    权利要求:
    Claims (13)
    [1]
    1. A conductive object made of plastic suitable for a housing with improved shielding against electromagnetic interference or with better electrostatic discharge properties, the object is produced by means of low pressure injection molding; the article contains at least 0.25 volume percent electrically conductive additives; the article has a cellular structure, this cellular structure is obtained by using a foaming agent, wherein at least 0.25 weight percent foaming agent is used.
    [2]
    A plastic conductive article according to claim 1, produced with between 0.25 and 10 weight percent foaming agent.
    [3]
    A plastic conductive article according to claim 2, produced with between 1 and 3 weight percent foaming agent.
    [4]
    A plastic conductive object according to any of the preceding claims, wherein the foaming agent is a chemical foaming agent.
    [5]
    A plastic conductive article according to any of the preceding claims, wherein the electrically conductive additives are selected from metal fibers, stainless steel fibers, titanium fibers, carbon fibers or nickel-coated carbon fibers.
    [6]
    A plastic conductive object according to any of the preceding claims, wherein the thickness of the plastic object is greater than 3 mm.
    [7]
    A plastic conductive object according to any of the preceding claims, wherein a significant amount of the electrically conductive additives protrude through the surface of the conductive object.
    [8]
    A plastic conductive object according to any of the preceding claims, wherein at least 30 electrically conductive additives per square centimeter protrude through the surface of the conductive object.
    [9]
    9. An assembly suitable for a housing with improved shielding against electromagnetic interference, this assembly consists of two plastic conductive objects according to any of the preceding claims, these plastic conductive objects are placed against each other, with and in intimate contact between them with a flexible electrically conductive seal.
    [10]
    A method of producing an article from plastic according to any of the preceding claims, wherein the method comprises the steps of (a) providing a plastic material; (b) providing a foaming agent; (c) provide electrically conductive additives; (d) bringing the plastic material, foaming agent and electrically conductive additives together under temperature and pressure and producing the object from plastic through low pressure.
    [11]
    A method as in claim 10 for producing an article from plastic, wherein more than 0.25 weight percent foaming agent is used.
    [12]
    A method as in claim 11 for producing an article from plastic, wherein between 0.25 and 10 weight percent foaming agent is used.
    [13]
    A method as in claim 12 for producing an article from plastic, wherein between 1 and 3 weight percent foaming agent is used.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    EP10165831|2010-06-14|
    EP10165831|2010-06-14|
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