CA1246815A - Protective garment of composite fabric containing sulphonated fluoropolymer film with metal ion groups - Google Patents
Protective garment of composite fabric containing sulphonated fluoropolymer film with metal ion groupsInfo
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- CA1246815A CA1246815A CA000467944A CA467944A CA1246815A CA 1246815 A CA1246815 A CA 1246815A CA 000467944 A CA000467944 A CA 000467944A CA 467944 A CA467944 A CA 467944A CA 1246815 A CA1246815 A CA 1246815A
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Abstract
ABSTRACT
A protective garment fabricated at least in part from a composite fabric which contains a layer of a highly fluorinated ion exchange polymer having sulfonic acid multivalent metal ion salt functional groups.
A protective garment fabricated at least in part from a composite fabric which contains a layer of a highly fluorinated ion exchange polymer having sulfonic acid multivalent metal ion salt functional groups.
Description
~L2~ 315 TITLE
Protective Garment of Composite Fabric Containing Sulpho~ated Fluoropolymer Film with Metal Ion Groups Background of the Invention Protective clothing of many types is now well-known for many and varied uses in protecting people from fire and harmful substances, such as suits for industrial workers, flame- and fire-resistant suits for firemen, forest fire fighters, race car drivers and airplane pilots, and suits for use by military personnel. Garments include not only complete, hermetic suits, but also individual garments such as trousers, jackets, gloves, boots, hats, head coverings, masks, etc.
Regulations restricting exposure to hazardous environments of various kinds, such as the Occupational Safety and ~ealth Act, make it increasingly necessary to have bettar and more effective kinds of protective garments.
Such garments presently available are almost invariably of thick construction and heavy in weight, and are often fabricated at least in part from materials impermeable to water or water vapor, such as natural and synthetic rubbers and elastomers, chlorinated rubbers, etc. In the case of garments impermeable to water vapor, there is considerable discomfort to those wearing them, especially when the garments are of the hermetic variety, because of the entrapment of perspiration and body heat. Entrapment of heat and perspiration results in considerable discomfort of itself, and the heat stress which results from the prevention of loss of heat by the ordinary mechanism of evaporation of perspiration can ., ~, rapidly reach a dangerous stage of hea~ prostral:ion ~or the person wear ing the garment .
It is an object of this invention ~o provide improved protective garments which possess the 5 abili'cy to permi~ 'che passage of water vapor through the ~abric of the garment, and ~hereby pro~ide improved comfort for the person wearing ~he garment.
It is another object of this invention to provide improved protective garments which possess not only the ability to permit the passage of water vapor ~hrough the fabric, but also the ability to act as a stable barrier to the passage of most organic substances, including toxic compounds, through the fabric. Such garments could protect those exposed to a wide variety of org nic or harmful compounds.
; It is a further objec~ to provide such garments which are thin and light weight and which thus will more readily permit loss of heat by virtue of their light weight construction.
Summarv of the Invention Briefly, the invention comprises using as a component of the fabric of a protective garment a layer of an ion exchange polymer, preerably a semipermeable fluorinated ion exchange polymer having sulfonic acid functional groups in the form of bi-, tri- or tetravalent metal salt. By ~semipermeable"
is meant permeable to water vapor but substantially impermeable to most organic substances.
More specifically, the present invention provides for the use in protective clothing of a composite fabric, said fabric containing as the essential component thereof a continuous film of a highly fluorinated ion exchange polymer having sulfonic acid metal ion salt functional groups, said metal ion having a valence of +2, +3 or ~4, there s q 3 being at least one ~luorine atom attached to each carbon atom to which each said unctional group is ; attached, said polymer having an equivalent weight no qreater than about 2000.
~here are also provided accordiny ~o the invention a protective yarment and a waterproof ; protective cover fabrica~ed at lea~t in part from the composite fabric described in the previous paragraph.
There is fur~her provided according to ~che 10 invention a process wherein (a) water permeates from a first space adjacent a first side o a barrier to a second space adjacent the second side of said barrier, said barrier having as the essential component thereof a continuous film of a highly - 15 fluorinated ion exchange polymer having sulfonic acid metal ion salt functional groups, said metal ion having a valence of +2, +3 or +4, there being at least one fluor ine atom attached to each carbon atom to which each said sulfonic acid group is attached, 20 said polymer having an equivalent weight no greater ~han about 2000, and ~b~ a hazardous substance, said substance being a toxic organophosphorus co~pound o having a -P OR moiety wherein R is a Cl to Clo alkyl group, or a blistering agent which contains ~wo or more chloroethyl groups, present in said second space (i) permeates only slowly into said barrier and (ii) that portion of said hazardous substance which 30 permeates into said barrier is detoxified at least in part by said polymer, whereby the rate of penetration of said hazardous substance into said first ~pace is substantially decreased.
. 35 ` Detailed De_cri~_ion of the_Inven~ion ~ he composite fabric from which protec~ive garments of ~he invention are made contains as the j essential component thereof a continuous film or -j 5 layer of a highly fluorinated ion exchange polymer having sulfonic acid functional groups in the form of 1 multivalent metal salt as set forth below, there being at least one and preferably two fluorine atoms attached to ~he carbon atom to which the sulfonic group is attached~ By ~hiqhly fl~orinated" is meant that the polymer in ion exchange form has at least as many C-F groups as it has C-H groups.
-` The highly fluorinated ion exchange polymers .can be copolymers of fluorinated monomers containing the sulfonic functional group with nonfunctional monomers such as tetra1uoroethylene, trifluoro-ethylene, vinylidene fluoride, chlorotrifluoro-ethylene, etc. ~he polymers are preferably per fluo~inated polymers prepared from perfluoro sulfonic monomers and tetrafluoroethylene. Such polymers and their preparation are now well-known in the art, and are described, e.~O, in U.S. Patent 3,282,875. Such polymers are unaffected by a large variety of ehemicals including typical decontamination systems used after exposure of a protective ga.ment to various toxic and harmful chemicals. Perfluorinated polymers of this type have retained good physical properties after exposure to chlorine sas and strong hot caustic solution within an operating chloralkali cell for times in excess of two years.
In accordance with the present invention, or use as a component of a fabric used in a protective garment or cover, the highly fluorinated ion exchange polymer should be in the form of a . ~ ~
multivalent metal ion salt thereof, in particular, a metal ion salt having a valence of ~2, ~3 or +4.
Y Examples of sui~able metal ions include Ca 2, Mg , Al 3, 2n+2,~e~3, Cet4 ~r+3 Ni~2 ~ 5 and Co 2. Use of ion exchange polymer in such ;-~ multivalent metal ion salt form i~ advantageo~s over use of polymer in the form of the ~ree ~ulfonic aeid ` or Na or R salt thereof, because the : mul~ivalent metal salt form provides improved 10 selectivity of transport rate of water versus toxic ~- organio compounds. More specifically, the multivalent metal sal~s provide better barrier properties against toxic organic compounds. Al~hough ; in some caces the water eransport rate of the lS multivalent metal salts is also lower t~an that of the Na or R forms, in other oases the water transport rate is comparable to that of the Na or K forms. Thus, Ca 2 is a highly preferred metal ion species, as it has a lower transport rate for 20 organic compounds, and a comparable transport rate for water, when compared with the Na an~ K
~orms.
The mul~ivalent metal ion salt forms of the highly fluorinated ion exchange polymer are suitably 25 and conveniently made by ion exchange from the H , Na or X forms with an aqueous solution containing the desired multivalent ion; aqueous solutions of any convenient compound, such as a hydroxide, chloride, nitrate, sulfate, etc., are 30 suitable. Immersion in the solution containing the multivalent metal ion for 2 hours or more is suitable, and 16 to 24 hours is generally ample.
The polymers, films, etc., referred to herein in multivalent metal ion salt form have at 35 least about 30 mol ~ of the sulfonate gr~ups of the ';
S
polymer in the multivalent metal ion salt form, and I generally at least about 90 mol ~ of the sulfona~e `~ groups in such form. The remainder of the groups, if ~j any, are usually in ~he form employed in the ; 5 preparative ion exchange procedure, generally the H , Na or K form.
So as to have a high moisture permeability which will provide a garment having comfortable wearing properties, the highly 1uorinated ion exchange polymer should have an equivalent weight of no great@r than abou~ 2000, preferably no greater than about 1500. (The equivalent weight of such a polymer is the number of grams of polymer which, when in H form, provides one mol of hydrogen ion.) Equivalent weights as low as 1100 and even 1000 provide exceptionally high water vapor transmission rates. The water vapor transmission rates of fabrics con~aining a layer of such polymer is sufficiently high to permit the loss by permeation of enough perspiration so that a person wearing the garment is substantially more comfortable than he would be if wearing an impermeable gar~ent. ~owever, with increase in equivalent weight, the suppleness of the highly fluorinated ion exchange polymer increases, such polymer is more easily extruded in thinner films, and mechanical properties such as flex life improve; sucn factors can be considered when selecting the equivalent weight of the polymer to be used in any particular composite fabric.
The thickness of the layer of nighly fluorinate~ ion e~:change polymer is not critical to the permeation rate of water vapor, which is so high that it is almost independent of the thickness of the film in the range of thickness dealt with herein. In some cases where a garment is to prote~t the wearer -;I 7 from exposur~ to a harmfu.l compound, extremely ~hin layers of the hi~hly fluor inated ion exchange polymer may not be suitable. In those cases where the composite fabric is made by lamination of one or more - 5 component fabrics with a preformed film of the highly fluor inated ion exchange polymer or a precursor polymer thereof, the thickness of the film used is generally in the range of about lO to 125 micrcmeters ~about 0.4 to 5 mils), preferably about lO to 50 micrometers. In those cases where one step in preparation of the composite Xabric is coating a component fabric with a solution of the highly fluorinated ion exchange polymer or a precursor thereof followed by removal of the solvent by drying~
composite fabrics con~aining a thinner layer of highly fluorinated ion exchange polymer, down to about 2.5 micrometers (0.1 mil) thick, and even down to about l micrometer (0.04 mil) thick~ can be made.
