CA1097154A - Chemical warfare glove and method of manufacture - Google Patents
Chemical warfare glove and method of manufactureInfo
- Publication number
- CA1097154A CA1097154A CA292,702A CA292702A CA1097154A CA 1097154 A CA1097154 A CA 1097154A CA 292702 A CA292702 A CA 292702A CA 1097154 A CA1097154 A CA 1097154A
- Authority
- CA
- Canada
- Prior art keywords
- butyl rubber
- article
- coating
- rubber
- latex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/0064—Producing wearing apparel
- B29D99/0067—Gloves
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
- A41D19/0058—Three-dimensional gloves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/4842—Outerwear
- B29L2031/4864—Gloves
Abstract
ABSTRACT OF THE DISCLOSURE
An article of clothing, particular a glove, which is highly resistant to chemical warfare agents, comprising a fabric substrate, normally pre-shaped to form the article, which is coated with an inner layer of a resilient elastomer, such as natural rubber deposited from a latex, which adheres to but does not penetrate the substrate, and then coated with an outer layer of a butyl rubber which may contain an inorganic filler. The fabric substrate provides wearer comfort while the combination of an inner layer having a high vapour retention capacity and an outer layer which is resistant to toxic chemicals in liquid form and has a low vapour permeability, provides a high resistance to toxic chemicals for periods of time not heretofore possible.
An article of clothing, particular a glove, which is highly resistant to chemical warfare agents, comprising a fabric substrate, normally pre-shaped to form the article, which is coated with an inner layer of a resilient elastomer, such as natural rubber deposited from a latex, which adheres to but does not penetrate the substrate, and then coated with an outer layer of a butyl rubber which may contain an inorganic filler. The fabric substrate provides wearer comfort while the combination of an inner layer having a high vapour retention capacity and an outer layer which is resistant to toxic chemicals in liquid form and has a low vapour permeability, provides a high resistance to toxic chemicals for periods of time not heretofore possible.
Description
1C)973L54 This invention relates to articles of clothing which are resistant to toxic chemicals. More particularly this invention relates to gloves which are resistant to chemical warfare agents for 12 hours or more.
Many items of protective clothing, and in particular gloves, have been developed for military and industrial uses over the years in many parts of the world. Some of these provide adequato chemical protection but are too thick and heavy to permit manipulation of small objects. In others, which are lighter and thinner, tactility and manual dexterity is obtained at the expense of chemical protection. Yet others, while providing good chemical protection for limited periods of time, of the order of two to three hours, ; deteriorate rapidly and become totally useless upon prolonged exposures of the order of 12 to 15 hours. Gloves are quite easily produced from natural-rubber and chloroprene latices but these materials do not give adequate protection against CW agents. One of the few polymers that will give this protection is butyl rubber and its halogenated derivatives. It is known to abricate gloves with a fabric liner and coated with natural rubber neoprene or butyl rubber and it is also known that the impermeability of butyl rubber to chemical agents and gases may be improved by the incorporation oE ammlca-cèous filler~
; 20 The prior art has, however, failed to contemplate that a multi-layered article of clothing comprising in combination an inner layer of a resilient elastomer having a high affinity or a toxic vapour and an outer layer of a butyl rubber being substantially impermeable to toxic liquid and having low vapour permeability, produces an improved, comfortable, flexible - glove which provides protection against chemical warfare agents for a period of time almost an order of magnitude greater than heretofore possi-ble. It is believed that there is a synergistic effect between the inner layer, preferably natural rubber or chloroprene, having a high ~1 - ~39715~
vapour ratention cal)acity, an(l the outer butyl r~lbber layar being substantially impermeable to a toxic liquid and having low vapour permeability, such that the protection afforded by the combination is far greater than the sum of the pro-tection afforded by the parts. Butyl rubber and more particularly butyl rubber which incorporates a suitable inorganic filler is not swollen by chem-ical warfare agents, such as mustard gas, and does not absorb them in liquid form. It acts therefore as a barrier to these substancas in liquid form. It also acts as a barrier to vapollr and possesses a very higll resistance to pene-tration by the vapours o~ chamical warfare agents. On the other hand, natural rubber and synthetic elastomers such as polyethyl acrylate, nitrile rubbers and neoprene have a greater afEinity for chemical warfare agents such as mus- `~
tarcl gas and are therefore unsuitable for use in the outer layer of a glove.
When proteete(l by an outer layer of the relatively impermeable butyl rubber, however, a layer o~ a material with a high aEfinity Eor G~ agents tends to ``
adsorb and retain the very small antounts of vapour which are transmitted by ~ ;
the ralativcly impermaabla outer layer, ancl thus provicles the wearer with greAtar proteetion ttlan woul(l otllerwise be available.
