Patent Application
20240006775
The present invention relates to an electromagnetic millimetre wave absorber material, preferably having a volume resistivity of more than 1 Ωcm, containing solid particles having an aspect ratio (length:diameter) of at least 5 of a first electrically conductive material, particles having an aspect ratio (length:diameter) of less than 5 of a second electrically conductive material and an electrically non-conductive polymer, wherein the absorber material is preferably capable of absorbing electromagnetic waves in a frequency region of 60 GHz to 200 GHz and wherein the electromagnetic millimetre wave absorber material comprises based on the total amount of the absorber material from 30 wt.-% to 93 wt.-% of the electrically non-conductive polymer, from 6.5 wt.-% to 10 wt.-% of the first electrically conductive material, from 0.5 wt.-% to 0.9 wt.-% of the second electrically conductive material, and from 0 wt.-% to 59.1 wt.-% of one and more additives. The invention also relates to its use and method for absorbing as well as a sensor apparatus comprising said absorber material.
Current engineering plastics cannot be used for the application of absorption of electromagnetic radiation in a frequency range of 60-90 GHz. Current materials are transparent for this type of radiation or reflect significant amounts. The aim of the absorbing material is to lower the electromagnetic interference on the sensor, by the absorption of unwanted electromagnetic radiation. A current solution is available as semi-finished goods from which the right size sample needs to be cut out. This is an undesirable process, since it creates much more waste and the geometry of the samples is limited to 2 dimensional semi-finished goods. A solution which can be injection molded is much more desirable.
JP 2017/118073 A2 describes an electromagnetic wave absorbing material capable of absorbing electromagnetic waves in a high frequency region of 20 GHz or more. The electromagnetic wave absorbing material contains an insulating material and a conductive material and has a volume resistivity of 102 Ω·cm or more and less than 9×105 Ω·cm. The electromagnetic wave absorbing material is provided as a film containing carbon nanotubes. However, nanotubes are difficult to handle due to toxicity reasons. In addition, carbon nanotubes are expensive. Carbon nanotubes are also described in WO 2012/153063 A1. Fibrous carbon nanostructures in an electromagnetic wave adsorption material is described in EP 3 397 039 A1.
Also U.S. Pat. No. 4,606,848 A describes a film-like composition in form of a paint in a lower GHz frequency range unsuitable for autonomous driving, wherein a radar attenuating paint composition for absorbing and scattering incident microwave radiation is described having a binder composition with a plurality of dipole segments made of electrically conductive fibers uniformly dispersed therein.
Also WO 2010/109174 A1 describes a film-like composition as dried coating derived from an electromagnetic radiation absorbing composition comprising a carbon filler comprising elongate carbon elements with an average longest dimension in the range of 20 to 1000 microns, with a thickness in the range of 1 to 15 microns and a total carbon filler content in the range of from 1 to 20 volume % dried, in a nonconductive binder.
Also WO 2017/110096 A1 describes an electromagnetic wave absorber with a plurality of electromagnetic wave absorption layers each including carbon nanostructures and an insulating material.
F. Quin et al., Journal of Applied Physics 111, 061301 (2012), give an overview of microwave absorption in polymer composites filled with carbonaceous particles.
US 2011/168440 A1 described an electromagnetic wave absorbent which contains a conductive fiber sheet which is obtained by coating a fiber sheet base with a conductive polymer and has a surface resistivity within a specific range. The conductive fiber sheet is formed by impregnating a fiber sheet base such as a nonwoven fabric with an aqueous oxidant solution that contains a dopant, and then bringing the resulting fiber sheet base into contact with a gaseous monomer for a conductive polymer, so that the monomer is oxidatively polymerized thereon.
JP 2004/296758 A1 described a plate-like millimeter wave absorber having an absorbing layer laminated on a reflective layer. The absorbent layer has a thickness of 1.0 mm to 5.0 mm and contains 1 to 30 parts by weight of carbon black with respect to 100 parts by weight of a resin of a resin or a rubber.
JP 2004/119450 A1 describes a radio wave absorbing layer made of a composite material containing carbon short fibers and nonconductive short fibers and a resin and a radio wave reflecting layer provided on the back surface of the radio wave absorbing layer and in a frequency range of 2 to 20 GHz.
JP H11-87117 A describes a high frequency electromagnetic wave absorber characterized by dispersing a soft magnetic flat powder having a thickness of 3 μm or less in an insulating base material.
A. Dorigato et al., Advanced Polymer Technology 2017, 1-11, describe synergistic effects of carbon black and carbon nanotubes on the electrical resistivity of poly(butylene-terephthalate) nanocomposites.
S. Motojima et al., Letters to the Editor, Carbon 41 (2003) 2653-2689, describe electromagnetic wave absorption properties of carbon microcoils/PMMA composite beads in W-bands (see also S. Motojima et al., Transactions of the Materials Research Society of Japan (2004), 29(2), 461-464).
Further absorbing materials are describes in WO 2010/109174 A1, CN 104 262 929 A, WO 2018/199008 A1, CN 107 622 980 A as well as by Q. J. Krueger et al., Advances in Polymer Technology 22 (2003), 96-111.
