US20060182877A1

US20060182877A1 - Flame retardant, electrically conductive shielding materials and methods of making the same

Info

Publication number: US20060182877A1
Application number: US11/389,301
Authority: US
Inventors: Larry Creasy; Kevin Hug
Original assignee: Laird Technologies Inc
Current assignee: Laird Technologies Inc
Priority date: 2002-03-08
Filing date: 2006-03-24
Publication date: 2006-08-17
Also published as: KR20040101278A; ATE508623T1; KR100885012B1; JP2009111408A; DE60336990D1; US20040157955A1; CN100393188C; WO2003077627A1; EP1483949B1; TWI339561B; JP4289669B2; JP2005520331A; TW200406143A; US7060348B2; AU2003217977A1; EP1483949A1; CN1653877A

Abstract

Flame retardant EMI shielding materials with improved retention of shielding properties are disclosed. The shielding materials are provided with a dispersed flame retardant on the surfaces of the internal interstices. Methods of making the flame retardant shielding materials are also disclosed.

Description

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of presently allowed U.S. patent application Ser. No. 10/093,667 filed Mar. 8, 2002. The disclosure of the above application is incorporated herein by reference.

FIELD

The present disclosure relates to flame retardant electrically conductive EMI shielding materials, and more particularly to flame retardant electrically conductive EMI shielding materials that exhibit improved retention of shielding properties.

BACKGROUND

The statements in this background section merely provide background information related to the present disclosure and may not constitute prior art.
A common problem in the operation of electronic devices is the generation of electromagnetic radiation within the electronic circuitry of the equipment. Such radiation results in “electromagnetic interference” or “EMI”, which can interfere with the operation of other electronic devices within a certain proximity.
A common solution to ameliorate the effects of EMI has been the development of shielding materials capable of absorbing and/or reflecting EMI energy. These shielding materials are employed to localize EMI within its source, and to insulate other devices proximal to the EMI source. In fact, in the United States, EMI shielding materials must comply with the commercial Federal Communication Commission (FCC) EMC regulations to be sold as EMI shielding materials.
Moreover, an objective for all EMI shielding materials to be used in electronic devices is that they must not only comply with FCC requirements, but EMI shielding materials should also meet Underwriter's Laboratories (UL) standards for flame retardancy. In this context, EMI shielding materials need to be made flame retardant, e.g., achieving a rating of V-0 under UL Std. No. 94, “Tests for Flammability of Plastic Materials for Parts in Devices and Appliances” (1991), without compromising the shielding properties necessary for meeting EMI shielding requirements.
Several attempts have been made to provide EMI shielding materials (or gaskets) that exhibit flame retardancy. Typically, an EMI gasket is provided with a distinct flame retardant layer through the use of a highly viscous flame retardant material which is subsequently cured. For example, U.S. Pat. No. 4,857,668, which is directed to a conductive fabric-on-foam EMI gasket, discloses a distinct flame retardant urethane layer being disposed on the interior side of the conductive fabric. Likewise, U.S. Pat. No. 6,248,393, which is also directed to a conductive fabric-on foam EMI gasket, discloses the formation of a distinct flame retardant layer on the interior side of the conductive fabric by the delimited penetration of the fabric with a highly viscous flame retardant composition. The delimited penetration of the fabric allows the exterior of the gasket to remain substantially coating free and thus conductive. However, the coated portions of the fabric lose conductivity due to the flame retardant coating. Thus, while these gasket materials exhibit surface resistivity, any z-axis conductivity or bulk resistivity exhibited by these materials will be drastically diminished due to the flame retardant.

SUMMARY

Exemplary aspects of the present disclosure provide flame retardant electrically conductive EMI shielding materials, which can include porous materials having internal interstices where the internal surfaces of the interstices are electrically conductive, and contain an effective amount of flame retardant. In some embodiments, the surfaces of the interstices are electrically conductive due to at least one conductive metal or non-metal layer disposed on internal surfaces.
Other aspects of the present disclosure relate to methods of producing or making flame retardant, electrically conductive EMI shielding materials. In one embodiment, a method generally includes impregnating a porous material having internal interstices with an effective amount of flame retardant that provides the impregnated shielding material with at least horizontal flame rating while at the same time retaining z-axis conductivity or bulk resistivity sufficient for EMI shielding applications. The flame retardant can be dispersed such that the impregnated shielding material is substantially free of occluded interstices.
Further aspects and features of the present disclosure will become apparent from the detailed description provided hereinafter. In addition, any one or more aspects of the present disclosure may be implemented individually or in any combination with any one or more of the other aspects of the present disclosure. It should be understood that the detailed description and specific examples, while indicating exemplary embodiments of the present disclosure, are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