'l`hus by ona asl)eet o~ this invantion there is provicled a multi-layered artiele of clothing eomprising, in combination, an inner layer of a resilient elastomer selected from the group consisting of natural rubber, poly-acrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene -~
and polychloroprene, and an outer layer of a butyl rubber completely covering and integrai with the inner layer, said inner layer having a high affinity for ~
a toxic chemical vapour and being impermeable to said toxic chemical vapour, ! -and said outer butyl rubber layer being substantially impermeable to a toxic ~
chemical liquid and having a low toxic vapour permeability, thereby providing - ~
high resistance to toxic chemicaIs in liquid and vapour form. ~
~- By another aspect of this invention there is provided a method for ~ -`~ producing an article of clothing which is resistant to chemical warfare agents in liquid and vapour form comprising the steps of:
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. dipping the coated former into a latex dispersion of resilient ;~ B 2 -7~Sgl elastomer selected Lrom Lhe group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elas-tomer coated former;
d. coating the elastomer coated former with a butyl rubber;
e. drying said butyl rubber, and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affiniLy Lor a toxic chemical vapour and is impermeable to said toxic chemical vapour, and wherein said butyl rubber coating is substantially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour pcrmeability.
The invention will be described hereinunder with reEerence to the accompflnying (Irawings in wbich Figure 1 is a sketch oE a glove according to the invention; and Figure 2 is a schematic flow diagram oE the method of production use~ for the glove of Fi~,ure 1.
As shown in Fig~lre 1, a glove accorcling to tlle present invention comprises a moisture absorbtive reinforcing substrate l covered with an inner layer 2 of a resilient elastomer having a high affinity for a toxic vapour, such as natural rubber or chloroprene, and an outer layer 3 of a butyl rubber being substantially impermeable to a toxic liquid and having a low vapour permeability. It will be appreciated that the reinforcing substrate is inessen-tial to the invention and is only present in a preferred embodiment. The butyl rubber is preferably chloro-butyl rubber or bromo-butyl rubber and contains a suitable inorganic filler. A suitable inorganic Eiller is magnesium silicate.
The substrate may be any suitable fabric liner material known to ` those skilled in the art. Conveniently the fabric liner is a knitted cotton - fabric which has an interlocked structure which provides stretch in two direc-tions. Such fabrics provide ma~imum comfort to the wearer, are reasonably perspiration absorbent and facilitate donning and doffing.
7~5~
For maximum Elexibility of the finished product it is important that tl~e inner resilient elastomeric layer should adhere to the liner or substrate but should not impregnate or strike through the Iabric. The cotton liner is, therefore, mounted on a former and is first soaked with a rubber latex-coagulant agent, which will ge] or coagulate the elastomeric latex before it penetrates the Eabr;c. Conveniently, a l~osolution of acetic acid in methanol is used ns tlle coagulant.
The inner elastomeric layer is normally formed on tl-e coagulant soaked substrate by coating with a suitable latex dispersion, for example, natural latex, sucll as Lotol 185 h,lving a 61~/o solicl content ancl a viscosity of at least 800 centipoisc.
Latexes of other elastomeric materials such as polyacry1ates e.g.
polyethyl acrylate (llycar ~ ), polybutAdiene, styrene-butadiene copolymcr, acrylonitrile-butaclienc~r-lbber and neoprene (poly-ch1Oroprene) may aLso be employecl lor tl~is purpose.
The outer layer is produced by coating the previous]y latex-coated glove with a butyl rubber of suitable composition.
The coating is preferably effected from a solution of the butyl rubber composition in a suitable volatile organic solvent or from a latex dispersion of the butyl rubber composition in water. The latex method is preferred because of problems encountered in the handling of solvent vapour. Also, in industrial operations with solutions of butyl rubber the complete removal of trapped solvent from the coating and subsequent vulcani~ation without the formation of blisters in the finished article have been difficult.
Preferably, but not essentially, the outer butyl rubber layer is pr()duced by successive coatings with intermediate air ~ '`
~ ~9~154 drying steps so as to build up a composite butyl rubber layer and hence avoi(l flaws and bubbles which might expose the inner layer directly to a toxic chemical.
Butyl rubber has also given problems in attaining a high level of cross linking during vulcanization i.e. curing, giving rubber compounds which have low resiliency, high set and generally a dead or non-rubbery feel. The newer additions to the - butyl family of rubbers, i.e. chlorobutyl and bromobutyl, have given more cure-reactive polymers and consequently more resilient rubbers. Bromobutyl rubber being more reactive than chlorobutyl rubber gives slightly faster and tighter cures than do chlorobutyl-rubber compounds with similar vulcanization systems.
The halogenation of the isobutylene-isoprene copolymer (butyl rubber) is controlled to give a predominant substitution reaction and little of the unsaturation originally present in the molecule is lost. This gives a polymer chain with one halide atom to one double bond.