International patent applications WO 2020/244994 A1 and WO 2020/244995 A1 describe mixtures of fibrous and non-fibrous electrically conductive particles useful for absorber materials capable of absorbing electromagnetic waves in a frequency region of 60 GHz or more.
However, the use of fibrous electrically conductive particles results in anisotropy due to their anisotropic shape. Alignment of these fiber shaped particles occurs in the direction of flow during part processing. This alignment can be parallel or perpendicular to the electric field. This alignment changes the effective surface of the fibrous electrically conductive particles and thereby changing the dielectric properties in the two directions. This, in turn, results in a different absorbing effectiveness of the particles depending on the direction of the electric field relative to the melt flow direction. An anisotropy of the material as function of the flow direction of the melt is undesirable.
Thus, there is a need to provide absorber material that shows good absorption and reflection properties and that can be used as constructional element having also good mechanical properties (e.g. tensile strength) but also minimizes the above-mentioned anisotropy effect.
Accordingly, an object of the present invention is to provide such material and sensors.
This object is achieved by an electromagnetic millimetre wave absorber material, preferably having a volume resistivity of more than 1 Ωcm, containing solid particles having an aspect ratio (length:diameter) of at least 5 of a first electrically conductive material, particles having an aspect ratio (length:diameter) of less than 5 of a second electrically conductive material and an electrically non-conductive polymer, wherein the absorber material is preferably capable of absorbing electromagnetic waves in a frequency region of 60 GHz to 200 GHz, characterized in that the electromagnetic millimetre wave absorber material comprises based on the total amount of the absorber material
The object is also achieved by an electronic device containing a radar absorber in form of a radar absorber part or a radar absorbing housing, the radar absorber comprising
The object is also achieved by the use an absorber material of the present invention for the absorption of electromagnetic millimeter waves in a frequency region of 60 GHz to 200 GHz.
The object is also achieved by a method of absorbing electromagnetic millimeter waves in a frequency region of 60 GHz to 200 GHz, the method comprising the step of irradiating an absorber material of the present invention with electromagnetic millimeter waves in a frequency region of 60 GHz to 200 GHz.
Unexpectedly, the solution to this problem is the addition of electrically conductive fillers, preferably to an injection moldable matrix, where fibrous additives were combined with certain particulates. This leads to an increase of the absorption where this was not possible if a same amount of one type of fibers were added. This solution yields a low transmission, without a high reflection and with high absorption with different additives in various polymeric matrices in a frequency region of 60 GHz to 200 GHz. Dielectric parameters show strong frequency dependence, therefore not easy to expand to other frequency ranges. Different dielectric relaxation mechanisms are occurring depending on the frequency range. Advantageously, non-conductive fillers can be used to improve tensile strength and surprisingly even in fibrous or particulate form without affecting the absorption and reflection properties. In addition it was found that within a narrow range of amount of first and second electrically conductive particles and electrically non-conductive polymer the anisotropy effect can be reduced compared to compositions known from PCT/EP2020/0646697.
The absorber material of the present invention is preferably capable of absorbing electromagnetic waves in a frequency region of 60 GHz to 200 GHz, more preferably in the range of 70 GHz to 150 GHz, even more preferably from 71 GHz to 90 GHz, even more preferably in the range from 76 GHz to 81 GHz. Thus, the absorber material of the present invention represents an electromagnetic millimeter wave absorber.
The absorber material of the present invention contains the electrically non-conductive polymer, the first and the second electrically conductive material and optionally one or more additives. Accordingly, the absorber material can contain additional components and the total sum of wt. % of all components including the electrically non-conductive polymer, the first and the second electrically conductive material and the optionally one or more additives is 100 wt.-%.
However the absorber material can consist of the electrically non-conductive polymer, the first and the second electrically conductive material. In this case the wt.-% if these three components will sum up to 100 wt.-%. The absorber material can also consist of the electrically non-conductive polymer, the first and the second electrically conductive material and the one or more additives, which is preferred. In this case the wt.-% of the electrically non-conductive polymer, the first and the second electrically conductive material and the one or more additives will sum up to 100 wt.-%.
The absorber material of the present invention contains solid particles of a first electrically conductive material. The term “solid” means that the particles do not have any pipe-like channels, like carbon nanotubes. For avoidance of any doubt the term “solid” should not be interpreted to exclude porous material. The term solid is especially defined as to exclude carbon nanotubes.
The solid particles of the first conductive material have an aspect ratio (length:diameter) of at least 5. In case of a straight form of the particles the length correlates with the longitudinal distance. However, the particles can also show a curved or spiral form. For such geometries the contour length is used. Preferably, the solid particles have an aspect ratio (length:diameter) of at least 7, more preferably at least 10. Preferably at least the first electrically conductive material are solid fibre particles have an acicular or cylindrical shape or a turned chip like shape. The solid particles should having regular or irregular shape. It is possible that solid fibre particles having an acicular or cylindrical shape or a turned chip like shape with an aspect ratio of less than 5 can be present in the absorber material.