For garmen~s intended for protecting the wearer from exposure to a harmful substance, the layer of highly fluorinated ion exchange polymer should be continuous, i~e., it should be substantially free of pinholes, so as to prevent leakaye of organic substances to within the garment. A layer of highly fluorinated ion exchange polymer about i2 tv 50 micrometers (0.5-2 mil) thick is most preferred.
The highly fluorinated ion exchange polymer should be of high enough molecular weight to be film forming and to have adequate toughness to survive conditions of wear without developing leaks which would destroy its integrity, and can be, e.g., linear or branched.
The component fabrics used in making the composite fabric are many ~nd varied in type. ~hey can be, but are not limited to, cotton, rayon, wool, ;8~5 silk, linen, polyester such as polyethylene terepllthalate, polyamides such as polyhexamethylene adipamide, polyhexamethylene decanedicarboxamide, polyhexamethylene dodecanedicarboxamide, poly-epsilon-caproamide or the polyamide of bis-para-aminocyclohexylmethane and dodecanedicarboxylic acid, aramids such as poly-meta-phenylene isophthalamide or poly-para-phenylene terephthalamide, polyolefins such as polyethylene, polypropylene or polytetrafluoro-ethylene, acrylics such as polyacrylonitrile,polybenzimidazoles, polyarylene sulfides, polyarylene-imide-amides, polyphenol-formaldehyde, polyimides, glass, flame-retardant cotton, etc., and blends of two or more of the foregoing. Carbonized cotton, acrylic, etc., fiber or fahric, or other adsorptive materials in any form such as activated carbon, can also be included as components of the composite fabrics. A component fabric can be woven, including e.g., plain and ripstop weaves, knitted, nonwoven, felted, spunbonded, or poromeric fabric, or a fibrillated film, or a film or extrudate made or treated by any means to make it porous or microporous. In the case of such microporous components, those having a pore size of at least about 0.5 micrometer are preferred. Activated carbon or other adsorptive substances can be incorporated in the composite fabric by distributing it in a thin foamed layer included as one component of the composite fabric, or in any one layer or between two layers of said ion exchange polymer, or in any other suitable manner.
It is preferred, but not essential, that all of the components of the composite fabric of the invention, whether they be fabrics or continuous films, should be hydrophilic in nature. The term ~hydrophilic~, when used i~ reference to a film, means that such film will transfer ubstantial amoun~s of water thro~gh the film by absorbing water on one side where the water vapor concentration ls high, and desorbing or evaporating it on ~he opposite side where the water vapor concen~ration is low~ The term ~hydropnilic", when used in reference to a fabric, means tha~ water will spread on the fabric and wick into its porous structure. In the case of ~hose component fabrics listed in ~he previous paragraph which are not hydrophilic, such as microporous polytetrafluoroethylene fabric, they can, if desired, be impregnated throughout the structure and on both surfaces with sufficient hydrophilic polymer to render them, in effect, reinforced hydrophilic films; non-hydrophilic materials when so impregnated and coated lose their non-hydrophilic character and behave as hydrophilic components.
Films of the highly fluorinated ion exchange polymers referred to hereinabove are hydrophilic, and such polymers are suitable for renderin~ hydrophilic those component fabrics which would otherwise be non-hydrophilic.
~he composite fabric can take any of manifold forms. In addition to the layer of highly fluorinated ion exchange polymer, the CQmpOsite fabric further comprises at least one layer o~
component fabric, preferably at least two layers of component fabric which may be the same or different.
When the composite fabric contains at least two layers of component fabric, preferably there will be at least one layer of component fabric on each side of the layer of ion exchange polymer so as to provide protection to the latter from mechanical damage. It is further preferred to use as one of the outermost component abrics a layer of a flame resistant and/or wear-resistan~ fabric, and to fabricate the garment with such co~ponent fabric being on the outside of the garment.
~ preferred embodiment of the composite ~abric is that made from only one layer of component fabric in addition to the layer of highly fluorinated ion e~change polymer . Such composite fabr ic is intended to be used in a protective garment with the layer of h i g h ly f lu or i na ted i on ex ch ange polyme r on - the outside of the garment, and the romponent fabric side of the composite fabric on the inside of the garment; this orientation of the composite fabric presents a smooth, non-porous, barrier surface against a cloud of toxic gas or liquid droplets, and thereby does not absorb or trap any of the toxic substance in pores or interstices of the composite fabric, thus permitting eaey decontamination after exposure to the ~oxic substance. Garments which are fabricated with a porous or microporous surface toward the outside, once contaminated by entrapment of a toxic substance in the pores 9 are ~t least extremely difficult, and often impossible, to decontaminate, and when decontamination is impossible must be carefully disposed of after but a single use. ~hose protective garments of the invention which do not contain a microporous layer are easily decontaminated, and thus provide for multiple reuse of ~he garment. With the indicated orientation of the composite fabric, there is the further advantage that the inner layer of hydrophilic component fabric soaks up perspiration and brings it into direct contact with the outer layer of moisture-transporting ion exchange polymer. Accordingly, ~uch a eomposite fabric is a preferred fabric, in that it possesses advantages over fabrics which contaln a hydrophobic microporous layer as a component thereof~
It should be noted that ~here are some situations in which an exposed ou~er layer of highly 5 fluorinated ion exchange polymer coul~ be damaged, in which case ~he loss of integrity of the barrier layer of the garment would endanger the person wearing the garment; in those situations, it is advisable tha~ a wear-resistant outergarment be worn over the 10 protective garment to aid in precluding damage to the - latter. 5uch overgarments, following contamination, oan either be laundered for reuse, or be of inexpensive, light-weight construction adapted for disearding after expos~re to a toxic ~ubstance.
The composite fabric ~an be made from the component fabrics and either a film of highly fluorinated ion exchange polymer or a fabr ic either melt- or solution-coated with a continuo~s layer of highly fluorinated ion exchange polymer. ~he composite fabric is made in -ome rases by the u~e of heat and either vacuum or pressure, and in other cases by using ~uitable adhesives or meltable or solu~le polymers to adhere the several components toqether. In some cases, the hiqhly fluorin~ted ion exchanqe polymer is maintained in the form of a melt-fabricable precursor, e.g., with functional groups such as -SO2F, during formation of the composite fabric, ~nd after the composite fabric has been made the melt-fabricable precursor is hydrolyzed 0 and con~erted to the metal salt form defined above.
ln those cases where a precursor of a hiqhly fluorinated ion exchange polymer having functional groups such as -~O2F groups is used in combination with a component fabric of polyolefin or polyfluorinated polyo:Lefin, hydrolysis can be under ~.2~
any ~ui~able conditions uch as those used with hydrolysis bath A in ~he examples below, bu~ when ~uch a pol~mer ~s u~ed in combination w~th ~
componen~ ~abric of a nylon, cotton, wool or other 5 polyme~ which may be damaged by vigorous hydrolysis conditions, hydrolysis after fabrication o~ compo5ite fabric prepared therefrom sho~ld be under ~ilder conditions such ~s with ammonium hydroxide. The polymer ean ~l~ernatively ~e put into the form of the sulfonic acid or an alkali metal, ammonium or amine ~alt thereof (preferred amines include p-toluidine and tsiethanolamine~ before forming a composite ~abric therefrom, and in such cases the ~omposite fabric can be prepared by using a small ~mount of a 15 hi~hly fluorinated ion exchange polymer having, e.g.
-COOCH3 functional gro~ps as an adhesive bonding agent, which can be hydrolyzed under mild conditions, or by using other ~ypes of adhesive such as ethylene/vinyl acetate ~ased hot ~elt ~dhesives or 2D two-component epoxy adhesives. Composite fabrics t made without an Ddhesive bonding agent ~re preferred, inas~uch as most bonding agents interfere with passage of water thrQugh the composite fabric, and to the extent used, reduce the active are2 through which water per~eates. If such an adhesive bonding a~ent is used, a hishly fluorinated ion exchange polymer having, e.g., -COOCH3 functional groups is preferred, as it can be hydrolyzed to alkali metal ~`arboxylate fonm, which has a high permeability to water; such polymers are known in the art, e.g., in Belgian Patent 866,121, of D. C. England et al, granted October 19, 1978. The vaLious salt forms of a functional gr~u~ can freely be interoonverted from one to ~nother, ~nd to or fr9m the free acid form, in either a ~omponent ~aterial or ~ composite fabric, a-~
desired, by treatment with a solution containing the ~-~z~
cation of the desired form. The composite fabric can be made from the components in some cases in a single operation, and in other cases by a series of seguential steps.
The composite fabrics described above can be used in fabrication of protective garments by techniques known in the art, including ~ealing of ~eams and joints by use of radio frequency heating or o~her known electronic bonding techniques, or by heat and pressure, in some cases with the aid of adhesives or sealants at the seams and joints to prevent leaks at those points. Garm~nts can also be ~ade by sewing, but in cases where a leak-free construction i desired the sewn seams should also contain a sealant or adhesive~
The composite fabrics and qarments made therefrom are highly permeable to water vapor.
Accordingly, a person wearing such a garment does not ~uffer heat stress which results from interruption of the usual mechanism of loss of body heat by evaporation of ~he water of perspiration, and discomfort from the retention of the water of perspiration within the garment is reduced. While the composite fabrics are also permeable to a few low molecular weight organic compounds such as methanol and etha~ol., and while the permeation rate for an orqanic compound depends on the type of compound and its molecular weight, the permeation rates foz most organic co~lpounds are extremely low and in the case of many organic compounds the composite fabric is - substantially impermeable to the compound~ It is believed that the composite fabrics described herein possess barrier properties against a variéty of hazardous substances, poisonous compounds, blistering ~gents, lachrymators, and irritants. As will be 1~
~een, the composite fabrics permit the passage of large amounts of water ~apor.