DRAWINGS

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
FIG. 1 is a plot graph illustrating far field shielding effectiveness (SE) as a function of frequency for shielding materials (1.75 millimeter foam) with a dispersed flame retardant in accordance with aspects of the present disclosure: uncoated control; polymer coated; flame retardant coated; and polymer and flame retardant.
FIG. 2 is a force displacement resistance graph illustrating bulk resistance as a function of material compression for shielding materials (1.75 millimeter foam) with a dispersed flame retardant in accordance with aspects of the present disclosure: uncoated control; polymer coated; flame retardant coated; and polymer and flame retardant.
FIG. 3 is a plot graph illustrating far field shielding effectiveness (SE) as a function of frequency for shielding materials (1.5 millimeter fabric-on-foam) with a dispersed flame retardant in accordance with aspects of the present disclosure: uncoated control; polymer coated; flame retardant coated; and polymer and flame retardant.
FIG. 4 is a force displace resistance graph illustrating bulk resistance as a function of material compression for shielding materials (1.5 millimeter fabric-on-foam) with a dispersed flame retardant in accordance with aspects of the present disclosure: uncoated control; polymer coated; flame retardant coated; and polymer and flame retardant.

DETAILED DESCRIPTION

The following description is merely exemplary in nature and is in no way intended to limit the present disclosure, application, or uses.
The inventors hereof have recognized a need for EMI shielding materials that are flame retardant and exhibit z-axis conductivity or bulk resistivity suitable for electromagnetic shielding applications. Accordingly, various aspects of the present disclosure relate to flame retardant EMI shielding materials that exhibit z-axis conductivity or bulk resistivity and methods of producing these materials.
Exemplary aspects of the present disclosure provide flame retardant electrically conductive EMI shielding materials, which include porous materials having internal interstices where the internal surfaces of the interstices are electrically conductive, and contain an effective amount of flame retardant. In some embodiments, the surfaces of the interstices are preferably electrically conductive due to at least one conductive layer being disposed on internal surfaces, with a metallized layer being more preferred in some embodiments. A wide range of metals can be used for the metallized layer, including copper, nickel, silver, palladium, platinum, nickel-plated-silver, aluminum, tin, alloys thereof, etc.
In various exemplary embodiments, the flame retardant is in the form of a particulate dispersed throughout the interstices of the shielding material. In such embodiments, the particulate preferably occupies no more than about 30% of the total internal surface area defined by the interstices, with no more than about 20% being more preferable in some embodiments, and with no more than about 10% being even more preferable in other embodiments.
In other exemplary embodiments, the flame retardant is in the form of a coating on the internal surfaces of the interstices. In such embodiments, the coating preferably has a thickness of about 12 microns or less, with about 5 microns or less being more preferable in some embodiments, and with about 2 microns or less being even more preferable in other embodiments. In these embodiments, the shielding material is preferably substantially free of occluded interstices. Some preferred embodiments include a porous material comprising open-cell foam having at least one metallized layer throughout, which can optionally include a porous scrim. An example of open-cell foam is polyurethane foam.
Accordingly, various embodiments provide shielding materials of that advantageously exhibit bulk resistance and flame retardance. In exemplary embodiments, the shielding material preferably has a bulk resistivity of about 20 ohm•cm or less, with about 1 ohm•cm or less being more preferable in some embodiments, and with about 0.05 ohm•cm or less being even more preferable in other embodiments. The effective amount of flame retardant preferably provides the shielding material with at least one of following UL94 flame ratings: at least HF-1; at least HB; at least V2; at least V1; or V0. An example of a flame retardant that can be used is a phosphate-based flame retardant, such as an ammonium phosphate salt. In other embodiments, the flame retardant is halogen free. The flame retardant can optionally include a polymeric carrier (e.g., polyurethane) such as water-soluble or water-dispersible polymer. In various embodiments, the shielding materials preferably exhibit an average shielding effectiveness of at least about 65 decibels.
Aspects of the present disclosure also relate to methods of producing any one or more of the above-described shielding materials. In one embodiment, a method generally includes impregnating a porous material having internal interstices (the internal surfaces of which are electrically conductive) with a flame retardant to provide an effective amount of the flame retardant on the internal surfaces of the interstices. The flame retardant is preferably in the form an aqueous composition, which can optionally include a polymeric carrier (e.g., polyurethane, etc.) such as water-soluble or water-dispersible polymer. Preferably, the solvent for the aqueous composition is water and water-miscible organic solvents and can optionally be free of a non-water-miscible organic solvent. The method preferably includes curing the impregnated shielding material. Advantageously, this exemplary method of providing an effective amount of the flame retardant results in no more than about a 10 fold increase in bulk resistivity, with no more than a 1 fold increase in bulk resistivity being more preferable in some embodiments. Other preferred embodiments are as described herein.