fll3 I''3 C.l3 --C~2 _ 7 ~ c~ = c c~ C~12 CH2 _ C
~ isobutylene halogenated isopreneisobutylene ;` unit unit unit ~ where X - chlorine or bromine atom. -- . ;
~ Besides supplying additional sites for cross linking with metal `~ o~ides the halogen enhances the reactivity of the double bond. Thus, bromobutyl and chlorobutyl rubbers were selected for preparatlon and evaluation. The butyl rubber solution preferably contains an inorganic filler in an amount from about 5% to about lOO'~o by ~ weight of contained rubber, in addition to conventional curing agents, ; accelerators, softeners, antioxidants, pigments and the like, known to those in the art. If desirecl, the successive coatings may be of the same butyl -rubber composition or alternatively the ~ 1019711S~
pigmenL constituent may be contIined only in the final coating composition. The inorganic filler material preEerabLy has a plate-like - particle structure such as a micaceous material or flake aluminum.Powder talc is also suitable and d preferred material i5 Mistron Vapour which is an ultra fine magnesium silicate. Any solvent commonly used in rubber technology may be employed e.g. xylene, as may any conventional pigments, antioxidants and the like. A suitable butyl rubber has been found to be Polysar ~ Bromo-Butyl X2. ;~
With refercnce now to Figure 2, wIlich shows a schematic flow sheet of a preferred method according to the present invention, -~
it will be seen that a conventional knitted or interlocked cotton fabric is cut to shape and sewn to form a cotton glove substrate whicIl is then placed on IIO11OW porcelain former having a gla~ed ;
impermeab]e outer surface. The formers are carriecl on racks by conveyor through a coagulant agent bath containing I~T/~acetic acicl in metIlanol. Ipon removal from the bath the coagulant is allowed to drain or 2 to 4 minutes, the Eormers are turned and drained for a ~urther 2 to 4 minutes to allow evaI-oration oc the methanol.
The treated substrates are then dipped in a bath containing natural : . :
latex dispersion (having 61% solids and a viscosity of at least 800 centipoise). The latex dipped gloves are then air dried for about .. : . .
24 hours at ambient temperatures to produce a rubber coated former.
Alternatively, the latex dipped gloves may be dried in an oven at temperatures up to about 150 F for up to about 3 hours.
Following the solution method mentioned above, the natural rubber coated gloves are then dipped in a butyl rubber composition dissolved in a suitable volatile organic solvent e.g. xylene, and then air dried at room temperature for 2 to 4 hours depending upon temperature and humidity conditions~ Following air drying, further drying in an oven at about 165 1i for about l hour is performed.
Preclrying at ambient ternperature is a pre~erred but not essential ~ 6 ~
. . ' ~ . ;) . :
, ~'~)97~54 step as blistering an(l bubbllng problems ancl ~he risk of retaining pockets of the xylene solvent are minimized. The gloves are withdrawn from the butyl rubber coating bath at about 6 inches per minute and this is sufficient to build up a layer between 0.001 and 0.010 inches and generally about 0.006 inch on the substrate. Following oven drying and cooling the dipping and drying steps are repeated up to four or five times so as to build up sufficient thickness to provide the amount of CW agent protection required. The basic -requirements of the gloves were to give at least 12 hours protection against mustard gas (H-agent, dichlorodiethylsulphide), to have as little effect as possible on manual dexterity, to withstand at least three weeks wear under combat conditions and to impose as ~`
little discomfort as possible on the wearer in hot or cold weather.
Because hese recluirements were not compatible, a compromise was necessary in the choice of design and materiaL. Normally a total thickness of up to about 0.030 inch is required and this is normally produced in Eour c~r five dipping and drying steps. For convenience and simplicity only two dippLng and drying cycLes are shown in Figure 2. As previously inclicated the pig;nent components of the ~:. ~ . .
dipping solution may be omittttd` if desired, from all-but the last ` dipping stage. Following the final dip, drying,and cooling,the -.: .
gloves are lightly dusted with a magnesium carbonate powder and cured ~3 at elevated temperature and pressure in an autoclave. Curing at ~, :
about 27 psi of saturated steam at 127 C (260 F) Eor 2 hours has been found satisfactory although the pressure may be increased to ~` - about 50 psi with a corresponding reduction in curing time. Hot air may also be used instead of steam. The pressure cure of the :, .:
~` autoclave permitted vulcanization of both the resilient natural ~;
rubber and the butyl rubber coating compositions, without any formation of bubbles or aLr bListers. FoLlowing curing, the gloves are stripped from the porcelain forms whiLe llot and, when cool, are trimmed and washecl in soapy water. A final dusting with zinc stearate powder facilitates packaging.
. ::. . .. :... :
~097~L54 ::
'I`he pIeEerretI butyl ruhbeI- composition when using the solution method i.e. a solution of a butyl rubber composition in a suitable volatile organic solvent e.g. xylene, is as follows.
TABLE IA -~
PARTS BY DRY WEIGIIT
a butyl rubber (selected from butyl, bromobutyl and chlorobutyl) 100 zinc oxide 3 to 8 L0 stearic acid 0.1 to 2.0 antioxidant (e.g. octamine) 0.1 to 3.0 Coumarone-i~ndene resin0 to 15.0 -~
magnesium silicate filler 0 to 100 zlnc cliethyldithiocarbamate 0.1 to 3.0 During the course of the development we were able to show ; that xylene was the preLerred soLvent for tiliS application (Table 1).
~: ,: . .' `~ Certain other solvents and azeotropic: mixtures oE solvents gave blisters during cIrying and vulcanlzing.
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:~:, P ~1 h ~ I Ql O ~ :
o m ~ ~ O '' ~ '' O O ~ ~ O O
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:~ ? ~J ii~ g $ O O ~;t ~ ~ c~ O u~ g Oo Oo . ~ O p:~ ~ ~1 ~ ~ cP~ ~ ~ O u~ ~1 0 ~I Ll') ~1 ~ T-l u:l ~ ~.