~ he protective garment of ~his invention is believed to have the ability to protect ~he wearer against hazardous substances, such as certain toxic organophosphorous compounds tha~ are anticholines~erases, which compounds have the common feature that they o contain a -P OR moiety where R is a Cl to Clo ~lkyl group, and halogenated organic sulfides and amines such as the blistering agents which contain two or more chloroethyl gro~ps, e.g., compounds of the formula ~ClCH2CH2)2Z, where Z is S or NQ, and Q is CH3-, C2H5- or ClCH2C~2 .
been ound that ~he perfluorinated sulfona~e polymer when in ~he form of the calcium or masnesium salt has a lower tranpsrt rate for dimethyl methylphosphonate than the same pol~mer in the hydrogen form or sodium or potassium salt form, and it ic thus believed that garments made of fabric containing æ layer of such polymer in ~he calcium, magnesium, or other multivalent salt for~ will provide better pro~ec~ion asainst other phosphonates such as anticholinesterases, and against other ha~ardous ~ubstances, than garments made of fabric containing a iayer of such polymer in hydrogen, sodium or potassium form. The essential component of the composite fabric used in making the protective garment, a highly fluorinated polymer having multivalent metal ion sulfonate functional groups and at least one fluorine atom attached to each carbon ~tom to which each such ~roup is attached, is believed to be capable in many cases of complexing with and/o~ detoxifyin~ such o~ganic substances. The ability o~ the highly fluorinated ion exchange poly~er to act as a barrier to such organic substances, and additionally to complex with and/or detoxify at least in part that portion which permeates into the barrier, thus substantially retards the rate of penetration of such organic substances into the space within a protective garment of the invention.
The composite fabrics have good mechanical properties, such as toughness, strength and flex life. Both the composite fabrics and garments fabricated from them have good storage stability, such that the garments can be retained for long periods before actual use of them.
To further illustrate the innovative aspects of the present invention, the following examples are provided.
In the examples, water transport rates were measured using an inverted cup technique similar to that of ASTM (American Society for Testing Materials) method E 96-66. Transport rates of substances other than water were measured by a similar technique, except at a different relative humidity as specified. The weight of the cup and its contents was plotted vs. time, and the line which best fitted the linear portion of the curve was drawn; the magnitude of the slope of the line was taken as the mass transfer rate.
In Examples 9, 10, K, L and M, apparatus for continuous preparation of composite fabric was employed which comprises a hollow roll with an internal heater and an internal vacuum source. The hollow roll contained a series of circumferential 5 slots on its surface which allowed the internal vacuum source to dra~ component materials in the direction of the hollow roll. A curved sta~ionary pla~e wi~h a radiant heater faced the top ~urface of the hollow roll with a spacing of about 6 mm (1/4 inch) between their two surfac@s.
During a lamination run, porous release paper was used in contac~ing the hollow roll as a upport material to prevent adherence of any component material to the roll surface and ~o allow vacuum to pull component materials in the direction of the hollow roll. Feed and takeoff Means were provided for the component materials and product. ~n ~he feed means one idler roll of smaller diameter than the hollow roll was proYided for release paper 15 and component materials. The feed and takeoff means were positioned ~o allow component materials to pass around the hollow roll over a length of about S/6 of its circumference. A further îdler roll was provided for the release paper allowing its separation from ~he other materials. Takeoff means were provided for the release paper and a composite fabric.
Exam~les 1 and 2, and ComParatiVe Exam A film of a copolymer of tetrafluoroethylene (herein referred to as TFE) ~nd perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) ~herein referred to as PSEPVE), having an equivalent weight of 1200 and a thickness of 0.13 mm (5 mils) was hydrolyzed to -SO3K form with a hydrolysis bath consisting of 15~ by wt. of potassium hydroxide, 25% by wt. of dimethylsulfoxide and 60~ by wt. of water (herein referred to as hydrolysis bath A), and converted to ~S03H form by washing with aqueous nitric acid. A piece of this film was retained (Comp. Æx. A). Other pieces of the film were separately ~onverted to salts of various metal ions by immersion for ca. 16 hours in aqueous ~olutions of NaOH (20 9/1), ROH (30 g/l)~ CaC12 (29 9 of CaC12.2H2O/l), and M~C12(40 ~ of S MgC12.6H2O~l). Rates o~ transport of dimethyl ~ethylphosphonate (herein referred to as DMt~lP), CH3PO(OCH3~, a chemical compound employed as a sim~lant of anticholinesterases, were measured. The resul ts are sunuT ar i zed in Table I .
Table_ ~
- DMMP wt .DMMP
loss intransport Me tal 6 h ra te Ex. Ion Conditions (g) (g/m2.24 h) 1 Ca~' 24~C! 22% RH 0.G192 17.5 15 2 Mg+2 23.5C,2$.3~ RH 0.0310 25.5 A H 24C, 22~ RH 2.6833 3450 B Na 24C, 22~ 12H 2.6500 375Q
C K 24C, 22~ R~ 0. B772 1650 Examples 3 and 4,_and Comparative l~xample D
2n Pieces of a film of ~FE/PSEPVE copolymer having an equivalent weight of 1350 and a thickress of 0.13 ~m were hydrolyzed and separately converted to salts of vario~s metal ions as described in the first group of examples. Transport ra~es for DMMP
25 were measured, and are sununarized in ~able II.
T a DMMP wt. D~
loss intr~nsport Me tal 6 h ra te 3:x. Ion onditions (g) (g/m2.24 h) 30 3 Ca+2 22C, 21~6~ RH0.0424 18.5 4 Mg ~ 24C, 32% RH 0.0064 601 D Na 23C, 23.4~ RH1.2365 1720 ~_ ,7 p f~ g ;r~ , 7-;
lEI
~m~ 5 and ~ nd Co~r _ Pieces ~f a film of TFE~PS~PV~ copslymer having an equivalent weigh~ of 1~50 and a ~hiekness of 0.05 mm (2 mils) were hydrolyzed and separately converted to sal~s of metal ions as described in the first groups of examples. Transport rate~ for water were measureds and are summarized in Table III.
Tab X
Water transport Me ~al ra te - Ex~ Ion Conditions(g/m2.24 h) S Ca~ 25C, 30~ RH14,700 6 ~9+ 25C, 30% RH14,800 E ~ 25., 30~ R~ 23,500 ~ Na 25C, 30% RH 12,100 Exam~les 7 and~ and Comparative ~xamples G~ H and J
In order to ascer~ain the effect of water on DMMP transport, experiments were carried ou~ using a cell in which the ilm to be tested was in contact with ~MMP on one side (top) and distilled water on ~he other (kottom). The upper compartment Df the cell was closed with a loose fi~ting glass cover, and the lower compar~ment was eguipped with a small port, so that samples could be periodically removed from each compartment for analysis by gas chromatography.
The film sample was clamped between the two compartments with a neoprene gasket on each ~ide of the film to be tested. The exposed area of film in the test was circular, 7.62 cm (3 in) in diameter.
The bottom compartment wa5 filled with water tca.
185 ml), so that it would contact the lower surface of the fiLm, and the water was stirred by a magnetically impelled stirrins bar. In the top compartment was placed 50 ml of DMMP. ~dditional ~amples of ~ilm like those of Exs. 1 and 2 ~nd Comp.
Exs, A~ B and C were thus ~ested over a peri~d of 6-6.5 hours.
For ea~h time of analysi , the number of grams of DMMP that had passed throuqh the membrane into the water oompartment was calculated by using the equations:
lOOD _ = B and loo ~WD-D) ~ W H) (wD-D) ~ ~
where ~ is the weight percen~ DMMP in the b~ttom IwaterJ compartment, ~ he weight per~ent DMMP in the top eo~partmentt WD is the original weight.of DMMP in the top compartment (here, 56.3 grams), ~
is the original weight of distilled water ~here, lB5 grams), D is ~he number of grams of DMMP that have diffused into the bottom compartment, and H is the number of grams of water that have pa~sed through the mem~rane into the DMMP compartment. In this determination, the ~moun~ of water and DMMP in the fiLm was ignored, ~s ~here is no easy way to 20 determine those amounts. These simultaneous equations were ~olved for D and H. D was plotted against time of measurement ~hours), and a mass tr~nsfer rate was calculated by finding the slope of the best-fit line ~or ~he linear portion of the ~urve, multiplying by 24 ~nd dividing by the exposed film area (45.60xlO m ~. The results are summarized in Table I~.
. 35 ~o Table V
Meta7 Transport Rate ~g~m2.24 h~
~:x. Ion DMMP~MMP
7 c~2 495n 5930 5 8 Mg 17100 10400 G H 14200* 42900 H Na 17000 15000 ~Rate was significant1y non1inear; aver3ge rate 1~ wa5 19600.
The test described in thi~ set o~ examples is a very severe test, and embodies conditions r~ot necessarily encountered during actua1 use. In any case, it is noted that the Ca+2 foxm of the po1ymer exhibited significantly lower transport rate of D~
than the other forms teste~.