Accordingly, exemplary embodiments can provide shielding materials that advantageously exhibit flame retardance and electrical properties previously unattainable. Exemplary embodiments provide flame retardant electrically conductive EMI shielding materials that exhibit flame retardance without a substantial decrease in shielding capacity. Advantageously, the inventors hereof have found that electrically conductive shielding materials can be rendered flame retardant without a substantial degradation of electrical properties, which has been found to occur with the conventional application of flame retardants. These and other advantages and aspects will be more readily apparent from the description set forth herein.
In various embodiments, flame retardant shielding materials include a porous material having internal interstices in which the internal surfaces of the interstices are electrically conductive and include an effective amount of a flame retardant. Porous materials having internal interstices (or pores) with electrically conductive surfaces are well known in the art and are commonly used for EMI shielding applications. The internal surfaces of the interstices (or pores) define an “internal surface area” through an interconnected network of interstices or pores exhibited throughout the material. In preferred embodiments, the porous material is open cell polymeric foam, such as foam made from a thermoplastic elastomer (e.g., polyurethane foam, etc.). In such embodiments, polymeric foams are preferred due to their deformable nature, which is beneficial for certain shielding applications. In more preferred embodiments, the foams have about 5 to 120 pores per inch, with about 50 to 70 pores per inch being more preferred in some embodiments.
In shielding applications, the internal surfaces of the porous materials are rendered electrically conductive by depositing at least one layer of an electrically conductive material throughout the internal surface area of the material. Typically, electrically conductive in shielding applications means a surface resistivity of about 300 ohm/square or less. The conductive material can be in the form of a conductive filler, a metal layer, or a conductive non-metal layer. Examples of conductive fillers used in EMI shielding applications include, but are not limited to, carbon graphite, metal flakes, metal powder, metal wires, metal plated particles, combinations thereof, etc. In various embodiments, the porous material is impregnated with the filler to disperse the filler throughout the material. The metallized layers are typically applied by plating or sputtering, both well known processes in the art. Metals that are often used to render porous materials electrically conductive include, but are not limited to, copper, nickel, silver, palladium, platinum, nickel-plated-silver, aluminum, tin, alloys thereof, etc. Examples of non-metallic materials that can be used to render the internal surface area of porous materials electrically conductive include, but are not limited to, inherently conductive polymers, such as d-polyacetylene, d-poly (phenylene vinylene), d-polyaniline, combinations thereof, etc.
In various embodiments, the porous shielding materials can also include a scrim or outer fabric layer to provide abrasion resistance to the shielding material. The scrim can be in the form of woven, non-woven, or knitted fabrics. In such exemplary embodiments, the scrim comprises porous material.
The porous shielding materials should preferably exhibit a high degree of shielding effectiveness. In this regard, the shielding effectiveness of a shielding device is a measure of the attenuation of a signal transmitted through the material. In accordance with aspects of the present disclosure, the porous shielding material preferably exhibits an average shielding effectiveness of at least 65 decibels (dB) measured from 1 Megahertz (MHz) to 1 Gigahertz (GHz) by a transfer impedance test. More preferable for some embodiments, the average shielding effectiveness (SE) is at least about 80 dB, with at least about 90 dB being more preferred for other embodiments.
In a particularly preferred embodiment, the porous material comprises metallized foam in which the internal surface area of the foam material has at least one metal layer deposited thereon. Examples of metallized foams are commercially available from a variety of sources. One commercial provider is Eltech System Corp., located in Chardon, Ohio. Another commercial provider is Laird Technologies Inc., located in St. Louis, Mo.
In accordance with aspects of the present disclosure, the internal surfaces of the porous material are provided with an effective amount of a flame retardant. Stated otherwise, the flame retardant is dispersed throughout the material by being disposed on the surfaces of the interconnected interstices (or pores). In the context of the present disclosure, an “effective amount” is an amount of the flame retardant that provides the shielding material with at least horizontal flame rating while at the same time retaining a z-axis conductivity or bulk resistivity sufficient for EMI shielding applications. Flame retardance is determined using the Underwriters Laboratories Standard. No. 94, “Tests for Flammability of Plastic Materials for Parts in Devices and Appliances” (5^thEdition, Oct. 29, 1996). In preferred embodiments, the effective amount provides the shielding material with a UL94 flame rating of at least HF-1 or HB. More preferable is a UL94 vertical flame