The absorber material of the present invention also contains particles of a second electrically conductive material. The first and second electrically conductive material can be the same or different materials. However, the particles of the second electrically conductive material and the particles of the first conductive material show different shape and thus can be differentiated.
The particles of the second electrically conductive material have an aspect ratio (length:diameter) of less than 5, preferably, less than 3. Preferably, the particles are non-fibrous particles having a spherical or lamellar shape.
The absorber material of the present invention also contains an electrically non-conductive polymer. This polymer can be a homopolymer, a copolymer or a mixture of two or more, like three four or five, homo- and/or copolymers. Preferably, the electrically non-conductive polymer is a thermoplast, thermoplastic elastomers, thermoset or a vitrimer, preferably a thermoplastic material and more preferably a polycondensate, more preferably a polyester and most preferably poly(butylene terephthalate).
Examples of the electrically non-conductive polymer are an epoxy resin, a polyphenylene sulfide, a polyoxymethylene, an aliphatic polyketone, a polyaryl ether ketone, a polyether ether ketone, a polyamide, a polycarbonate, a polyimide, a cyanate ester, a terephthalate, like poly(butylene terephthalate) or poly(ethylene terephthalate) or poly(trimethylene terephthalate), a poly(ethylene naphthalate), a bismaleimide-triazine resin, a vinyl ester resin, a polyester, a polyaniline, a phenolic resin, a polypyrrole, a polymethyl methacrylate, a phosphorus-modified epoxy resin, a polyethylenedioxythiophene, polytetrafluoroethylene, a melamine resin, a silicone resin, a polyetherimide, a polyphenylene oxide, a polyolefin such as polypropylene or polyethylene or copolymers thereof, a polysulfone, a polyether sulfone, a polyarylamide, a polyvinyl chloride, a polystyrene, an acrylonitrile-butadiene-styrene, an acrylonitrile-styrene-acrylate, a styrene-acrylonitrile, or a mixture of two or more of the above mentioned polymers.
Preferably, the particles of the first and second electrically conductive material are homogenously distributed in the absorber material. This can be achieved by merely mixing the components together where the polymer is in the molten form or with or without solvent, i.e. as homogenous dispersion or in dry form.
The absorber material can be shaped in order to represent a constructional element, like an element of a sensor apparatus. Thus, in a preferred embodiment the absorber material of the present invention is subject to injection molding, thermoforming, compression molding or 3D printing, preferably injection molding. Methods for shaping are well-known in the art and a practitioner in the art can easily adopt method parameters in order to obtain the absorber material of the present invention as shaped element.
Preferably, the electromagnetic millimetre wave absorber material comprises based on the total amount of the absorber material
More preferably, the electromagnetic millimetre wave absorber material comprises based on the total amount of the absorber material
Even more preferably, the electromagnetic millimetre wave absorber material comprises based on the total amount of the absorber material
Even more preferably, the electromagnetic millimetre wave absorber material comprises based on the total amount of the absorber material
Even more preferably, the electromagnetic millimetre wave absorber material comprises based on the total amount of the absorber material
Preferably, the first and second electrically conductive material is carbon or a metal. Accordingly, in a first aspect of the present invention the first and second electrically conductive material is carbon. In a second aspect of the present invention the first and second electrically conductive material is metal. In a third aspect of the present invention the first electrically conductive material is a metal and the second electrically conductive material is carbon. In a fourth aspect of the present invention, the first electrically conductive material is carbon and the second electrically conductive material is metal. The third aspect is most preferred.
Preferably, the metal is zinc, nickel, copper, tin, cobalt, manganese, iron, magnesium, lead, chromium, bismuth, silver, gold, aluminum, titanium, palladium, platinum, tantalum, or an alloy thereof, preferably iron or an alloy, especially an iron alloy. Even more preferably, the iron or iron alloy material is stainless-steel.
In a preferred embodiment of the present invention, the first and the second electrically conductive material is different, more preferably the first electrically conductive material is iron or steel and the second conductive material is carbon.
Preferably, the particles of the second electrically conductive material are carbon black.
Preferably, the particles of the first electrically conductive material have a length of from 0.01 to 100 mm, preferably from 10 μm to 10 mm, even more preferably from 10 μm to 1000 μm, even more preferably from 50 μm to 750 μm, even more preferably from 100 μm to 500 μm.
Preferably, the particles of the first electrically conductive material have a diameter of from 0.1 μm to 100 μm, preferably from 1 μm to 100 μm, even more preferably from 2 μm to 70 μm, even more preferably from 3 μm to 50 μm, even more preferably from 5 μm to 40 μm.
The absorber material of the present invention optionally contains one or more additives. Preferably, the one or more additives are selected from the group consisting of at least one electrically non-conductive filler, preferably at least one fibrous or particulate filler, more preferably at least one fibrous filler, especially glass fibers and/or other additives, like antioxidants, lubricants, nucleating agents, impact modifying polymers or other processing aids, preferably at least a lubricant. In case the one or more additives are contained, their amount is in general at least 0.01 wt.-%.