Using apparatus as described hereinabove, a oomposite fabric was made by heat laminating a film Of TFE/PSEPVE copolymer, having an e~uivalent weight of 1350 and a thickness of .036 mm 11.4 mils), tha~
had been hydrolyzed on only one surface to a depth of 0.015 mm, and a ~omponent woven fabric of a blend of 95~ poly-meta-phenylene isophthalamide fibers and 5%
poly-para~phenylene terephthalamide fibers, said abric having a basis wei~ht of 150 g/m2;
lamination was carried out with the component fabric against the release paper, and the unhydrolyzed side of the film against the component fabric. The radiant heater on the curved plate was at 360C, the hollow roll was at 240~C and was operated at a vacuum of 7.1 x 104 pascals (21 inches of mercury), and the line speed was 0.3 m/min (1 ft/min). ~he produc~
~as immersed for 48 hours in a 1:1 volume mixture o~
conc. ammonium hydroxide and methanol to hydrolyze ~SO~F groups, rinsed with water, immersed for 5 hours in a 2 . 8S% by wt. aqueous solution of sodium chloride to ion-exchange the functional groups to -SO3Na form, again rinsed wi~h water, and dried, to provide a composite fabric in Na~ form. Portions of the composite fabric in Na form were separately immersed in aqueous 2N hydrochloric acid for 5.5 hrs to provide fabric in H form, and in aqueous potassium hydroxide solution (30 9 RO~l) for ca. lS
hrs to provide fabric in K fsrm~ A portion of the ccmposite abric in Na form was i~mersed for l9 hours in a 5.48% by wt. aqueous solution of CaC12.2H2O to ion-exchange Na ~or Ca 2;
dnalysis by atomic absorption of the extracted metal ions indicated that the composite fabric contained 0.33% by wt. Ca~ and 230 ppm (wt.) Na~, and ~hat in a minimum of 94 ~ol % of the sulfonate groups, sodium had bee~ replaced by calcium. Another portion of the composite fabric in Na+ form was immersed for 19 hrs in a 7.41% by wt. aqueous solution of ~gCl2.6H2O to exchange Na for Mg : an~lysis indicated that the composite fabric contained 0.29%
by wt. ~9 and 240 ppm (wt.) Na , and that in a minimum of 95 mol ~ of the sulfonate groups, sodium had been replaced by magnesium.
Transport rates for DMMP and water were measured using test cells having two compartments and a port in each compartment for use in removing saMples for analysis. The exposed area of composite fabric in the test cell was 20.27 cm2. Test samples were checked for leaks after mounting in a test cell by attaching a water-containing bubbler to the top compartment, and raising the air pressure 61ightly in the bottom compartment; if bubbles appeared the ~ample was rejected. In the compartment adjacent the component fabric ~ide of the composite fabric was placed 30 ml of distilled water, and in the compartment adjacent the componen~ film side of the composite fabric was placed 13.5 g of DMMP. The ports were closed with rubber caps, and the cell was mounted on a shaker to assure that adequate mixing occurred in each compartment~ Samples removed periodically from each compartment were analyzed by qas chromatography. The amounts of wa~er and DM~.P
transported were calculated with the formula as - ~escribed in the pre~ious set of examples, using Ww=3Q g and ~D=13.5 9. Transpor~ rates were then ~alculated, using 20.27 x 10 4m2 as the exposed area. The results are summarized in Table V.
Table V
DMMP Water Test DMMP trans- Wa~er trans-Dur= trans- port trans- port Me~al ation ported rate ported rate Ex. Ion (hours) (9) (g/m2.24h) (9) (g/m2.24h) 20 9 Ca~ 6 . 51. 542800 5. 60 7430 6.5 1.492730 5.476960 M9~2 6 . 53 . 496070 6. 87 9010 6 2 . 755200 S .49 9110 6 2. 034410 7. 91 1~000 25 ~ R+ 6 . S2 . 414350 7. 97 3320 6 2. 614990 7. 54 12Ç~0 6 3.256310 3.95 5830 L Na+ 4.5 3.536820 6.16 13100 6 2.326750 15.530900 M H~ 2 2.1411800 4.64 58900 3.5 4.038~70 8.33 24700 6 6.1211400 4.56 ~470 Exam les 11-20 and Com~arative Examples N, P and Q
_ P
Addi~iona1 p i eces of the film in -S03H
form of Exs. 1-2 were separately converted to salts 35 of var ious other metal ions by inunersion in a~eous ~ 3 sc:lutions of Al(N03)3 (100-0 9 of Al (N03) 3- 9H2()~1), BaC12 ( g BaC12.2H20~ e(NC\~)3 ~77.~ ~ c)f CelN03)3.6il~0/1, not all dissolved~, 5 CoCl2(9502 9 of CoC12.6~12C)fl), CrC13~71.0 9 of CrC13. 6H20/1), NiS04 (105 . 2 9 of NiS0,~ . 6H2t)/1), ZnC12 (45 . 3 g of ZnC12/1), and Ce (N03) 4 (aqueous solution 0. 5N in Ce (N03) 4 and 2N in HN03). Rates of transport of DMMP and water were measured, and the results are summarized in Table VI. The results for wa~er are expressed as water vapor permeabilities (averages o~ two to four runs measured at different relative humidi~ies) inasmuch as they incorporate into the numerical values reported the relative humidity (R8). The water vapor permeab~lity P is obtained from the water transport rate R (in g/cm2.h) with the formula P = ~ . t V
20 where t is the sample thickness (cm) and V is the di~ference in vapor pressure of water on the two sides of the sample, which is determined by the formula V ~ ) (Vt) where R~ is, the relative humidity expressed as a decimal, and Vt is the vapor pressure of water at the temperature o the experiment, expressed in torr.
k;~
TABLE VI
DMMP
~ransport Water vapor Metal rate* permeability Ex~ Ion (g~m2.24h) (g.cm/cm~.h.torr) 5 11 Al+3 10.6*
12 ~a+2 34.4 2.24 x 10-5 13 Ce+3 14.4 2.96 x 10 5 14 Co~2 5,93 4.67 x 10 5 15 Cr~3 568 3.66 x 10 5 10 1~ Ni 80.6 4.44 x 10 5 17 zn+2 4~ 4.65 x 10 5 1~ Ce+4 336* 3.06 x 10-5 19 Ca~2 20.C 4.18 x 10-5 20 Mg 25.5 4.83 x 10 5 15 N ~a 3920 4.31 x 10 5 P H 3240 6.46 x 10 5 Q K~ 1650 * Averages of 2 to 4 values (single value ln Exo 16 measured at 21.5 to 2~C and 14 to 30~ RH. The rate is over a 5- to 6.5-hour period, except for Ex. 11, which is over a 1- to 2-hour period, after which there was a net gain in weight, apparently due to uncontrolled high humidity. For Ex. 18, a transport rate of 1200 in one run is presumed to be incorrect due to leak in f ilm.
Exam~es 21 and 22 and Comparative Examples R, S and T
25 Additional pieces of the films of Exs. 1 and
Protective Garment of Composite Fabric Containing Sulpho~ated Fluoropolymer Film with Metal Ion Groups Background of the Invention Protective clothing of many types is now well-known for many and varied uses in protecting people from fire and harmful substances, such as suits for industrial workers, flame- and fire-resistant suits for firemen, forest fire fighters, race car drivers and airplane pilots, and suits for use by military personnel. Garments include not only complete, hermetic suits, but also individual garments such as trousers, jackets, gloves, boots, hats, head coverings, masks, etc.
Regulations restricting exposure to hazardous environments of various kinds, such as the Occupational Safety and ~ealth Act, make it increasingly necessary to have bettar and more effective kinds of protective garments.
Such garments presently available are almost invariably of thick construction and heavy in weight, and are often fabricated at least in part from materials impermeable to water or water vapor, such as natural and synthetic rubbers and elastomers, chlorinated rubbers, etc. In the case of garments impermeable to water vapor, there is considerable discomfort to those wearing them, especially when the garments are of the hermetic variety, because of the entrapment of perspiration and body heat. Entrapment of heat and perspiration results in considerable discomfort of itself, and the heat stress which results from the prevention of loss of heat by the ordinary mechanism of evaporation of perspiration can ., ~, rapidly reach a dangerous stage of hea~ prostral:ion ~or the person wear ing the garment .
It is an object of this invention ~o provide improved protective garments which possess the 5 abili'cy to permi~ 'che passage of water vapor through the ~abric of the garment, and ~hereby pro~ide improved comfort for the person wearing ~he garment.
It is another object of this invention to provide improved protective garments which possess not only the ability to permit the passage of water vapor ~hrough the fabric, but also the ability to act as a stable barrier to the passage of most organic substances, including toxic compounds, through the fabric. Such garments could protect those exposed to a wide variety of org nic or harmful compounds.
; It is a further objec~ to provide such garments which are thin and light weight and which thus will more readily permit loss of heat by virtue of their light weight construction.
Summarv of the Invention Briefly, the invention comprises using as a component of the fabric of a protective garment a layer of an ion exchange polymer, preerably a semipermeable fluorinated ion exchange polymer having sulfonic acid functional groups in the form of bi-, tri- or tetravalent metal salt. By ~semipermeable"
is meant permeable to water vapor but substantially impermeable to most organic substances.
More specifically, the present invention provides for the use in protective clothing of a composite fabric, said fabric containing as the essential component thereof a continuous film of a highly fluorinated ion exchange polymer having sulfonic acid metal ion salt functional groups, said metal ion having a valence of +2, +3 or ~4, there s q 3 being at least one ~luorine atom attached to each carbon atom to which each said unctional group is ; attached, said polymer having an equivalent weight no qreater than about 2000.
~here are also provided accordiny ~o the invention a protective yarment and a waterproof ; protective cover fabrica~ed at lea~t in part from the composite fabric described in the previous paragraph.
There is fur~her provided according to ~che 10 invention a process wherein (a) water permeates from a first space adjacent a first side o a barrier to a second space adjacent the second side of said barrier, said barrier having as the essential component thereof a continuous film of a highly - 15 fluorinated ion exchange polymer having sulfonic acid metal ion salt functional groups, said metal ion having a valence of +2, +3 or +4, there being at least one fluor ine atom attached to each carbon atom to which each said sulfonic acid group is attached, 20 said polymer having an equivalent weight no greater ~han about 2000, and ~b~ a hazardous substance, said substance being a toxic organophosphorus co~pound o having a -P OR moiety wherein R is a Cl to Clo alkyl group, or a blistering agent which contains ~wo or more chloroethyl groups, present in said second space (i) permeates only slowly into said barrier and (ii) that portion of said hazardous substance which 30 permeates into said barrier is detoxified at least in part by said polymer, whereby the rate of penetration of said hazardous substance into said first ~pace is substantially decreased.