rating of at least V1, V2 or V0. Likewise, the shielding material preferably exhibits a bulk resistivity (when compressed by 50 percent) of about 20 ohm•centimeters (Ω•cm) or less in various embodiments, with about 1 Ω•cm or less being more preferred, and about 0.05Ω•cm or less being even more preferred in some embodiments. One method of ascertaining bulk resistivity is by using the ASTM D991 standard. As will be apparent to one skilled in the art, the actual amount of the flame retardant to be dispersed throughout the material is variable due to variety of factors. Generally, the amount of the flame retardant dispersed throughout the material should be about 10 ounces per square yard (opsy) or less, with about 5 opsy or less being more preferred in some embodiments, with about 3 opsy or less being even more preferred in other embodiments. These parameters, however, can be easily ascertained by one skilled in the art following the teachings of the present disclosure.
The flame retardant materials in various embodiments have the flame retardant disposed on the internal surfaces of the material in a variety of forms. In one embodiment, the flame retardant is dispersed throughout the material as a relatively thin coating. In another embodiment, the flame retardant is dispersed throughout the material as a particulate adhered to the internal surfaces. While not wishing to be limited by theory, it is believed that the property of the flame retardant shielding materials of the present disclosure being substantially free of occluded interstices (or pores) due to the dispersed nature of the flame retardant facilitates a dramatic retention of the electrical properties of the shielding material. Electrical contact between the electrically conductive surfaces of the shielding material is thus allowed to occur especially during deformation. This is the contrary of prior flame retardant EMI shielding materials in which the flame retardant coatings are of such thicknesses that blockage or occlusion of the interstices or pores occur thereby reducing electrical contact. Reference to “substantially free” of occluded interstices (or pores) means that less than a majority of the interstices (or pores) of the porous material provided with the flame retardant are occluded or blocked. In more preferred embodiments, less than about 25 percent of the interstices (or pores) are occluded, with less than about 10 percent being even more preferred in other embodiments.
In one particular embodiment, the flame retardant is in the form of particulate disposed on the internal surfaces. In a more preferred embodiment, the particulate occupies about 30 percent or less of the total internal surface area of the shielding material provided with the flame retardant, with about 20 percent or less being preferred, and about less than 10 percent being more preferred. In another embodiment, the flame retardant is in the form a thin coating having a thickness of about 12 microns or less, with about 5 microns or less being more preferred, and about 2 microns or less being even more preferred.
Flame retardants that can be used include any flame retardant, such as halogen-based and non-halogen based flame retardants. In one embodiment, a phosphate-based flame retardant is used. Examples of phosphate-based flame retardants that can be used are ammonium phosphates, alkyl phosphates, phosphonate compounds, combinations thereof, etc. Representative examples of flame retardants that can used include, but are not limited to, decabromodiphenyloxide, decabromodiphenylether, antimony trioxide, hexabromocyclododecane, ethylenebis-(tetrabromophthalimide), bis(hexachlorocyclopentadieno)cyclooctane, chlorinated parrafin, aluminum trihydrate, magnesium hydroxide, zinc borate, zinc oxidetri-(1,3-dicholoroisopropyl) phosphate, phosphonic acid, oligomeric phosphonate, ammonium polyphosphate (APP), ammonium dihydrogen phosphate (ADP), triphenyl phosphate (TPP), diammonium and monoammonium phosphate salt or any mixture thereof. In another embodiment, the flame retardant is substantially free of halogens to provide a halogen-free flame retardant material. Particular examples of commercially available flame retardants are sold by Clariant Corporation located in Germany, Apex Chemical Company located in Spartanburg, S.C., and Akzo Nobel located in Dobbs Ferry, New York.
In another embodiment, a polymeric coating is optionally disposed between the internal surface of the interstices (or pores) and the flame retardant. It has been advantageously found that the shielding material may be provided with a polymeric coating without a substantial increase in flammability. The amount provided to the shielding material is any amount that does not substantially decrease the shielding effectiveness of the material while at the same time increasing flammability. Examples of polymeric materials that can be used are homopolymers, copolymers, and mixtures thereof such as poly(ethylene), poly(phoshphazene), poly(acrylonitrile), poly(styrene), poly(butadiene), plasticized poly(vinyl chloride), polychloroprene (Neoprene), polycarbonate, poly(vinyl acetate), alkylcelluloses, poly(ethylene terephthalate), phosphate and polyphosphonate esters, epoxy resins, copolymers of styrene and maleic anhydride, melamine-formaldehyde resins, and urethanes. Preferably, the polymeric material for the coating is a water-soluble or water-dispersible polymer. In one particular embodiment, the internal surface area of the porous material is provided with a urethane polymer coating with a dried coating weight of less than about 1 ounce per square yard (opsy), with less than about 0.6 opsy being more preferred. As will be apparent to one skilled in the art, the actual amount of the polymeric coating is variable so long as the shielding effectiveness and flammability of the shielding material is not detrimentally affected.