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co ~ ~1 0 0 ~ O a~
X O ~ ~ O O ~ O ~ ~ ~ ~3 ~1 0 ~
IJ ~ ~ O h h~ h h ~ o X X ~
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_ 9 --.: -: :: : :, ,: ' ` " ,, 1~97~5~
A final neoprene-rubber coating may be added to give increased abrasion resistance. Tests showed that vulcanized bromobutyl rubber had sufficient stability to abrasion and wear without any extra protective layer needed. Penetration tests showed the neoprene gave reduced times with H-agent as shown in Table II.
TABLE II
The Effect of Neoprene as an Abrasive-Resistant Outerla er on Penetration of H
Y , ~
Composition of Glove Coating Penetration Time, Layer- of:-` ' The above me~hod of fabrication used butyl rubber compositions containing a large proportion of ultra-fine magnesium silicate (Table III).
; This material, which has a platy micaceous structure gave improved i.e. ~
lower penetration times on the Congo red mirror test with H-agent, Table IV ;
(which is a comparison of two formulations differing only in the presence and absence, respectively, of the filler)O The actual butyl-rubber formu-lations used which are presented in Table III include a chlorobutyl- and bromobutyl-rubber compoundj CF 266 and CF 268, which are compared in Table V
for penetration with H-agent~ Only very slight differences in times were noted and these could be due to the small difference in thickness of the - 10 - . ~
~` .
,' " ' ~ ~;
- 1~97~lS~
samples. When compared with a commercially available neoprene-rubber latex however, a definite superiority of butyl rubber can be seen.
TABLE III
~ = .
Butyl-Rubber Formula ions CE 266 GF 267~CF 268 CF 269 ~ '' . Chlorobutyl Rubber 100.00 - - - : :
Bromobutyl Rubber - lOOoOO100~00 100~00 Zinc Oxide 5.00 5.00 5.00 5.00 Stearic Acid - loOO 1~00 1~00 Zinc Stearate 1.50 . Activated Magnesium Oxide 0.50 0O50 Antioxidant (octamine) 1.00 loOO 1~00 1~00 Coumarone-indene Resin (Cumar ) 3.00 3.00 3.00 3.00 - Magnesium Silicate (Mistroll~ lOOoOOlOOoOO 100~00 ~ .
;; 20 Benzo~hiaæole Disulphide2.00 2.00 - ~ `
- Tetramethyl Thiuram Disulphide 1.00 1.00 Zinc Diethyl Dithiocarbamate - - loOO 1~00 Colour to Olive Drab : '.
All formulations dissolved in xylene ";
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- 11 - .
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~97~5i~
TABLE IV
Comparison of Mica-Filled(CF 268) with Non-Filled(CF 269) ..~.~
Bromobutyl Rubber Using Cell Penetration Test r Compound Thickness Total H Collected,ug mm (4 h)(7 h) (16 h) (23.8 h)(32 h) . _ -_. . _ _.
CF 268 0O15 88 670 _ _ _ CF 269 0.15 2189 _ _ _ _ ~, ~
CF 268 0O25 0 9 433 _ _ CF 269 0~25 13 171 1241 _ _ .
CF 268 0.36 0 0 44 _ _ CF 269 0036 0 0 126 _ _ CF 2690.48 0 0 109 417 838 CF 2680.64 0 0 0 0 0 CF 2690.64 0 0 0 0 :54 CF 2680.81 0 0 0 0 0 . _ ... ~ . _ The improvement in penetration times exhibi.ted by the formulations containing -the filler is believed to be due to a tortuous path created by the presence of the filler.
. . . .
1~9715~
TABLE V
Comparison of Penetration Times of Chloro-and Bromo-Butyl Rubber with Neoprene at Various Thickness Type of Rubber Thickness,Penetration Chlorobutyl 0.18 4O5 Bromobutyl 0.15 3.3 ' Chlorobutyl 0.25 10.0 ;-, Bromobutyl 0.23 7.0 Chlorobutyl 0.35 15~0 Bromobutyl 0.28 14.0 Neoprene Latex 0.56 1.5 0.76 2.0 Improvements in penetration times noted with the solution-deposited bromobutyl rubber with additions of mica-type fillers were attempted with the natural-rubber latex dipping method. Due to critical pH and solids content of the natural-rubber latex we were not able to significantly change the penetration times without changing the nature of the dipping bathO The modified natural-rubber latex gave strike-through and film-buildup problems on the cotton substrate and did not allow suitable materials to be fabricated.
Accordingly, the addition of the fillers using -the latex dispersion method was dropped. `~
Results of penetration tests carried out on the final materials used are presented in Table VI which clearly indicates the superiority of our natural rubberlbutyl rubber combination over natural-rubber. H-agent penetra-tion: - Two methods of obtaining penetration data were used.