. 35 ` Detailed De_cri~_ion of the_Inven~ion ~ he composite fabric from which protec~ive garments of ~he invention are made contains as the j essential component thereof a continuous film or -j 5 layer of a highly fluorinated ion exchange polymer having sulfonic acid functional groups in the form of 1 multivalent metal salt as set forth below, there being at least one and preferably two fluorine atoms attached to ~he carbon atom to which the sulfonic group is attached~ By ~hiqhly fl~orinated" is meant that the polymer in ion exchange form has at least as many C-F groups as it has C-H groups.
-` The highly fluorinated ion exchange polymers .can be copolymers of fluorinated monomers containing the sulfonic functional group with nonfunctional monomers such as tetra1uoroethylene, trifluoro-ethylene, vinylidene fluoride, chlorotrifluoro-ethylene, etc. ~he polymers are preferably per fluo~inated polymers prepared from perfluoro sulfonic monomers and tetrafluoroethylene. Such polymers and their preparation are now well-known in the art, and are described, e.~O, in U.S. Patent 3,282,875. Such polymers are unaffected by a large variety of ehemicals including typical decontamination systems used after exposure of a protective ga.ment to various toxic and harmful chemicals. Perfluorinated polymers of this type have retained good physical properties after exposure to chlorine sas and strong hot caustic solution within an operating chloralkali cell for times in excess of two years.
In accordance with the present invention, or use as a component of a fabric used in a protective garment or cover, the highly fluorinated ion exchange polymer should be in the form of a . ~ ~
multivalent metal ion salt thereof, in particular, a metal ion salt having a valence of ~2, ~3 or +4.
Y Examples of sui~able metal ions include Ca 2, Mg , Al 3, 2n+2,~e~3, Cet4 ~r+3 Ni~2 ~ 5 and Co 2. Use of ion exchange polymer in such ;-~ multivalent metal ion salt form i~ advantageo~s over use of polymer in the form of the ~ree ~ulfonic aeid ` or Na or R salt thereof, because the : mul~ivalent metal salt form provides improved 10 selectivity of transport rate of water versus toxic ~- organio compounds. More specifically, the multivalent metal sal~s provide better barrier properties against toxic organic compounds. Al~hough ; in some caces the water eransport rate of the lS multivalent metal salts is also lower t~an that of the Na or R forms, in other oases the water transport rate is comparable to that of the Na or K forms. Thus, Ca 2 is a highly preferred metal ion species, as it has a lower transport rate for 20 organic compounds, and a comparable transport rate for water, when compared with the Na an~ K
~orms.
The mul~ivalent metal ion salt forms of the highly fluorinated ion exchange polymer are suitably 25 and conveniently made by ion exchange from the H , Na or X forms with an aqueous solution containing the desired multivalent ion; aqueous solutions of any convenient compound, such as a hydroxide, chloride, nitrate, sulfate, etc., are 30 suitable. Immersion in the solution containing the multivalent metal ion for 2 hours or more is suitable, and 16 to 24 hours is generally ample.
The polymers, films, etc., referred to herein in multivalent metal ion salt form have at 35 least about 30 mol ~ of the sulfonate gr~ups of the ';
S
polymer in the multivalent metal ion salt form, and I generally at least about 90 mol ~ of the sulfona~e `~ groups in such form. The remainder of the groups, if ~j any, are usually in ~he form employed in the ; 5 preparative ion exchange procedure, generally the H , Na or K form.
So as to have a high moisture permeability which will provide a garment having comfortable wearing properties, the highly 1uorinated ion exchange polymer should have an equivalent weight of no great@r than abou~ 2000, preferably no greater than about 1500. (The equivalent weight of such a polymer is the number of grams of polymer which, when in H form, provides one mol of hydrogen ion.) Equivalent weights as low as 1100 and even 1000 provide exceptionally high water vapor transmission rates. The water vapor transmission rates of fabrics con~aining a layer of such polymer is sufficiently high to permit the loss by permeation of enough perspiration so that a person wearing the garment is substantially more comfortable than he would be if wearing an impermeable gar~ent. ~owever, with increase in equivalent weight, the suppleness of the highly fluorinated ion exchange polymer increases, such polymer is more easily extruded in thinner films, and mechanical properties such as flex life improve; sucn factors can be considered when selecting the equivalent weight of the polymer to be used in any particular composite fabric.
The thickness of the layer of nighly fluorinate~ ion e~:change polymer is not critical to the permeation rate of water vapor, which is so high that it is almost independent of the thickness of the film in the range of thickness dealt with herein. In some cases where a garment is to prote~t the wearer -;I 7 from exposur~ to a harmfu.l compound, extremely ~hin layers of the hi~hly fluor inated ion exchange polymer may not be suitable. In those cases where the composite fabric is made by lamination of one or more - 5 component fabrics with a preformed film of the highly fluor inated ion exchange polymer or a precursor polymer thereof, the thickness of the film used is generally in the range of about lO to 125 micrcmeters ~about 0.4 to 5 mils), preferably about lO to 50 micrometers. In those cases where one step in preparation of the composite Xabric is coating a component fabric with a solution of the highly fluorinated ion exchange polymer or a precursor thereof followed by removal of the solvent by drying~
composite fabrics con~aining a thinner layer of highly fluorinated ion exchange polymer, down to about 2.5 micrometers (0.1 mil) thick, and even down to about l micrometer (0.04 mil) thick~ can be made.
For garmen~s intended for protecting the wearer from exposure to a harmful substance, the layer of highly fluorinated ion exchange polymer should be continuous, i~e., it should be substantially free of pinholes, so as to prevent leakaye of organic substances to within the garment. A layer of highly fluorinated ion exchange polymer about i2 tv 50 micrometers (0.5-2 mil) thick is most preferred.
The highly fluorinated ion exchange polymer should be of high enough molecular weight to be film forming and to have adequate toughness to survive conditions of wear without developing leaks which would destroy its integrity, and can be, e.g., linear or branched.
The component fabrics used in making the composite fabric are many ~nd varied in type. ~hey can be, but are not limited to, cotton, rayon, wool, ;8~5 silk, linen, polyester such as polyethylene terepllthalate, polyamides such as polyhexamethylene adipamide, polyhexamethylene decanedicarboxamide, polyhexamethylene dodecanedicarboxamide, poly-epsilon-caproamide or the polyamide of bis-para-aminocyclohexylmethane and dodecanedicarboxylic acid, aramids such as poly-meta-phenylene isophthalamide or poly-para-phenylene terephthalamide, polyolefins such as polyethylene, polypropylene or polytetrafluoro-ethylene, acrylics such as polyacrylonitrile,polybenzimidazoles, polyarylene sulfides, polyarylene-imide-amides, polyphenol-formaldehyde, polyimides, glass, flame-retardant cotton, etc., and blends of two or more of the foregoing. Carbonized cotton, acrylic, etc., fiber or fahric, or other adsorptive materials in any form such as activated carbon, can also be included as components of the composite fabrics. A component fabric can be woven, including e.g., plain and ripstop weaves, knitted, nonwoven, felted, spunbonded, or poromeric fabric, or a fibrillated film, or a film or extrudate made or treated by any means to make it porous or microporous. In the case of such microporous components, those having a pore size of at least about 0.5 micrometer are preferred. Activated carbon or other adsorptive substances can be incorporated in the composite fabric by distributing it in a thin foamed layer included as one component of the composite fabric, or in any one layer or between two layers of said ion exchange polymer, or in any other suitable manner.
It is preferred, but not essential, that all of the components of the composite fabric of the invention, whether they be fabrics or continuous films, should be hydrophilic in nature. The term ~hydrophilic~, when used i~ reference to a film, means that such film will transfer ubstantial amoun~s of water thro~gh the film by absorbing water on one side where the water vapor concentration ls high, and desorbing or evaporating it on ~he opposite side where the water vapor concen~ration is low~ The term ~hydropnilic", when used in reference to a fabric, means tha~ water will spread on the fabric and wick into its porous structure. In the case of ~hose component fabrics listed in ~he previous paragraph which are not hydrophilic, such as microporous polytetrafluoroethylene fabric, they can, if desired, be impregnated throughout the structure and on both surfaces with sufficient hydrophilic polymer to render them, in effect, reinforced hydrophilic films; non-hydrophilic materials when so impregnated and coated lose their non-hydrophilic character and behave as hydrophilic components.
Films of the highly fluorinated ion exchange polymers referred to hereinabove are hydrophilic, and such polymers are suitable for renderin~ hydrophilic those component fabrics which would otherwise be non-hydrophilic.
~he composite fabric can take any of manifold forms. In addition to the layer of highly fluorinated ion exchange polymer, the CQmpOsite fabric further comprises at least one layer o~
component fabric, preferably at least two layers of component fabric which may be the same or different.
When the composite fabric contains at least two layers of component fabric, preferably there will be at least one layer of component fabric on each side of the layer of ion exchange polymer so as to provide protection to the latter from mechanical damage. It is further preferred to use as one of the outermost component abrics a layer of a flame resistant and/or wear-resistan~ fabric, and to fabricate the garment with such co~ponent fabric being on the outside of the garment.