In various embodiments, the flame retardant shielding materials are prepared by impregnating the above-described shielding materials with a flame retardant under conditions sufficient to dispose an effective amount of the flame retardant on the internal surfaces of the interstices. The porous materials are impregnated using any technique known in the art. For example, the porous material can be immersed in a liquid composition containing the flame retardant. Other methods of impregnating the porous materials with flame retardant include spraying, air knife coating, top and bottom direct coating, slot die (extrusion) coating, knife over roll (gap) coating, metering rod coating, and dual reverse roll coating.
In one preferred embodiment, the porous material is impregnated by immersing the material in a liquid flame retardant composition of sufficient viscosity and for a time sufficient for the composition to diffuse throughout the material. The excess flame retardant is removed (e.g., by nipping the impregnated material) to minimize the occurrence of occlusions, after which the impregnated material is cured by any technique known in the art. More preferably, an aqueous composition is used for impregnating a polymeric foam to minimize (or at least reduce) potential swelling of the foam material. In the context of the present disclosure, “aqueous” means that the majority of the solvent for the liquid composition is water or a combination of water and water-miscible organic solvents. More preferable, the solvent is free of non-water miscible organic solvents. In one embodiment, curing is effected by drying the material (e.g., at ambient temperature or with an oven). But as will be apparent to one skilled in the art, the choice of curing means is dependent on the components contained in the composition.
Liquid flame retardant compositions that can be used for impregnating the foam material are readily available from various suppliers such as Clariant Corporation, Apex Chemical Company and Akzo Nobel, which are described above. The viscosity of the liquid composition should be sufficiently low to readily diffuse and permeate through the porous material. Preferably, the liquid flame retardant composition should have a viscosity of about 1000 centapoise per second (cps) or less, with about 500 cps or less being more preferred, and about 100 cps or less being even more preferred. Thus, the viscosity of the commercially available flame retardants may be adjusted to facilitate diffusion throughout the porous material in addition to altering coating weights. Optionally, liquid composition can also include a wetting agent to facilitate diffusion of flame retardant composition. Wetting agents that can be used include, but are not limited to, surfactants (e.g., cationic, anionic, non-ionic and zwitterionic). The wetting agent can be incorporated in the composition in an amount of about ten percent by weight or less, with about four percent by weight or less being preferred, and about two percent by weight or less being even more preferred.
In another embodiment, the liquid flame retardant compositions also include a polymeric carrier to facilitate the formation of a thin flame retardant coating on the internal surfaces of the interstices (or pores) of the porous shielding material. Polymeric carriers to be used include the polymeric materials described above, with water-soluble or water-dispersible polymers being preferred. In one particular embodiment, a water-based urethane polymer composition is utilized. The ratio of flame retardant to polymeric carrier should range from about 1:1 to about 5:1 on a dried weight basis, with a ratio of about 2:1 to about 3:1 on a dried weight basis being more preferred.
As previously described, the shielding materials can be optionally provided with a polymeric coating without increasing the flammability of the shielding material. In this embodiment, the shielding material is first impregnated with the polymeric coating composition. The excess polymeric coating material is removed from the impregnated shielding material to minimize (or at least significantly reduce) occluded interstices and optionally cured (e.g., dried) prior to the application of the flame retardant.
In accordance with aspects of the present disclosure, the process or step of impregnating the porous shielding material with the flame retardant results in flame retardant dispersed throughout the material. One significant advantage of the method of this embodiment is that equivalent or greater quantities of flame retardant can be disposed in the material as compared to prior methods in which only a distinct portion of the material is provided with a flame retardant. The distinct layers of flame retardant produced with prior methods significantly reduces the z-axis conductivity or bulk resistivity of the material. In preferred embodiments of the present disclosure, the methods of providing the shielding material with the flame retardant should result in no more than a 10 fold increase in bulk resistivity for the shielding material, with no more than about a 1 fold increase in bulk resistivity being preferred, and no more than a 0.1 fold increase being even more preferred. Likewise, the average shielding effectiveness of the shielding material once provided with the flame retardant preferably decreases by no more than 30 percent, with 20 percent or less being more preferred, and 10 percent or less being even more preferred.
The following non-limiting examples illustrate unique properties of the flame retardant foams produced in accordance with aspects of the present disclosure.