In a further embodiment of the present invention the absorber material additionally may contain at least one electrically non-conductive filler, preferably at least one fibrous or particulate filler, more preferably at least one fibrous filler, especially glass fibers.
In one embodiment of the present invention the absorber material of the present invention additionally contains a further filler component with one or more, like two three or four, further fillers. The fillers are different to the first and second electrically conductive material and the electrically non-conductive polymer. In a more specific embodiment of the present invention, the filler component contains at least one electrically non-conductive filler, preferably a fibrous or particulate filler.
Exemplary fillers are glass fibers, glass beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar. Preferably, the filler component contains or consists of glass fibres. Typically, the additional filler component can be present in the absorber material of the present invention in an amount of up to 59.1% by weight, in particular up to 50.2% by weight and typically at least 0.01% by weight, preferably at least 0.1% by weight, each based on the total amount of the absorber material.
Preferred fibrous electrically non-conductive fillers which may be mentioned are aramid fibers and Basalt fibers, wood fibers, quartz fibers, aluminum oxide fibers and particular preference is given to glass fibers in the form of E glass. These may be used as rovings or in the commercially available forms of chopped glass.
The fibrous fillers may have been surface-pretreated with a silane and further compounds, especially to improve compatibility with a thermoplastic.
Suitable silane compounds have the formula (X—(CH2)n)k—Si—(O—CmH2m+1)4−k, where:
Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes which contain a glycidyl group as substituent X.
The amounts of the silane compounds generally used for surface-coating are from 0.05 to 5% by weight, preferably from 0.1 to 1% by weight and in particular from 0.2 to 0.8% by weight based on total amount of the fibrous filler.
Acicular mineral fillers are also suitable.
For the purposes of the present invention, acicular mineral fillers are mineral fillers with strongly developed acicular character. An example is acicular wollastonite. The mineral preferably has an aspect ratio of from 8:1 to 35:1, preferably from 8:1 to 11:1. The mineral filler may, if desired, have been pretreated with the abovementioned silane compounds, but the pretreatment is not essential.
Other fillers which may be mentioned are kaolin, calcined kaolin, talc and chalk.
The absorber material of the present invention may comprise usual molding processing aids as further fillers of the filler component, such as stabilizers, oxidation retarders, agents to counteract decomposition due to heat and decomposition due to ultraviolet light, lubricants and mold-release agents, colorants, such as dyes and pigments, nucleating agents, plasticizers, etc.
Examples which may be mentioned of oxidation retarders and heat stabilizers are sterically hindered phenols and/or phosphites, hydroquinones, aromatic secondary amines, such as diphenylamines, various substituted members of these groups, and mixtures of these in concentrations of up to 1.5% by weight, based on the weight of the absorber material of the present invention.
Exemplary UV stabilizers which may be mentioned, and are generally used in amounts of up to 2% by weight, based on the absorber material, are various substituted resorcinol, salicylates, benzotriazoles, hindered amine light stabilizers and benzophenones.
Colorants which may be added are inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide, and carbon black, and also organic pigments, such as phthalocyanines, quinacridones and perylenes, and also dyes, such as nigrosine and anthraquinones.
Nucleating agents which may be used are sodium salts of weak acids and preferably talc.
Lubricants and mold-release agents which may be used in amounts of up to 1.5% by weight are known in the art. Preference is given to long-chain fatty acids (e.g. stearic acid or behenic acid), salts of these (e.g. calcium stearate or zinc stearate), esters of these with fatty acid alcohols or multi-functional alcohols (e.g. glycerine, pentaerytrithol, trimethylol propane), amides from difunctional amines (e.g. ethylene diamine), or montan waxes (mixtures of straight-chain saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms), or calcium montanate or sodium montanate, or oxidized low-molecular-weight polyethylene waxes.
Preferably, a lubricant is present in the electromagnetic millimetre wave absorber material, preferably in the amount from 0.01 wt. % to 1 wt.-%, preferably, from 0.1 wt.-% to 1 wt.-%, more preferably from 0.3 to 0.8 wt.-% based on the total amount of the absorber material.
Hydrolysis stabilizers which may be used are carbodiimides like bis(2,6-diisopropylphenyl)carbodiimide, polycarbodiimides (e.g. Lubio® Hydrostab 2) or epoxides such as, adipic acid bis(3,4-epoxycylcohexylmethyl)ester, triglycidylisocyanurate, trimethylol propane tryglycidylether, epoxidize plant oils or prepolymers of bisphenol A and epychlorohydrine (especially required when polyesters are the electrically non-conductive polymer).
Examples of plasticizers which may be mentioned are dioctyl phthalates, dibenzyl phthalates, butyl benzyl phthalates, hydrocarbon oils and N-(n-butyl)benzene-sulfonamide.
Suitable additives that may be comprised in the absorber material of the present invention are described in US 2003/195296 A1.
Additives may be sterically hindered phenols. Suitable sterically hindered phenols are in principle any of the compounds having a phenolic structure and having at least one bulky group on the phenolic ring.