~ preferred embodiment of the composite ~abric is that made from only one layer of component fabric in addition to the layer of highly fluorinated ion e~change polymer . Such composite fabr ic is intended to be used in a protective garment with the layer of h i g h ly f lu or i na ted i on ex ch ange polyme r on - the outside of the garment, and the romponent fabric side of the composite fabric on the inside of the garment; this orientation of the composite fabric presents a smooth, non-porous, barrier surface against a cloud of toxic gas or liquid droplets, and thereby does not absorb or trap any of the toxic substance in pores or interstices of the composite fabric, thus permitting eaey decontamination after exposure to the ~oxic substance. Garments which are fabricated with a porous or microporous surface toward the outside, once contaminated by entrapment of a toxic substance in the pores 9 are ~t least extremely difficult, and often impossible, to decontaminate, and when decontamination is impossible must be carefully disposed of after but a single use. ~hose protective garments of the invention which do not contain a microporous layer are easily decontaminated, and thus provide for multiple reuse of ~he garment. With the indicated orientation of the composite fabric, there is the further advantage that the inner layer of hydrophilic component fabric soaks up perspiration and brings it into direct contact with the outer layer of moisture-transporting ion exchange polymer. Accordingly, ~uch a eomposite fabric is a preferred fabric, in that it possesses advantages over fabrics which contaln a hydrophobic microporous layer as a component thereof~
It should be noted that ~here are some situations in which an exposed ou~er layer of highly 5 fluorinated ion exchange polymer coul~ be damaged, in which case ~he loss of integrity of the barrier layer of the garment would endanger the person wearing the garment; in those situations, it is advisable tha~ a wear-resistant outergarment be worn over the 10 protective garment to aid in precluding damage to the - latter. 5uch overgarments, following contamination, oan either be laundered for reuse, or be of inexpensive, light-weight construction adapted for disearding after expos~re to a toxic ~ubstance.
The composite fabric ~an be made from the component fabrics and either a film of highly fluorinated ion exchange polymer or a fabr ic either melt- or solution-coated with a continuo~s layer of highly fluorinated ion exchange polymer. ~he composite fabric is made in -ome rases by the u~e of heat and either vacuum or pressure, and in other cases by using ~uitable adhesives or meltable or solu~le polymers to adhere the several components toqether. In some cases, the hiqhly fluorin~ted ion exchanqe polymer is maintained in the form of a melt-fabricable precursor, e.g., with functional groups such as -SO2F, during formation of the composite fabric, ~nd after the composite fabric has been made the melt-fabricable precursor is hydrolyzed 0 and con~erted to the metal salt form defined above.
ln those cases where a precursor of a hiqhly fluorinated ion exchange polymer having functional groups such as -~O2F groups is used in combination with a component fabric of polyolefin or polyfluorinated polyo:Lefin, hydrolysis can be under ~.2~
any ~ui~able conditions uch as those used with hydrolysis bath A in ~he examples below, bu~ when ~uch a pol~mer ~s u~ed in combination w~th ~
componen~ ~abric of a nylon, cotton, wool or other 5 polyme~ which may be damaged by vigorous hydrolysis conditions, hydrolysis after fabrication o~ compo5ite fabric prepared therefrom sho~ld be under ~ilder conditions such ~s with ammonium hydroxide. The polymer ean ~l~ernatively ~e put into the form of the sulfonic acid or an alkali metal, ammonium or amine ~alt thereof (preferred amines include p-toluidine and tsiethanolamine~ before forming a composite ~abric therefrom, and in such cases the ~omposite fabric can be prepared by using a small ~mount of a 15 hi~hly fluorinated ion exchange polymer having, e.g.
-COOCH3 functional gro~ps as an adhesive bonding agent, which can be hydrolyzed under mild conditions, or by using other ~ypes of adhesive such as ethylene/vinyl acetate ~ased hot ~elt ~dhesives or 2D two-component epoxy adhesives. Composite fabrics t made without an Ddhesive bonding agent ~re preferred, inas~uch as most bonding agents interfere with passage of water thrQugh the composite fabric, and to the extent used, reduce the active are2 through which water per~eates. If such an adhesive bonding a~ent is used, a hishly fluorinated ion exchange polymer having, e.g., -COOCH3 functional groups is preferred, as it can be hydrolyzed to alkali metal ~`arboxylate fonm, which has a high permeability to water; such polymers are known in the art, e.g., in Belgian Patent 866,121, of D. C. England et al, granted October 19, 1978. The vaLious salt forms of a functional gr~u~ can freely be interoonverted from one to ~nother, ~nd to or fr9m the free acid form, in either a ~omponent ~aterial or ~ composite fabric, a-~
desired, by treatment with a solution containing the ~-~z~
cation of the desired form. The composite fabric can be made from the components in some cases in a single operation, and in other cases by a series of seguential steps.
The composite fabrics described above can be used in fabrication of protective garments by techniques known in the art, including ~ealing of ~eams and joints by use of radio frequency heating or o~her known electronic bonding techniques, or by heat and pressure, in some cases with the aid of adhesives or sealants at the seams and joints to prevent leaks at those points. Garm~nts can also be ~ade by sewing, but in cases where a leak-free construction i desired the sewn seams should also contain a sealant or adhesive~
The composite fabrics and qarments made therefrom are highly permeable to water vapor.
Accordingly, a person wearing such a garment does not ~uffer heat stress which results from interruption of the usual mechanism of loss of body heat by evaporation of ~he water of perspiration, and discomfort from the retention of the water of perspiration within the garment is reduced. While the composite fabrics are also permeable to a few low molecular weight organic compounds such as methanol and etha~ol., and while the permeation rate for an orqanic compound depends on the type of compound and its molecular weight, the permeation rates foz most organic co~lpounds are extremely low and in the case of many organic compounds the composite fabric is - substantially impermeable to the compound~ It is believed that the composite fabrics described herein possess barrier properties against a variéty of hazardous substances, poisonous compounds, blistering ~gents, lachrymators, and irritants. As will be 1~
~een, the composite fabrics permit the passage of large amounts of water ~apor.
~ he protective garment of ~his invention is believed to have the ability to protect ~he wearer against hazardous substances, such as certain toxic organophosphorous compounds tha~ are anticholines~erases, which compounds have the common feature that they o contain a -P OR moiety where R is a Cl to Clo ~lkyl group, and halogenated organic sulfides and amines such as the blistering agents which contain two or more chloroethyl gro~ps, e.g., compounds of the formula ~ClCH2CH2)2Z, where Z is S or NQ, and Q is CH3-, C2H5- or ClCH2C~2 .
been ound that ~he perfluorinated sulfona~e polymer when in ~he form of the calcium or masnesium salt has a lower tranpsrt rate for dimethyl methylphosphonate than the same pol~mer in the hydrogen form or sodium or potassium salt form, and it ic thus believed that garments made of fabric containing æ layer of such polymer in ~he calcium, magnesium, or other multivalent salt for~ will provide better pro~ec~ion asainst other phosphonates such as anticholinesterases, and against other ha~ardous ~ubstances, than garments made of fabric containing a iayer of such polymer in hydrogen, sodium or potassium form. The essential component of the composite fabric used in making the protective garment, a highly fluorinated polymer having multivalent metal ion sulfonate functional groups and at least one fluorine atom attached to each carbon ~tom to which each such ~roup is attached, is believed to be capable in many cases of complexing with and/o~ detoxifyin~ such o~ganic substances. The ability o~ the highly fluorinated ion exchange poly~er to act as a barrier to such organic substances, and additionally to complex with and/or detoxify at least in part that portion which permeates into the barrier, thus substantially retards the rate of penetration of such organic substances into the space within a protective garment of the invention.
The composite fabrics have good mechanical properties, such as toughness, strength and flex life. Both the composite fabrics and garments fabricated from them have good storage stability, such that the garments can be retained for long periods before actual use of them.
To further illustrate the innovative aspects of the present invention, the following examples are provided.
In the examples, water transport rates were measured using an inverted cup technique similar to that of ASTM (American Society for Testing Materials) method E 96-66. Transport rates of substances other than water were measured by a similar technique, except at a different relative humidity as specified. The weight of the cup and its contents was plotted vs. time, and the line which best fitted the linear portion of the curve was drawn; the magnitude of the slope of the line was taken as the mass transfer rate.
In Examples 9, 10, K, L and M, apparatus for continuous preparation of composite fabric was employed which comprises a hollow roll with an internal heater and an internal vacuum source. The hollow roll contained a series of circumferential 5 slots on its surface which allowed the internal vacuum source to dra~ component materials in the direction of the hollow roll. A curved sta~ionary pla~e wi~h a radiant heater faced the top ~urface of the hollow roll with a spacing of about 6 mm (1/4 inch) between their two surfac@s.
During a lamination run, porous release paper was used in contac~ing the hollow roll as a upport material to prevent adherence of any component material to the roll surface and ~o allow vacuum to pull component materials in the direction of the hollow roll. Feed and takeoff Means were provided for the component materials and product. ~n ~he feed means one idler roll of smaller diameter than the hollow roll was proYided for release paper 15 and component materials. The feed and takeoff means were positioned ~o allow component materials to pass around the hollow roll over a length of about S/6 of its circumference. A further îdler roll was provided for the release paper allowing its separation from ~he other materials. Takeoff means were provided for the release paper and a composite fabric.
Exam~les 1 and 2, and ComParatiVe Exam A film of a copolymer of tetrafluoroethylene (herein referred to as TFE) ~nd perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) ~herein referred to as PSEPVE), having an equivalent weight of 1200 and a thickness of 0.13 mm (5 mils) was hydrolyzed to -SO3K form with a hydrolysis bath consisting of 15~ by wt. of potassium hydroxide, 25% by wt. of dimethylsulfoxide and 60~ by wt. of water (herein referred to as hydrolysis bath A), and converted to ~S03H form by washing with aqueous nitric acid. A piece of this film was retained (Comp. Æx. A). Other pieces of the film were separately ~onverted to salts of various metal ions by immersion for ca. 16 hours in aqueous ~olutions of NaOH (20 9/1), ROH (30 g/l)~ CaC12 (29 9 of CaC12.2H2O/l), and M~C12(40 ~ of S MgC12.6H2O~l). Rates o~ transport of dimethyl ~ethylphosphonate (herein referred to as DMt~lP), CH3PO(OCH3~, a chemical compound employed as a sim~lant of anticholinesterases, were measured. The resul ts are sunuT ar i zed in Table I .