EXAMPLES

Example 1

Commercially available wholly metallized fabric-on-foam shielding materials were coated with undiluted Apex 911 flame retardant (viscosity of 25 cps) available from Apex Chemical Company. The fabric-on-foam shielding materials in two different thicknesses (1.0 millimeter and 3.2 millimeter) were taken from line runs of Laird Technologies fabric-on-foam products CF0040-4 and CF01 25-4, respectively, 5″×11″ sheets of conductive foam were dipped in a 5″×12″ pan containing the flame retardant. The foam sheets were then nipped with a dual rubber nip roller at 10 psi. After padding, the coated foam sheets were dried in an oven at 110 degrees Celsius for approximately 25 minutes. The coated foam sheets were visually observed to be free of occluded pores. The coating weights of the Apex 911 were determined to be 4.34 opsy for the 3.2 millimeter material, and 1.76 opsy for the 1.0 millimeter material. Specimens were cut into 5″×½″ bar samples and subjected to the UL94 Vertical Burn (V) test. The burn test results are listed in Table 1 below.

TABLE 1


UL 94-V Flammability Test Results

1.0 mm FR conductive foam

3.2 mm FR conductive foam

				Pass/					Pass/
Sample	T1	T2	T3	Fail	Sample	T1	T2	T3	Fail

1	0	0	0	PASS	1	0	0	0	PASS
2	0	0	0	PASS	2	1	0	0	PASS
3	0	0	0	PASS	3	0	0	0	PASS
4	0	0	0	PASS	4	7	0	0	PASS
5	3	0	0	PASS	5	0	0	0	PASS

Total

3

Total

8

Afterflame

Test Result	V-0	Test Result	V-0

Both samples of the flame retardant fabric-on-foam passed the UL94 Burm Test with a V0 rating. The V0 rating was also independently confirmed for these materials by Underwriters Laboratories. In-house V0 burn ratings were also obtained with other flame retardants Apex 2080 and Fyrol FR-2 (AKZO Nobel) applied in the manner described above.

Example 2

Samples of 1.75 millimeter thick conductive foam commercially available fron Eltech Systems Corp. of Chardron, Ohio were obtained and treated in accordance with aspects of the present disclosure. The conductive foams were carbon coated polyurethane foam plated with 30 grams/square meter of nickel, which is sold under the product code number 2620. One group of foam samples (n=5) were not treated and served as a control. A second group of 5″×7″ sheets conductive foam (n=5) were dipped in a 5″×12″ pan containing undiluted Flame Proof 911 coating by Apex Chemical Company and 1 percent by weight Pentrapex 1924 (wetting agent) also available from Apex Chemical Company. The foam sheets were then nipped with a dual rubber nip roller at 10 psi. After padding, the coated foam sheets were dried at 110 degrees Celsius for approximately 25 minutes. A third group of foam samples (n=5) were first coated with a water-based urethane coating (Solucote 1024-4C by Soluol Chemical Company. 5″×7″ sheets of conductive foam were submerged in a 5″×12″ plastic pan containing a solution of diluted water-based urethane coating (200 gram urethane (Solucote) in 800 grams deionized water). After the foam sheets were dipped in the urethane coating, they were padded with a dual rubber nip roller at 10 psi. Afer padding, the coated foam sheets were dried in an oven at 140 degrees Celsius for approximately 20 minutes. After the samples dried, they were dipped in undiluted Flame Proof 911 following the above described proceure and dried with the oven temperature at 110 degrees Celsius. A fourth group of foam samples (n=5) were coated with the urethane only. The coated samples were visually observed to be free of occluded pores. Specimens from three (3) groups (uncoated, 911 coated, and urethane coated plus 911 coated) were cut into 5″ long by ½″ wide bar samples and subjected to the UL94 vertical (V) burn test. The results of the burn tests are listed in Table 2. The specimens were also analyzed for coating weights, surface resistivities (4-point), shielding effectiveness (SE), and force resistance characteristics. The coating weights and surface resistivittes are listed in Table 3. The shielding effectiveness and force resistance acteristics (i.e., bulk resistance as a function of compression) are graphically depicted in FIGS. 1 and 2, respectively.