Examples of compounds whose use is preferred are those of the formula
where: R1 and R2 are alkyl, substituted alkyl or a substituted triazole group, where R1 and R2 may be identical or different, and R3 is alkyl, substituted alkyl, alkoxy or substituted amino.
Antioxidants of the type mentioned are described, for example, in DE-A 27 02 661 (U.S. Pat. No. 4,360,617).
Another group of preferred sterically hindered phenols derives from substituted benzenecarboxylic acids, in particular from substituted benzenepropionic acids.
Particularly preferred compounds of this class have the formula
where R4, R5, R7 and R8, independently of one another, are C1-C8-alkyl which may in turn have substitution (at least one of these is a bulky group) and R6 is a bivalent aliphatic radical which has from 1 to 10 carbon atoms and may also have C—O bonds in its main chain. Preferred compounds are
The examples of sterically hindered phenols which should be mentioned are: 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazylamine, 2-(2′-hydroxy-3′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole-, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4′-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine and N,N′-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide.
Compounds which have proven especially effective and which are therefore preferably used are 2,2′-methylenebis(4-methyl-6-tert-butylphenyl), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl]propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
The amounts present of the antioxidants as additives-if present-, which may be used individually or as mixtures, are usually up to 2% by weight, preferably from 0.005 to 2% by weight, in particular from 0.1 to 1% by weight, based on the total weight of the absorber material.
Sterically hindered phenols which have proven particularly advantageous, in particular when assessing color stability on storage in diffuse light over prolonged periods, in some cases have no more than one sterically hindered group in the ortho position to the phenolic hydroxyl.
The polyamides which can be used as additives are known per se. Use may be made of partly crystalline or amorphous resins as described, for example, in the Encyclopedia of Polymer Science and Engineering, Vol. 11, John Wiley & Sons, Inc., 1988, pp. 315 489. The melting point of the polyamide here is preferably below 225° C., and particularly preferably below 215° C.
Examples of these are polyhexamethylene azelamide, polyhexamethylene sebacamide, polyhexamethylene dodecanediamide, poly-11-aminoundecanamide and bis(p-aminocyclohexyl)methyldodecanediamide, and the products obtained by ring-opening of lactams, for example polylaurolactam. Other suitable polyamides are based on terephthalic or isophthalic acid as acid component and trimethylhexamethylenediamine or bis(p-aminocyclohexyl)propane as diamine component and polyamide base resins prepared by copolymerizing two or more of the abovementioned polymers or components thereof.
Particularly suitable polyamides which may be mentioned are copolyamides based on caprolactam, hexamethylenediamine, p,p′-diaminodicyclohexylmethane and adipic acid. An example of these is the product marketed by BASF SE under the name Ultramid® 1 C.
Other suitable polyamides are marketed by Du Pont under the name Elvamide®.
The preparation of these polyamides is also described in the abovementioned text. The ratio of terminal amino groups to terminal acid groups can be controlled by varying the molar ratio of the starting compounds.
The proportion of the polyamide in the molding composition of the invention is up to 2% by weight, by preference from 0.005 to 1.99% by weight, preferably from 0.01 to 0.08% by weight.
The dispersibility of the polyamides used can be improved in some cases by concomitant use of a polycondensation product made from 2,2-di(4-hydroxyphenyl)propane (bisphenol A) and epichlorohydrin.
Condensation products of this type made from epichlorohydrin and bisphenol A are commercially available. Processes for their preparation are also known to the person skilled in the art.
The molecular weight of the polycondensates can vary within wide limits. In principle, any of the commercially available grades is suitable.
Other stabilizers which may be present as additives are one or more alkaline earth metal silicates and/or alkaline earth metal glycerophosphates in amounts of up to 2.0% by weight, preferably from 0.005 to 0.5% by weight and in particular from 0.01 to 0.3% by weight, based on the total weight of the absorber material. Alkaline earth metals which have proven preferable for forming the silicates and glycerophosphates are calcium and, in particular, magnesium. Useful compounds are calcium glycerophosphate and preferably magnesium glycerophosphate and/or calcium silicate and preferably magnesium silicate. Particularly preferable alkaline earth silicates here are those described by the formula Me·x SiO2·n H2O where: Me is an alkaline earth metal, preferably calcium or in particular magnesium, x is a number from 1.4 to 10, preferably from 1.4 to 6, and n is greater than or equal to 0, preferably from 0 to 8.
The compounds are advantageously used in finely ground form. Particularly suitable products have an average particle size of less than 100 μm, preferably less than 50 μm.
Preference is given to the use of calcium silicates and magnesium silicates and/or calcium glycerophosphates and magnesium glycerophosphates. Examples of these may be defined more precisely by the following characteristic values:
Calcium silicate and magnesium silicate, respectively: content of CaO and MgO, respectively: from 4 to 32% by weight, preferably from 8 to 30% by weight and in particular from 12 to 25% by weight, ratio of SiO2 to CaO and SiO2 to MgO, respectively (mol/mol): from 1.4 to 10, preferably from 1.4 to 6 and in particular from 1.5 to 4, bulk density: from 10 to 80 g/100 ml, preferably from 10 to 40 g/100 ml, and average particle size: less than 100 μm, preferably less than 50 μm.