Table_ ~
- DMMP wt .DMMP
loss intransport Me tal 6 h ra te Ex. Ion Conditions (g) (g/m2.24 h) 1 Ca~' 24~C! 22% RH 0.G192 17.5 15 2 Mg+2 23.5C,2$.3~ RH 0.0310 25.5 A H 24C, 22~ RH 2.6833 3450 B Na 24C, 22~ 12H 2.6500 375Q
C K 24C, 22~ R~ 0. B772 1650 Examples 3 and 4,_and Comparative l~xample D
2n Pieces of a film of ~FE/PSEPVE copolymer having an equivalent weight of 1350 and a thickress of 0.13 ~m were hydrolyzed and separately converted to salts of vario~s metal ions as described in the first group of examples. Transport ra~es for DMMP
25 were measured, and are sununarized in ~able II.
T a DMMP wt. D~
loss intr~nsport Me tal 6 h ra te 3:x. Ion onditions (g) (g/m2.24 h) 30 3 Ca+2 22C, 21~6~ RH0.0424 18.5 4 Mg ~ 24C, 32% RH 0.0064 601 D Na 23C, 23.4~ RH1.2365 1720 ~_ ,7 p f~ g ;r~ , 7-;
lEI
~m~ 5 and ~ nd Co~r _ Pieces ~f a film of TFE~PS~PV~ copslymer having an equivalent weigh~ of 1~50 and a ~hiekness of 0.05 mm (2 mils) were hydrolyzed and separately converted to sal~s of metal ions as described in the first groups of examples. Transport rate~ for water were measureds and are summarized in Table III.
Tab X
Water transport Me ~al ra te - Ex~ Ion Conditions(g/m2.24 h) S Ca~ 25C, 30~ RH14,700 6 ~9+ 25C, 30% RH14,800 E ~ 25., 30~ R~ 23,500 ~ Na 25C, 30% RH 12,100 Exam~les 7 and~ and Comparative ~xamples G~ H and J
In order to ascer~ain the effect of water on DMMP transport, experiments were carried ou~ using a cell in which the ilm to be tested was in contact with ~MMP on one side (top) and distilled water on ~he other (kottom). The upper compartment Df the cell was closed with a loose fi~ting glass cover, and the lower compar~ment was eguipped with a small port, so that samples could be periodically removed from each compartment for analysis by gas chromatography.
The film sample was clamped between the two compartments with a neoprene gasket on each ~ide of the film to be tested. The exposed area of film in the test was circular, 7.62 cm (3 in) in diameter.
The bottom compartment wa5 filled with water tca.
185 ml), so that it would contact the lower surface of the fiLm, and the water was stirred by a magnetically impelled stirrins bar. In the top compartment was placed 50 ml of DMMP. ~dditional ~amples of ~ilm like those of Exs. 1 and 2 ~nd Comp.
Exs, A~ B and C were thus ~ested over a peri~d of 6-6.5 hours.
For ea~h time of analysi , the number of grams of DMMP that had passed throuqh the membrane into the water oompartment was calculated by using the equations:
lOOD _ = B and loo ~WD-D) ~ W H) (wD-D) ~ ~
where ~ is the weight percen~ DMMP in the b~ttom IwaterJ compartment, ~ he weight per~ent DMMP in the top eo~partmentt WD is the original weight.of DMMP in the top compartment (here, 56.3 grams), ~
is the original weight of distilled water ~here, lB5 grams), D is ~he number of grams of DMMP that have diffused into the bottom compartment, and H is the number of grams of water that have pa~sed through the mem~rane into the DMMP compartment. In this determination, the ~moun~ of water and DMMP in the fiLm was ignored, ~s ~here is no easy way to 20 determine those amounts. These simultaneous equations were ~olved for D and H. D was plotted against time of measurement ~hours), and a mass tr~nsfer rate was calculated by finding the slope of the best-fit line ~or ~he linear portion of the ~urve, multiplying by 24 ~nd dividing by the exposed film area (45.60xlO m ~. The results are summarized in Table I~.
. 35 ~o Table V
Meta7 Transport Rate ~g~m2.24 h~
~:x. Ion DMMP~MMP
7 c~2 495n 5930 5 8 Mg 17100 10400 G H 14200* 42900 H Na 17000 15000 ~Rate was significant1y non1inear; aver3ge rate 1~ wa5 19600.
The test described in thi~ set o~ examples is a very severe test, and embodies conditions r~ot necessarily encountered during actua1 use. In any case, it is noted that the Ca+2 foxm of the po1ymer exhibited significantly lower transport rate of D~
than the other forms teste~.
Using apparatus as described hereinabove, a oomposite fabric was made by heat laminating a film Of TFE/PSEPVE copolymer, having an e~uivalent weight of 1350 and a thickness of .036 mm 11.4 mils), tha~
had been hydrolyzed on only one surface to a depth of 0.015 mm, and a ~omponent woven fabric of a blend of 95~ poly-meta-phenylene isophthalamide fibers and 5%
poly-para~phenylene terephthalamide fibers, said abric having a basis wei~ht of 150 g/m2;
lamination was carried out with the component fabric against the release paper, and the unhydrolyzed side of the film against the component fabric. The radiant heater on the curved plate was at 360C, the hollow roll was at 240~C and was operated at a vacuum of 7.1 x 104 pascals (21 inches of mercury), and the line speed was 0.3 m/min (1 ft/min). ~he produc~
~as immersed for 48 hours in a 1:1 volume mixture o~
conc. ammonium hydroxide and methanol to hydrolyze ~SO~F groups, rinsed with water, immersed for 5 hours in a 2 . 8S% by wt. aqueous solution of sodium chloride to ion-exchange the functional groups to -SO3Na form, again rinsed wi~h water, and dried, to provide a composite fabric in Na~ form. Portions of the composite fabric in Na form were separately immersed in aqueous 2N hydrochloric acid for 5.5 hrs to provide fabric in H form, and in aqueous potassium hydroxide solution (30 9 RO~l) for ca. lS
hrs to provide fabric in K fsrm~ A portion of the ccmposite abric in Na form was i~mersed for l9 hours in a 5.48% by wt. aqueous solution of CaC12.2H2O to ion-exchange Na ~or Ca 2;
dnalysis by atomic absorption of the extracted metal ions indicated that the composite fabric contained 0.33% by wt. Ca~ and 230 ppm (wt.) Na~, and ~hat in a minimum of 94 ~ol % of the sulfonate groups, sodium had bee~ replaced by calcium. Another portion of the composite fabric in Na+ form was immersed for 19 hrs in a 7.41% by wt. aqueous solution of ~gCl2.6H2O to exchange Na for Mg : an~lysis indicated that the composite fabric contained 0.29%
by wt. ~9 and 240 ppm (wt.) Na , and that in a minimum of 95 mol ~ of the sulfonate groups, sodium had been replaced by magnesium.
Transport rates for DMMP and water were measured using test cells having two compartments and a port in each compartment for use in removing saMples for analysis. The exposed area of composite fabric in the test cell was 20.27 cm2. Test samples were checked for leaks after mounting in a test cell by attaching a water-containing bubbler to the top compartment, and raising the air pressure 61ightly in the bottom compartment; if bubbles appeared the ~ample was rejected. In the compartment adjacent the component fabric ~ide of the composite fabric was placed 30 ml of distilled water, and in the compartment adjacent the componen~ film side of the composite fabric was placed 13.5 g of DMMP. The ports were closed with rubber caps, and the cell was mounted on a shaker to assure that adequate mixing occurred in each compartment~ Samples removed periodically from each compartment were analyzed by qas chromatography. The amounts of wa~er and DM~.P
transported were calculated with the formula as - ~escribed in the pre~ious set of examples, using Ww=3Q g and ~D=13.5 9. Transpor~ rates were then ~alculated, using 20.27 x 10 4m2 as the exposed area. The results are summarized in Table V.
Table V
DMMP Water Test DMMP trans- Wa~er trans-Dur= trans- port trans- port Me~al ation ported rate ported rate Ex. Ion (hours) (9) (g/m2.24h) (9) (g/m2.24h) 20 9 Ca~ 6 . 51. 542800 5. 60 7430 6.5 1.492730 5.476960 M9~2 6 . 53 . 496070 6. 87 9010 6 2 . 755200 S .49 9110 6 2. 034410 7. 91 1~000 25 ~ R+ 6 . S2 . 414350 7. 97 3320 6 2. 614990 7. 54 12Ç~0 6 3.256310 3.95 5830 L Na+ 4.5 3.536820 6.16 13100 6 2.326750 15.530900 M H~ 2 2.1411800 4.64 58900 3.5 4.038~70 8.33 24700 6 6.1211400 4.56 ~470 Exam les 11-20 and Com~arative Examples N, P and Q
_ P
Addi~iona1 p i eces of the film in -S03H
form of Exs. 1-2 were separately converted to salts 35 of var ious other metal ions by inunersion in a~eous ~ 3 sc:lutions of Al(N03)3 (100-0 9 of Al (N03) 3- 9H2()~1), BaC12 ( g BaC12.2H20~ e(NC\~)3 ~77.~ ~ c)f CelN03)3.6il~0/1, not all dissolved~, 5 CoCl2(9502 9 of CoC12.6~12C)fl), CrC13~71.0 9 of CrC13. 6H20/1), NiS04 (105 . 2 9 of NiS0,~ . 6H2t)/1), ZnC12 (45 . 3 g of ZnC12/1), and Ce (N03) 4 (aqueous solution 0. 5N in Ce (N03) 4 and 2N in HN03). Rates of transport of DMMP and water were measured, and the results are summarized in Table VI. The results for wa~er are expressed as water vapor permeabilities (averages o~ two to four runs measured at different relative humidi~ies) inasmuch as they incorporate into the numerical values reported the relative humidity (R8). The water vapor permeab~lity P is obtained from the water transport rate R (in g/cm2.h) with the formula P = ~ . t V
20 where t is the sample thickness (cm) and V is the di~ference in vapor pressure of water on the two sides of the sample, which is determined by the formula V ~ ) (Vt) where R~ is, the relative humidity expressed as a decimal, and Vt is the vapor pressure of water at the temperature o the experiment, expressed in torr.
k;~
TABLE VI
DMMP
~ransport Water vapor Metal rate* permeability Ex~ Ion (g~m2.24h) (g.cm/cm~.h.torr) 5 11 Al+3 10.6*
12 ~a+2 34.4 2.24 x 10-5 13 Ce+3 14.4 2.96 x 10 5 14 Co~2 5,93 4.67 x 10 5 15 Cr~3 568 3.66 x 10 5 10 1~ Ni 80.6 4.44 x 10 5 17 zn+2 4~ 4.65 x 10 5 1~ Ce+4 336* 3.06 x 10-5 19 Ca~2 20.C 4.18 x 10-5 20 Mg 25.5 4.83 x 10 5 15 N ~a 3920 4.31 x 10 5 P H 3240 6.46 x 10 5 Q K~ 1650 * Averages of 2 to 4 values (single value ln Exo 16 measured at 21.5 to 2~C and 14 to 30~ RH. The rate is over a 5- to 6.5-hour period, except for Ex. 11, which is over a 1- to 2-hour period, after which there was a net gain in weight, apparently due to uncontrolled high humidity. For Ex. 18, a transport rate of 1200 in one run is presumed to be incorrect due to leak in f ilm.