,~
~7~i4 a. The Congo red mirror method i.e. MIL STD 282 Method 204.1.1 was employed to give time of penetration of H-agent and;
b. the H-agent vapour which penetrated a sample of material clamped in the conventional penetration test cell was swept by a stream of air into an absorption bubbler containing diethyl succinnate, and the amount of H-agent vapour collected therein was determined by the gas chromatographic method of Gibson et al in Journal 10 of Chromatography Vol. 92 (1974) p.p. 162 to 165 TABLE VI
Tests were carried out at a temperature of 30 C and the test material was contaminated with five one milligram drops of H-agent.
Penetration Results of Natural-Rubber and A Natural-Rubber/Butyl-Rubber Laminate (Glove Material) _ -- -Composition Thickness, Total H Collected, ~g mm 4h 7h 16h 23.8 h 32h ¦
_ _ ~ _ _ Natural Rubber 0.48 8963 _ _ _ _ Natural Rubber 0048 _ _ ~ 0 0 0 0 24.5 Butyl Rubber 0.l28 _ _ ~ _ The alternative method mentioned above for applying the butyl rubber coating involves latex dippingO The advantages of latex dipping over solution dipping in rubber glove manufacture are numerous. The use of flammable, toxic solvents and long drying periods makes solution dipping unpopular as does difficulties in vulcanization or curing of the deposited layerO
~r :
" ~J97~LS~
.
laLex clipping on the ,ther hand is relatively simple, less hazarclous and less costly. Removal of water requires less equipment than the solvents used in solution dipping and is a much safer process (fire, toxicity and pressure curing). Moreover, .
- a glove can be produced in a shorter time using a latex system rather than with a solvent system.
-~ The latex dipping method is essentially the same as the -~' solution dipping method, with the exception that the butyl rubber ~ ~`
` coating cornposition is applied in the form of a latex dispersion .. . .
of the butyl rubber composition in water.
- The preferred butyl rubber composition for use in forming the latex dispersion is as follows~
`~. `'.
TABLE Vll A
I'ARTS BY DRY WElG~lT
ButyL rubber latex (selected from butyl, bromobutyl ~lnd chlorobutyl latexes) 100 sulpllur 0.5 to 5.0 zinc dibutylditlliocarbam~te 0.1 to 5.0 ~illC oxide 3 to 8 - dithiocarbamate rubber accelerator 0.1 to 5.0 -~
A cotton knitted fabric glove blank was placed on a porcelain former, flamed to smooth off the surface and dipped into a coagulant bath. This consisted of a 10% acetic acid solution in acetone. The former ~las allowed to dry whilst being rotated for about
Many items of protective clothing, and in particular gloves, have been developed for military and industrial uses over the years in many parts of the world. Some of these provide adequato chemical protection but are too thick and heavy to permit manipulation of small objects. In others, which are lighter and thinner, tactility and manual dexterity is obtained at the expense of chemical protection. Yet others, while providing good chemical protection for limited periods of time, of the order of two to three hours, ; deteriorate rapidly and become totally useless upon prolonged exposures of the order of 12 to 15 hours. Gloves are quite easily produced from natural-rubber and chloroprene latices but these materials do not give adequate protection against CW agents. One of the few polymers that will give this protection is butyl rubber and its halogenated derivatives. It is known to abricate gloves with a fabric liner and coated with natural rubber neoprene or butyl rubber and it is also known that the impermeability of butyl rubber to chemical agents and gases may be improved by the incorporation oE ammlca-cèous filler~
; 20 The prior art has, however, failed to contemplate that a multi-layered article of clothing comprising in combination an inner layer of a resilient elastomer having a high affinity or a toxic vapour and an outer layer of a butyl rubber being substantially impermeable to toxic liquid and having low vapour permeability, produces an improved, comfortable, flexible - glove which provides protection against chemical warfare agents for a period of time almost an order of magnitude greater than heretofore possi-ble. It is believed that there is a synergistic effect between the inner layer, preferably natural rubber or chloroprene, having a high ~1 - ~39715~
vapour ratention cal)acity, an(l the outer butyl r~lbber layar being substantially impermeable to a toxic liquid and having low vapour permeability, such that the protection afforded by the combination is far greater than the sum of the pro-tection afforded by the parts. Butyl rubber and more particularly butyl rubber which incorporates a suitable inorganic filler is not swollen by chem-ical warfare agents, such as mustard gas, and does not absorb them in liquid form. It acts therefore as a barrier to these substancas in liquid form. It also acts as a barrier to vapollr and possesses a very higll resistance to pene-tration by the vapours o~ chamical warfare agents. On the other hand, natural rubber and synthetic elastomers such as polyethyl acrylate, nitrile rubbers and neoprene have a greater afEinity for chemical warfare agents such as mus- `~
tarcl gas and are therefore unsuitable for use in the outer layer of a glove.
When proteete(l by an outer layer of the relatively impermeable butyl rubber, however, a layer o~ a material with a high aEfinity Eor G~ agents tends to ``
adsorb and retain the very small antounts of vapour which are transmitted by ~ ;
the ralativcly impermaabla outer layer, ancl thus provicles the wearer with greAtar proteetion ttlan woul(l otllerwise be available.