Calcium glycerophosphates and magnesium glycerophosphates, respectively: content of CaO and MgO, respectively: above 70% by weight, preferably above 80% by weight, residue on ashing: from 45 to 65% by weight, melting point: above 300° C., and average particle size: less than 100 μm, preferably less than 50 μm.
Preferred lubricants as additives which may be present in the absorber material of the present invention are, in amounts of up to 5, preferably from 0.09 to 2 and in particular from 0.1 to 0.7% by weight, at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having from 10 to 40 carbon atoms, preferably from 16 to 22 carbon atoms, with polyols or with saturated aliphatic alcohols or amines having from 2 to 40 carbon atoms, preferably from 2 to 6 carbon atoms, or with an ether derived from alcohols and ethylene oxide.
The carboxylic acids may be mono- or dibasic. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and, particularly preferably, stearic acid, capric acid and also montanic acid (a mixture of fatty acids having from 30 to 40 carbon atoms).
The aliphatic alcohols may be mono- to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol and pentaerythritol, and preference is given to glycerol and pentaerythritol.
The aliphatic amines may be mono- to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine and di(6-aminohexyl)amine, and particular preference is given to ethylenediamine and hexamethylenediamine. Correspondingly, preferred esters and amides are glycerol distearate, glycerol tristearate, ethylenediammonium distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
It is also possible to use mixtures of different esters or amides or esters with amides combined, in any desired mixing ratio.
Other suitable compounds are polyether polyols and polyester polyols which have been esterified with mono- or polybasic carboxylic acids, preferably fatty acids, or have been etherified.
Suitable products are available commercially, for example Loxiol® EP 728 from Henkel KGaA.
Preferred ethers, derived from alcohols and ethylene oxide, have the formula RO (CH2 CH2 O)n H where R is alkyl having from 6 to 40 carbon atoms and n is an integer greater than or equal to 1.
R is particularly preferably a saturated C16 to C18 fatty alcohol with n of about 50, obtainable commercially from BASF as Lutensol® AT 50.
The absorber material of the present invention may comprise from 0 to 5%, preferably from 0.001 to 5% by weight, particularly preferably from 0.01 to 3% by weight and in particular from 0.05 to 1% by weight, of a melamine-formaldehyde condensate. This is preferably a crosslinked, water-insoluble precipitation condensate in finely divided form. The molar ratio of formaldehyde to melamine is preferably from 1.2:1 to 10:1, in particular from 1.2:1 to 2:1. The structure of condensates of this type and processes for their preparation are found in DE-A 25 40 207.
The absorber material of the present invention may comprise from 0.0001 to 1% by weight, preferably from 0.001 to 0.8% by weight, and in 10 particular from 0.01 to 0.3% by weight, of a nucleating agent as additive.
Possible nucleating agents are any known compounds, for example melamine cyanurate, boron compounds, such as boron nitride, silica, pigments, e.g. Heliogenblue (copper phthalocyanine pigment; registered trademark of BASF SE), or branched polyoxymethylenes, which in these small amounts have a nucleating action.
Talc in particular is used as a nucleating agent and is a hydrated magnesium silicate of the formula Mg3[(OH)2/Si4O10] or MgO·4SiO2·H2O. This is termed a three-layer phyllosilicate and has a triclinic, monoclinic or rhombic crystal structure and a lamella appearance. Other trace elements which may be present are Mn, Ti, Cr, Ni, Na and K, and some of the OH groups may have been replaced by fluoride.
Particular preference is given to the use of talc in which 100% of the particle sizes are <20 μm.
The particle size distribution is usually determined by sedimentation analysis and is preferably:
Products of this type are commercially available as Micro-Talc I.T. extra (Norwegian Talc Minerals).
Examples of fillers which may be mentioned are potassium titanate whiskers, carbon fibers and preferably glass fibers. The glass fibers may, for example, be used in the form of glass wovens, mats, nonwovens and/or glass filament rovings or chopped glass filaments made from low-alkali E glass and having a diameter of from 5 to 200 μm, preferably from 8 to 50 μm. After they have been incorporated, the fibrous fillers preferably have an average length of from 0.05 to 1 μm, in particular from 0.1 to 0.5 μm.
Examples of other suitable fillers are calcium carbonate and glass beads, preferably in ground form, or mixtures of these fillers.
Other additives which may be mentioned are impact-modifying polymers (also referred to below as elastomeric polymers or elastomers).
Preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.
EPM rubbers generally have practically no residual double bonds, whereas EPDM rubbers may have from 1 to 20 double bonds per 100 carbon atoms.
Examples which may be mentioned of diene monomers for EPDM rubbers are conjugated dienes, such as isoprene and butadiene, non-conjugated dienes having from 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes, such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyl-tricyclo[5.2.1.0.2.6]-3,8-decadiene, or mixtures of these. Preference is given to 1,5-hexadiene-5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably from 0.5 bis 50% by weight, in particular from 1 to 8% by weight, based on the total weight of the rubber.