TABLE 2


Control-Eltech	Eltech 30 g Ni	Eltech 30 g Ni
30 g Ni (Uncoated)	(911 Coated)	(Urethane and 911)

Sample	T1	T2	T3	P/F	Sample	T1	T2	T3	P/F	Sample	T1	T2	T3	P/F

1	4-BTC			F	1	0	0	0	P	1	1	0	0	P
2	4-BTC			F	2	0	0	0	P	2	0	0	1	P
3				NT*	3	0	0	0	P	3	0	0	0	P
4				NT*	4	1	0	0	P	4	0	0	0	P
5				NT*	5	0	0	0	P	5	0	0	0	P
Total
		0			Total		1			Total		1
Afterflame					Afterflame					Afterflame

Test Result	FAILED	Test Result	PASSED	Test Result	PASSED

*NT-not tested due to earlier failure of material.

TABLE 3


Coating Weights Ounces Per Sciuare Yard (OPSY)

Unplated	Plated	Metal	Urethaned	U	911	911	U/911	911
OPSY	OPSY	Weight	(U) OPSY	Weight	OPSY	Weight	OPSY	Weight

2.10	2.93	0.83	3.157	0.227	5.024	2.094	4.728	1.571

Surface Resistivity

Uncoated	U	911	U/911
4-Point	4-Point	4-Point	4-Point

0.1036	0.3519	0.1973	0.4483
ohm/sq.	ohm/sq.	ohm/sq.	ohm/sq.

The data in Table 3 and FIGS. 1 and 2 shows that foam shielding materials provided with dispersed flame retardant exhibited properties substantially unchanged from the control. For example, the surface resistivities of the coated materials exhibited approximately a 4.3 fold increase at most (0.4483 ohm/sq divided by .0.1036 ohm/sq. equals 4.3). As shown in FIG. 1, shielding effectiveness of the materials decreased by no more 23 percent. Likewise, FIG. 2 shows that the force resistance patterns of the control and flame retardant samples were similar.

Example 3

Samples of a wholly conductive fabric-on-foam shielding material as in Example 1 having a thickness of 1.5 millimeter were impregnated with undiluted Apex 911 (with and without urethane) and with urethane alone. The material was obtained from a line run of Laird Technologies fabric-on-foam product CF0060-4. The samples of the material were impregnated following the procedure described in Example 2 with the exception that the 911 flame retardant included 0.2 percent by weight Pentrapex 1924. The coated samples were visually observed to be free of occluded pores. A specimen of sample 3 (urethane coating+911 coating) was also examined under an electron microscope to evaluate the dispersed nature of the flame retardant. The internal surfaces of the pores were observed to contain an adhered particulate occupying less than 10 percent of the internal surface area. The particulate was also determined to contain a phosphorous material which correlates to the ammonium phosphate salt found in Apex 911. The surface resistivities, coating weights, and UL94 V0 flame retardance of the coated materials and of an uncoated control are listed in Table 4. The shielding effectiveness of the materials along with the force resistance characteristics of the samples are shown in FIGS. 3 and 4, respectively.

TABLE 4


	Urethane		911
Uncoated	Only	Urethane + 911	only

4-Point	0.014	0.028 ohm/sq.	0.038 ohm/sq.	0.022
Resistivity	ohm/sq.			ohm/sq.
OPSY	7.35	7.63 −	10.68 − 7.63 = 3.05	2.75
		7.35 = 0.28
UL94 V0	Failed	Failed	Passed	Passed
Burn Test

The data in Table 4 and FIGS. 3 and 4 shows that fabric-on-foam shielding materials provided with the flame retardant exhibited shielding capabilities substantially unchanged from the control. The surface resisitivities of the coated material exhibited less than 3 fold increase at most (0.038 ohm/sq. divided by 0.014 ohm/sq. equals 2.71). As shown in FIG. 3, the control sample exhibited an average shielding effectiveness of 95 decibels while the samples with flame retardant alone and with a urethane precoating in addition to the flame retardant exhibited an average shielding effectiveness of 91 decibels and 90 decibels, respectively, which is less than a 10 percent decrease in shielding effectiveness. Likewise, FIG. 4 shows that the force resistance patterns of the control and flame retardant samples are substantially similar.
Certain terminology is used herein for purposes of reference only, and thus is not intended to be limiting. For example, terms such as “upper”, “lower”, “above”, and “below” refer to directions in the drawings to which reference is made. Terms such as “front”, “back”, “rear”, “bottom” and “side”, describe the orientation of portions of the component within a consistent but arbitrary frame of reference which is made clear by reference to the text and the associated drawings describing the component under discussion. Such terminology may include the words specifically mentioned above, derivatives thereof, and words of similar import. Similarly, the terms “first”, “second” and other such numerical terms referring to structures do not imply a sequence or order unless clearly indicated by the context.
When introducing elements or features of the present disclosure and the exemplary embodiments, the articles “a”, “an”, “the” and “said” are intended to mean that there are one or more of such elements or features. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements or features other than those specifically noted. It is further to be understood that the method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order or performance. It is also to be understood that additional or alternative steps may be employed.
The description of the disclosure is merely exemplary in nature and, thus, variations that do not depart from the gist of the disclosure are intended to be within the scope of the disclosure. Such variations are not to be regarded as a departure from the spirit and scope of the disclosure.