'l`hus by ona asl)eet o~ this invantion there is provicled a multi-layered artiele of clothing eomprising, in combination, an inner layer of a resilient elastomer selected from the group consisting of natural rubber, poly-acrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene -~
and polychloroprene, and an outer layer of a butyl rubber completely covering and integrai with the inner layer, said inner layer having a high affinity for ~
a toxic chemical vapour and being impermeable to said toxic chemical vapour, ! -and said outer butyl rubber layer being substantially impermeable to a toxic ~
chemical liquid and having a low toxic vapour permeability, thereby providing - ~
high resistance to toxic chemicaIs in liquid and vapour form. ~
~- By another aspect of this invention there is provided a method for ~ -`~ producing an article of clothing which is resistant to chemical warfare agents in liquid and vapour form comprising the steps of:
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. dipping the coated former into a latex dispersion of resilient ;~ B 2 -7~Sgl elastomer selected Lrom Lhe group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elas-tomer coated former;
d. coating the elastomer coated former with a butyl rubber;
e. drying said butyl rubber, and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affiniLy Lor a toxic chemical vapour and is impermeable to said toxic chemical vapour, and wherein said butyl rubber coating is substantially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour pcrmeability.
The invention will be described hereinunder with reEerence to the accompflnying (Irawings in wbich Figure 1 is a sketch oE a glove according to the invention; and Figure 2 is a schematic flow diagram oE the method of production use~ for the glove of Fi~,ure 1.
As shown in Fig~lre 1, a glove accorcling to tlle present invention comprises a moisture absorbtive reinforcing substrate l covered with an inner layer 2 of a resilient elastomer having a high affinity for a toxic vapour, such as natural rubber or chloroprene, and an outer layer 3 of a butyl rubber being substantially impermeable to a toxic liquid and having a low vapour permeability. It will be appreciated that the reinforcing substrate is inessen-tial to the invention and is only present in a preferred embodiment. The butyl rubber is preferably chloro-butyl rubber or bromo-butyl rubber and contains a suitable inorganic filler. A suitable inorganic Eiller is magnesium silicate.
The substrate may be any suitable fabric liner material known to ` those skilled in the art. Conveniently the fabric liner is a knitted cotton - fabric which has an interlocked structure which provides stretch in two direc-tions. Such fabrics provide ma~imum comfort to the wearer, are reasonably perspiration absorbent and facilitate donning and doffing.
7~5~
For maximum Elexibility of the finished product it is important that tl~e inner resilient elastomeric layer should adhere to the liner or substrate but should not impregnate or strike through the Iabric. The cotton liner is, therefore, mounted on a former and is first soaked with a rubber latex-coagulant agent, which will ge] or coagulate the elastomeric latex before it penetrates the Eabr;c. Conveniently, a l~osolution of acetic acid in methanol is used ns tlle coagulant.
The inner elastomeric layer is normally formed on tl-e coagulant soaked substrate by coating with a suitable latex dispersion, for example, natural latex, sucll as Lotol 185 h,lving a 61~/o solicl content ancl a viscosity of at least 800 centipoisc.
Latexes of other elastomeric materials such as polyacry1ates e.g.
polyethyl acrylate (llycar ~ ), polybutAdiene, styrene-butadiene copolymcr, acrylonitrile-butaclienc~r-lbber and neoprene (poly-ch1Oroprene) may aLso be employecl lor tl~is purpose.
The outer layer is produced by coating the previous]y latex-coated glove with a butyl rubber of suitable composition.
The coating is preferably effected from a solution of the butyl rubber composition in a suitable volatile organic solvent or from a latex dispersion of the butyl rubber composition in water. The latex method is preferred because of problems encountered in the handling of solvent vapour. Also, in industrial operations with solutions of butyl rubber the complete removal of trapped solvent from the coating and subsequent vulcani~ation without the formation of blisters in the finished article have been difficult.
Preferably, but not essentially, the outer butyl rubber layer is pr()duced by successive coatings with intermediate air ~ '`
~ ~9~154 drying steps so as to build up a composite butyl rubber layer and hence avoi(l flaws and bubbles which might expose the inner layer directly to a toxic chemical.
Butyl rubber has also given problems in attaining a high level of cross linking during vulcanization i.e. curing, giving rubber compounds which have low resiliency, high set and generally a dead or non-rubbery feel. The newer additions to the - butyl family of rubbers, i.e. chlorobutyl and bromobutyl, have given more cure-reactive polymers and consequently more resilient rubbers. Bromobutyl rubber being more reactive than chlorobutyl rubber gives slightly faster and tighter cures than do chlorobutyl-rubber compounds with similar vulcanization systems.