EPOM rubbers may preferably have also been grafted with other monomers, e.g. with glycidyl (meth)acrylates, with (meth)acrylic esters, or with (meth)acrylamides.
Copolymers of ethylene with esters of (meth)acrylic acid are another group of preferred rubbers. The rubbers may also contain monomers having epoxy groups. These monomers containing epoxy groups are preferably incorporated into the rubber by adding, to the monomer mixture, monomers having epoxy groups and the formula I or II
where R6 to R10 are hydrogen or alkyl having from 1 to 6 carbon atoms, and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.
R6 to R8 are preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are allyl glycidyl ether and vinyl glycidyl ether.
Preferred compounds of the formula II are acrylic and/or methacrylic esters having epoxy groups, for example glycidyl acrylate and glycidyl methacrylate.
The copolymers are advantageously composed of from 50 to 98% by weight of ethylene, from 0 to 20% by weight of monomers having epoxy groups, the remainder being (meth)acrylic esters.
Particular preference is given to copolymers made from 50 to 98% by weight, in particular from 55 to 95% by weight, of ethylene, in particular from 0.3 to 20% by weight of glycidyl acrylate, and/or from 0 to 40% by weight, in particular from 0.1 to 20% by weight, of glycidyl methacrylate, and from 1 to 50% by weight, in particular from 10 to 40% by weight, of n-butyl acrylate and/or 2-ethylhexyl acrylate.
Other preferred (meth)acrylates are the methyl, ethyl, propyl, isobutyl and tert-butyl esters.
Besides these, comonomers which may be used are vinyl esters and vinyl ethers.
The ethylene copolymers described above may be prepared by processes known per se, preferably by random copolymerization at high pressure and elevated temperature. Appropriate processes are well known.
Preferred elastomers also include emulsion polymers whose preparation is described, for example, by Blackley in the monograph “Emulsion Polymerization”. The emulsifiers and catalysts which may be used are known per se.
In principle it is possible to use homogeneously structured elastomers or those with a shell construction. The shell-type structure is determined, inter alia, by the sequence of addition of the individual monomers. The morphology of the polymers is also affected by this sequence of addition.
Monomers which may be mentioned here, merely as examples, for the preparation of the rubber fraction of the elastomers are acrylates, such as n-butyl acrylate and 2-ethylhexyl acrylate, and corresponding methacrylates, and butadiene and isoprene, and also mixtures of these. These monomers may be copolymerized with other monomers, such as styrene, acrylonitrile, vinyl ethers and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate.
The soft or rubber phase (with a glass transition temperature of below 0° C.) of the elastomers may be the core, the outer envelope or an intermediate shell (in the case of elastomers whose structure has more than two shells). When elastomers have more than one shell it is also possible for more than one shell to be composed of a rubber phase.
If one or more hard components (with glass transition temperatures above 20° C.) are involved, besides the rubber phase, in the structure of the elastomer, these are generally prepared by polymerizing, as principal monomers, styrene, acrylonitrile, methacrylonitrile. alpha.-methylstyrene, p-methylstyrene, or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate or ethyl methacrylate. Besides these, it is also possible to use relatively small proportions of other comonomers.
It has proven advantageous in some cases to use emulsion polymers which have reactive groups at their surfaces. Examples of groups of this type are epoxy, amino and amide groups, and also functional groups which may be introduced by concomitant use of monomers of the formula
where: R15 is hydrogen or C1- to C4-alkyl, R16 is hydrogen, C1- to C8-alkyl or aryl, in particular phenyl, R17 is hydrogen, C1- to C10-alkyl, C6- to C12-aryl or —OR18.
R18 is C1- to C8-alkyl or C6- to C12-aryl, if desired with substitution by O- or N-containing groups, X is a chemical bond, C1- to C10-alkylene or C6- to C12-aryl, or
The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups at the surface.
Other examples which may be mentioned are acrylamide, methacrylamide and substituted acrylates or methacrylates, such as (N-tert-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate and (N,N-diethylamino)ethyl acrylate.
The particles of the rubber phase may also have been crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate, butanediol diacrylate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP A 50 265.
It is also possible to use the monomers known as graft-linking monomers, i.e. monomers having two or more polymerizable double bonds which react at different rates during the polymerization. Preference is given to the use of those compounds in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups), for example, polymerize(s) significantly more slowly. The different polymerization rates give rise to a certain proportion of unsaturated double bonds in the rubber. If another phase is then grafted onto a rubber of this type, at least some of the double bonds present in the rubber react with the graft monomers to form chemical bonds, i.e. the phase grafted on has at least some degree of chemical bonding to the graft base.
Examples of graft-linking monomers of this type are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids, for example allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate, and the corresponding monoallyl compounds of these dicarboxylic acids. Besides these there is a wide variety of other suitable graft-linking monomers. For further details reference may be made here, for example, to U.S. Pat. No. 4,148,846.