Exam~es 21 and 22 and Comparative Examples R, S and T
25 Additional pieces of the films of Exs. 1 and
2 and Comparative Exs. A, B and C were used to test the rate of transport of beta-chlorodiethyl sul~ide (herein referred to as CDES), a chemical compound employed as a simulant of bis-beta-chloroethyl
3~ sulfide. Transport rates were measured over a 29- to 64-hour, generally 48-hour, period, under both dry ~10 m~ C~ES alone) and wet (8 ml CDES + 2 ml water) conditions. The test cells were the same ~s those described for Ex~. 9 and 10. The li~uid (CDES ~nd, if present, ~ater) was placed on the top side of the film. Air was blown ~hrough the compartment adjacent the bottom side of the film at a rate of 4 l/min and ~hen into a glass tube packed with 150 mg of coconut qhell charcoal adsorbent. The material collected on the adsoebent was desorbed by placing the lat~er in carbon disulfide and agitating it, and the carbon disulfide extract wa5 analyzed by gas chromatography.
The results are summarized in ~able VII.
Table VII
~etal Transport Rate of CDES (g~m~.24 hr) Ex. ~on 21 Ca 2 0.017* ND
22 Mg 2 0.07Z 0.916 R H 0.0 1.14 S Na ND~ 0.0~1 T K ND ND
* upper limi~; actual value may be lower.
** ND means "not detectable"
Industrial ApPlicability Composite fabrics containing a continuous film of a highly fluorinated ion exchange polymer as defined herein are useful in protective garments such as jackets, trousers, complete suits hermetically sealed, gloves~ boots, hats, head coverings, masks, etc. The garments are broadly useful for providirlg protection to workers in the chemical industry, firemen, forest fire fighters, race car drivers, crop dusters and airplane pilots, and they may have value 30 for defensive use by military personnel. They are believed to provide protection against blistering agents which contain chlocoethyl groups and toxic oryanophosphorus compounds by a dual açtion of preventing penetration by part of the subst~nce, and .. 35 of complexing with and/or detoxi~ying at least part of the substance which penetra~es into the ion exchange barrier layer of the garment. The garments provided herein are ~echnically advanced over those previQusly known in that they readily permit loss of perspiration and body heat while providing the needed protection~ The garments are also waterproof in ~he sense that gros amounts of liguid will not penetrate the ion exchange film. ~he water entry pressure of 10 the composite fabric is an order of magnitude above - that of ordinary wa~erproof fabrics. Garments of the composite fabrics are virtually ~water~ightW~ yet ~breathable". ~he composite fabrics can ~lso be used for rain or water protection in any kind of rainwear, such as rainsuits, coats, parkas, ponchos~ slickers, etc.
The results are summarized in ~able VII.
Table VII
~etal Transport Rate of CDES (g~m~.24 hr) Ex. ~on 21 Ca 2 0.017* ND
22 Mg 2 0.07Z 0.916 R H 0.0 1.14 S Na ND~ 0.0~1 T K ND ND
* upper limi~; actual value may be lower.
** ND means "not detectable"
Industrial ApPlicability Composite fabrics containing a continuous film of a highly fluorinated ion exchange polymer as defined herein are useful in protective garments such as jackets, trousers, complete suits hermetically sealed, gloves~ boots, hats, head coverings, masks, etc. The garments are broadly useful for providirlg protection to workers in the chemical industry, firemen, forest fire fighters, race car drivers, crop dusters and airplane pilots, and they may have value 30 for defensive use by military personnel. They are believed to provide protection against blistering agents which contain chlocoethyl groups and toxic oryanophosphorus compounds by a dual açtion of preventing penetration by part of the subst~nce, and .. 35 of complexing with and/or detoxi~ying at least part of the substance which penetra~es into the ion exchange barrier layer of the garment. The garments provided herein are ~echnically advanced over those previQusly known in that they readily permit loss of perspiration and body heat while providing the needed protection~ The garments are also waterproof in ~he sense that gros amounts of liguid will not penetrate the ion exchange film. ~he water entry pressure of 10 the composite fabric is an order of magnitude above - that of ordinary wa~erproof fabrics. Garments of the composite fabrics are virtually ~water~ightW~ yet ~breathable". ~he composite fabrics can ~lso be used for rain or water protection in any kind of rainwear, such as rainsuits, coats, parkas, ponchos~ slickers, etc.
Claims (18)
1. A protective garment fabricated at least in part from a composite fabric, said fabric containing as the essential component thereof a continuous film of a highly fluorinated ion exchange polymer having sulfonic acid metal ion salt functional groups, said metal ion having a valence of +2, +3 or +4, there being at least one fluorine atom attached to each carbon atom to which each said functional group is attached, said polymer having an equivalent weight no greater than about 2000.
2. The protective garment of Claim 1 wherein said polymer is a perfluorinated polymer.
3. The protective garment of Claim 2 wherein said metal ion is selected from the group consisting of Ca+2, Mg+2, Al+3, Zn+2, Ce+3, Ce+4, Cr+3, Ni+2 and Co+2.
4. The protective garment of Claim 3 wherein said metal ion is Ca+2.
5. The protective garment of Claim 2 or Claim 4 wherein said polymer has an equivalent weight no greater than about 1500, and the thickness of said film is in the range of about 2.5 to 125 micrometers.
6. The protective garment of Claim 2 or Claim 4 wherein said polymer has an equivalent weight no greater than about 1500, and the thickness of said film is in the range of about 10 to 50 micrometers.
7. The protective garment of Claim 1 wherein said composite fabric further comprises a microporous polyolefin cloth.
8. The protective garment of Claim 7 wherein said polyolefin is polytetrafluoroethylene or polypropylene.
9. The protective garment of Claim 1 wherein said composite fabric further comprises a component fabric of fibers of poly-meta-phenylene isophthalamide or poly-para-phenylene terephthalamide or a blend thereof.
10. The protective garment of Claim 1 wherein said composite fabric further comprises a component fabric of fibers of polyhexamethylene adipamide, polyhexamethylene decanedicarboxamide, polyhexamethylene dodecanedicarboxamide, poly-epsilon-caproamide or the polyamide of bis-para-aminocyclohexylmethane and dodecanedicarboxylic acid.
11. The protective garment of Claim 1 or Claim 4 wherein said composite fabric consists of one layer of said continuous film and one layer of component fabric, and said garment is fabricated from said composite fabric so disposed that said film is toward the outside of said garment and said component fabric is toward the inside of the said garment.
12. The protective garment of Claim 9 or Claim 10 wherein said composite fabric consists of one layer of said continuous film and one layer of component fabric, and said garment is fabricated from said composite fabric so disposed that said film is toward the outside of said garment and said component fabric is toward the inside of said garment.
13. A composite fabric comprising a microporous polyolefin cloth and a continuous film of a highly fluorinated ion exchange polymer having sulfonic acid metal ion salt functional groups, said metal ion having a valence of +2, +3, +4, there being at least one fluorine atom attached to each carbon atom to which each said functional group is attached, said polymer having an equivalent weight no greater than about 2000.
14. The composite fabric of Claim 13 wherein said polyolefin is polytetrafluoroethylene or polypropylene.
15. The composite fabric of Claim 13 or Claim 14 wherein said composite fabric further comprises at least one other component fabric.
16. A waterproof protective cover fabricated at least in part from a composite fabric, said fabric containing as the essential component thereof a continuous film of a highly fluorinated ion exchange polymer having sulfonic acid metal ion salt functional groups, said metal ion having a valence of +2, +3 or +4, there being at least one fluorine atom attached to each carbon atom to which each said functional group is attached, said polymer having an equivalent weight no greater than about 2000.
17. The waterproof protective cover of Claim 16 wherein said cover is a tent or shelter.
18. The waterproof protective cover of Claim 16 wherein said cover is a tarpaulin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000467944A CA1246815A (en) | 1984-11-15 | 1984-11-15 | Protective garment of composite fabric containing sulphonated fluoropolymer film with metal ion groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000467944A CA1246815A (en) | 1984-11-15 | 1984-11-15 | Protective garment of composite fabric containing sulphonated fluoropolymer film with metal ion groups |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1246815A true CA1246815A (en) | 1988-12-20 |
Family
ID=4129157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000467944A Expired CA1246815A (en) | 1984-11-15 | 1984-11-15 | Protective garment of composite fabric containing sulphonated fluoropolymer film with metal ion groups |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1246815A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111627586A (en) * | 2020-06-09 | 2020-09-04 | 上海孚邦实业有限公司 | Lead-free protective clothing |
-
1984
- 1984-11-15 CA CA000467944A patent/CA1246815A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111627586A (en) * | 2020-06-09 | 2020-09-04 | 上海孚邦实业有限公司 | Lead-free protective clothing |
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