The halogenation of the isobutylene-isoprene copolymer (butyl rubber) is controlled to give a predominant substitution reaction and little of the unsaturation originally present in the molecule is lost. This gives a polymer chain with one halide atom to one double bond.
fll3 I''3 C.l3 --C~2 _ 7 ~ c~ = c c~ C~12 CH2 _ C
~ isobutylene halogenated isopreneisobutylene ;` unit unit unit ~ where X - chlorine or bromine atom. -- . ;
~ Besides supplying additional sites for cross linking with metal `~ o~ides the halogen enhances the reactivity of the double bond. Thus, bromobutyl and chlorobutyl rubbers were selected for preparatlon and evaluation. The butyl rubber solution preferably contains an inorganic filler in an amount from about 5% to about lOO'~o by ~ weight of contained rubber, in addition to conventional curing agents, ; accelerators, softeners, antioxidants, pigments and the like, known to those in the art. If desirecl, the successive coatings may be of the same butyl -rubber composition or alternatively the ~ 1019711S~
pigmenL constituent may be contIined only in the final coating composition. The inorganic filler material preEerabLy has a plate-like - particle structure such as a micaceous material or flake aluminum.Powder talc is also suitable and d preferred material i5 Mistron Vapour which is an ultra fine magnesium silicate. Any solvent commonly used in rubber technology may be employed e.g. xylene, as may any conventional pigments, antioxidants and the like. A suitable butyl rubber has been found to be Polysar ~ Bromo-Butyl X2. ;~
With refercnce now to Figure 2, wIlich shows a schematic flow sheet of a preferred method according to the present invention, -~
it will be seen that a conventional knitted or interlocked cotton fabric is cut to shape and sewn to form a cotton glove substrate whicIl is then placed on IIO11OW porcelain former having a gla~ed ;
impermeab]e outer surface. The formers are carriecl on racks by conveyor through a coagulant agent bath containing I~T/~acetic acicl in metIlanol. Ipon removal from the bath the coagulant is allowed to drain or 2 to 4 minutes, the Eormers are turned and drained for a ~urther 2 to 4 minutes to allow evaI-oration oc the methanol.
The treated substrates are then dipped in a bath containing natural : . :
latex dispersion (having 61% solids and a viscosity of at least 800 centipoise). The latex dipped gloves are then air dried for about .. : . .
24 hours at ambient temperatures to produce a rubber coated former.
Alternatively, the latex dipped gloves may be dried in an oven at temperatures up to about 150 F for up to about 3 hours.
Following the solution method mentioned above, the natural rubber coated gloves are then dipped in a butyl rubber composition dissolved in a suitable volatile organic solvent e.g. xylene, and then air dried at room temperature for 2 to 4 hours depending upon temperature and humidity conditions~ Following air drying, further drying in an oven at about 165 1i for about l hour is performed.
Preclrying at ambient ternperature is a pre~erred but not essential ~ 6 ~
. . ' ~ . ;) . :
, ~'~)97~54 step as blistering an(l bubbllng problems ancl ~he risk of retaining pockets of the xylene solvent are minimized. The gloves are withdrawn from the butyl rubber coating bath at about 6 inches per minute and this is sufficient to build up a layer between 0.001 and 0.010 inches and generally about 0.006 inch on the substrate. Following oven drying and cooling the dipping and drying steps are repeated up to four or five times so as to build up sufficient thickness to provide the amount of CW agent protection required. The basic -requirements of the gloves were to give at least 12 hours protection against mustard gas (H-agent, dichlorodiethylsulphide), to have as little effect as possible on manual dexterity, to withstand at least three weeks wear under combat conditions and to impose as ~`
little discomfort as possible on the wearer in hot or cold weather.
Because hese recluirements were not compatible, a compromise was necessary in the choice of design and materiaL. Normally a total thickness of up to about 0.030 inch is required and this is normally produced in Eour c~r five dipping and drying steps. For convenience and simplicity only two dippLng and drying cycLes are shown in Figure 2. As previously inclicated the pig;nent components of the ~:. ~ . .
dipping solution may be omittttd` if desired, from all-but the last ` dipping stage. Following the final dip, drying,and cooling,the -.: .
gloves are lightly dusted with a magnesium carbonate powder and cured ~3 at elevated temperature and pressure in an autoclave. Curing at ~, :
about 27 psi of saturated steam at 127 C (260 F) Eor 2 hours has been found satisfactory although the pressure may be increased to ~` - about 50 psi with a corresponding reduction in curing time. Hot air may also be used instead of steam. The pressure cure of the :, .:
~` autoclave permitted vulcanization of both the resilient natural ~;
rubber and the butyl rubber coating compositions, without any formation of bubbles or aLr bListers. FoLlowing curing, the gloves are stripped from the porcelain forms whiLe llot and, when cool, are trimmed and washecl in soapy water. A final dusting with zinc stearate powder facilitates packaging.
. ::. . .. :... :
~097~L54 ::
'I`he pIeEerretI butyl ruhbeI- composition when using the solution method i.e. a solution of a butyl rubber composition in a suitable volatile organic solvent e.g. xylene, is as follows.
TABLE IA -~
PARTS BY DRY WEIGIIT
a butyl rubber (selected from butyl, bromobutyl and chlorobutyl) 100 zinc oxide 3 to 8 L0 stearic acid 0.1 to 2.0 antioxidant (e.g. octamine) 0.1 to 3.0 Coumarone-i~ndene resin0 to 15.0 -~
magnesium silicate filler 0 to 100 zlnc cliethyldithiocarbamate 0.1 to 3.0 During the course of the development we were able to show ; that xylene was the preLerred soLvent for tiliS application (Table 1).
~: ,: . .' `~ Certain other solvents and azeotropic: mixtures oE solvents gave blisters during cIrying and vulcanlzing.