The proportion of these crosslinking monomers is generally up to 5% by weight, preferably not more than 3% by weight, based on the total amount of additives.
Some preferred emulsion polymers are listed below. Mention is made firstly of graft polymers with a core and with at least one outer shell and the following structure:
Instead of graft polymers whose structure has more than one shell it is also possible to use homogeneous, i.e. single-shell, elastomers made from 1,3-butadiene, isoprene and n-butyl acrylate or from copolymers of these. These products, too, may be prepared by concomitant use of crosslinking monomers or of monomers having reactive groups.
The elastomers described as additives may also be prepared by other conventional processes, e.g. by suspension polymerization.
Other suitable elastomers which may be mentioned are thermoplastic polyurethanes, as described in EP-A 115 846, EP-A 115 847, and EP-A 117 664, for example.
It is, of course, also possible to use mixtures of the rubber types listed above.
The absorber material of the present invention may also comprise other conventional additives and processing aids. Merely by way of example, mention may be made here of additives for scavenging formaldehyde (formaldehyde scavengers), plasticizers, coupling agents, and pigments. The proportion of additives of this type is generally within the range from 0.001 to 5% by weight.
The absorber material of the present invention shows good (high) absorption and good (low) reflection. Thus, preferably the absorber material shows at least 70% absorption and less than 30% reflection. Furthermore, the absorber material of the present invention can have a melt volume rate of 120 cm3/10 min to 5 cm3/10 min measured at 250° C./min with a weight of 2.16 kg.
The wave absorber of the present invention can be used for absorbing electromagnetic waves in the above mentioned frequency region or range.
Accordingly, another aspect of the present invention is an electronic device containing a radar absorber in form of a radar absorber part or a radar absorbing housing, the radar absorber comprising
The absorber material and electronic device of the present invention are especially suitable for autonomous driving and thus forms part of a vehicle, like a car, a bus or a heavy goods vehicle, or telecommunication, 5G, anechoic chambers.
The following examples explain the invention in further details without limiting the invention to these.
Materials
Poly(butylene terephthalate) (PBT, Ultradur® B4500 NAT) were obtained from BASF SE. Black pearls 880 (aspect ratio<5) were obtained from Cabot corporation. The stainless-steel fiber (stainless steel 1.4113) with a broad length distribution including particles with aspect ratio>5) was obtained from Deutsche Metallfaserwerk.
Measurement of the Interaction with Electromagnetic Waves
The experimental setup for the characterization of the absorbers in the range 60-90 GHz is as follows.
A vectoral network analyzer Keysight N5222A (10 MHz-26.5 GHz), two Keysight T/R mm head modules N5256AW12, 60-90 GHz and as a sample holder a swissto12 corrugated waveguide WR12+, 55-90 GHz. The calibration of the corrugated waveguide (cw) is done by doing a thru and short measurement. For the thru measurements the flanges of the cw are connected, for the short measurement, a metal plate is inserted between the flanges. The field distribution of the cw is described in: IEEE Transactions on Microwave Theory and Techniques 58, 11 (2010), 2772.
After the calibration, the sample (minimum diameter 2 cm) is inserted between the flanges of the cw and the S11 (reflection) and S21 (transmission) parameters are measured in the range 60-90 GHz (amplitude and phase). From the measured S11 and S22 parameters, the absorption A of the sample was calculated as follows: A (%)=100−S11(%)−S21(%).
From the measured parameters, the dielectric parameters ε′ (dielectric permittivity) and ε″ (dielectric loss factor) of the sample material is calculated at each frequency point using the swissto12 materials measurement software.
In order to determine the absorption values at 0° and 90° the sample was measured twice in this set-up. Once the flow direction (i.e. orientation of the fibrous electrically conductive particles) from the injection molding of the sample was place parallel to the electric field (0°) and once was the sample rotated by 90° to yield the orientation of the fibrous electrically conductive particles where the flow direction is perpendicular to the electric field (90°). The Δabsorption is the difference between the absorption in the two orientations.
Preparation of the Comparative Example C1 to C5 and Inventive Example E1
General procedure of the preparation of inventive and comparative examples Poly(butylene terephthalate) (PBT, Ultradur® B4500 NAT) was obtained from BASF SE and dried to a water content below 0.04 wt %. The PBT, the lubricant and the carbon black batch were fed into to extruder (ZE25) with a barrel temperature of 270° C. and an output of 15 kg/h. Steel fibers were added directly in the melt in zone 4 of the extruder to prevent excessive shearing of the fibers. Material was granulated and dried to a water content below 0.04 wt %. The samples for the electromagnetic analysis (60×60×1 mm) were injection molded using 260° C. for melt temperature, 60° C. for mold temperature. All examples were prepared using this approach.
The compositions of the inventive (E1) and comparative examples (C1-C5) are shown in Table 1.
From these results it is clear that inventive sample E1 has a good absorption with an unexpected low anisotropy even though it contains high amount of fibrous electrically conductive particles.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20210594.6 | Nov 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/083228 | 11/26/2021 | WO |