Claims

1. A method of producing a flame retardant, electrically conductive EMI shielding material, the method comprising impregnating a porous material having internal interstices, the internal surfaces of which are electrically conductive, with an effective amount of flame retardant that provides the impregnated shielding material with at least horizontal flame rating while at the same time retaining z-axis conductivity or bulk resistivity sufficient for EMI shielding applications, wherein the flame retardant is dispersed such that the impregnated shielding material is substantially free of occluded interstices.

2. The method of claim 1, wherein the interstices are electrically conductive due to at least one electrically conductive metal or non-metal layer disposed on the internal surfaces.

3. The method of claim 1, wherein the flame retardant is halogen free.

4. The method of claim 1, wherein the flame retardant is in the form an aqueous composition.

5. The method of claim 4, wherein the aqueous composition includes a polymeric carrier.

6. The method of claim 5, wherein the polymeric carrier is water-soluble or water-dispersible polymer.

7. The method of claim 4, wherein the solvent for the aqueous composition is water or a combination of water and water-miscible organic solvents.

8. The method of claim 7, wherein the solvent is free of a non-water-miscible organic solvent.

9. The method of claim 1, further comprising curing the impregnated shielding material.

10. The method of claim 1, wherein the flame retardant comprises a phosphate-based flame retardant.

11. The method of claim 10, wherein the flame retardant comprises an ammonium phosphate salt.

12. The method of claim 1, wherein the effective amount of the flame retardant provides no more than about a ten fold increase in bulk resistivity.

13. The method of claim 1, wherein the effective amount of the flame retardant provides a UL94 flame rating of at least HB.

14. The method of claim 1, wherein the flame retardant is in the form of a particulate dispersed throughout the interstices.

15. The method of claim 1, wherein the flame retardant is in the form of a particulate occupying no more than about 30% of the total internal surface area defined by the interstices.

16. The method of claim 1, wherein the flame retardant is in the form of a coating on the internal surfaces of the interstices.

17. The method of claim 16, wherein the coating has a thickness of about 12 microns or less.

18. The method of claim 1, wherein the impregnated shielding material has a bulk resistivity of about 20 ohm•cm or less.

19. The method of claim 1, wherein the porous material comprises open-cell foam having at least one metallized layer throughout.

20. The method of claim 19, wherein the foam includes a porous scrim.

21. The method of claim 20, wherein the foam comprises polyurethane foam.

22. The method of claim 1, wherein the impregnated shielding material has an average shielding effectiveness of at least about 65 decibels.

23. The method of claim 1, wherein a polymeric coating is disposed between at least some of the internal surfaces of the interstices and the flame retardant.

24. A method of making a flame retardant, electrically conductive EMI shielding material, the method comprising providing a porous material having internal interstices, the internal surfaces of which are electrically conductive due to at least one electrically conductive metal or non-metal layer, with an effective amount of flame retardant that provides the impregnated shielding material with a UL94 flame rating of at least HB while at the same time retaining z-axis conductivity or bulk resistivity sufficient for EMI shielding applications, wherein the flame retardant is in the form of a particulate dispersed in a coating such that the impregnated shielding material is substantially free of occluded interstices with the particulate occupying no more than about 30% of the total internal surface area defined by the interstices.

25. The method of claim 24, wherein the flame retardant is halogen free.

26. The method of claim 24, wherein the effective amount of the flame retardant provides a UL94 flame rating of V0.

27. The method of claim 24, wherein the effective amount of the flame retardant provides no more than about a one fold increase in bulk resistivity.

28. The method of claim 24, wherein the shielding material has a bulk resistivity of about 0.05 ohm•cm or less.

29. The method of claim 24, wherein the particulate occupies no more than about 10% of the total internal surface area defined by the interstices.

30. The method of claim 24, wherein the impregnated shielding material has an average shielding effectiveness of at least about 90 decibels.