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o m ~ ~ O '' ~ '' O O ~ ~ O O
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:~ ? ~J ii~ g $ O O ~;t ~ ~ c~ O u~ g Oo Oo . ~ O p:~ ~ ~1 ~ ~ cP~ ~ ~ O u~ ~1 0 ~I Ll') ~1 ~ T-l u:l ~ ~.
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_ 9 --.: -: :: : :, ,: ' ` " ,, 1~97~5~
A final neoprene-rubber coating may be added to give increased abrasion resistance. Tests showed that vulcanized bromobutyl rubber had sufficient stability to abrasion and wear without any extra protective layer needed. Penetration tests showed the neoprene gave reduced times with H-agent as shown in Table II.
TABLE II
The Effect of Neoprene as an Abrasive-Resistant Outerla er on Penetration of H
Y , ~
Composition of Glove Coating Penetration Time, Layer- of:-` ' The above me~hod of fabrication used butyl rubber compositions containing a large proportion of ultra-fine magnesium silicate (Table III).
; This material, which has a platy micaceous structure gave improved i.e. ~
lower penetration times on the Congo red mirror test with H-agent, Table IV ;
(which is a comparison of two formulations differing only in the presence and absence, respectively, of the filler)O The actual butyl-rubber formu-lations used which are presented in Table III include a chlorobutyl- and bromobutyl-rubber compoundj CF 266 and CF 268, which are compared in Table V
for penetration with H-agent~ Only very slight differences in times were noted and these could be due to the small difference in thickness of the - 10 - . ~
~` .
,' " ' ~ ~;
- 1~97~lS~
samples. When compared with a commercially available neoprene-rubber latex however, a definite superiority of butyl rubber can be seen.
TABLE III
~ = .
Butyl-Rubber Formula ions CE 266 GF 267~CF 268 CF 269 ~ '' . Chlorobutyl Rubber 100.00 - - - : :
Bromobutyl Rubber - lOOoOO100~00 100~00 Zinc Oxide 5.00 5.00 5.00 5.00 Stearic Acid - loOO 1~00 1~00 Zinc Stearate 1.50 . Activated Magnesium Oxide 0.50 0O50 Antioxidant (octamine) 1.00 loOO 1~00 1~00 Coumarone-indene Resin (Cumar ) 3.00 3.00 3.00 3.00 - Magnesium Silicate (Mistroll~ lOOoOOlOOoOO 100~00 ~ .
;; 20 Benzo~hiaæole Disulphide2.00 2.00 - ~ `
- Tetramethyl Thiuram Disulphide 1.00 1.00 Zinc Diethyl Dithiocarbamate - - loOO 1~00 Colour to Olive Drab : '.
All formulations dissolved in xylene ";
: ~
- 11 - .
~ '~
, ~ ~
~97~5i~
TABLE IV
Comparison of Mica-Filled(CF 268) with Non-Filled(CF 269) ..~.~
Bromobutyl Rubber Using Cell Penetration Test r Compound Thickness Total H Collected,ug mm (4 h)(7 h) (16 h) (23.8 h)(32 h) . _ -_. . _ _.
CF 268 0O15 88 670 _ _ _ CF 269 0.15 2189 _ _ _ _ ~, ~
CF 268 0O25 0 9 433 _ _ CF 269 0~25 13 171 1241 _ _ .
CF 268 0.36 0 0 44 _ _ CF 269 0036 0 0 126 _ _ CF 2690.48 0 0 109 417 838 CF 2680.64 0 0 0 0 0 CF 2690.64 0 0 0 0 :54 CF 2680.81 0 0 0 0 0 . _ ... ~ . _ The improvement in penetration times exhibi.ted by the formulations containing -the filler is believed to be due to a tortuous path created by the presence of the filler.
. . . .
1~9715~
TABLE V
Comparison of Penetration Times of Chloro-and Bromo-Butyl Rubber with Neoprene at Various Thickness Type of Rubber Thickness,Penetration Chlorobutyl 0.18 4O5 Bromobutyl 0.15 3.3 ' Chlorobutyl 0.25 10.0 ;-, Bromobutyl 0.23 7.0 Chlorobutyl 0.35 15~0 Bromobutyl 0.28 14.0 Neoprene Latex 0.56 1.5 0.76 2.0 Improvements in penetration times noted with the solution-deposited bromobutyl rubber with additions of mica-type fillers were attempted with the natural-rubber latex dipping method. Due to critical pH and solids content of the natural-rubber latex we were not able to significantly change the penetration times without changing the nature of the dipping bathO The modified natural-rubber latex gave strike-through and film-buildup problems on the cotton substrate and did not allow suitable materials to be fabricated.
Accordingly, the addition of the fillers using -the latex dispersion method was dropped. `~
Results of penetration tests carried out on the final materials used are presented in Table VI which clearly indicates the superiority of our natural rubberlbutyl rubber combination over natural-rubber. H-agent penetra-tion: - Two methods of obtaining penetration data were used.
,~
~7~i4 a. The Congo red mirror method i.e. MIL STD 282 Method 204.1.1 was employed to give time of penetration of H-agent and;
b. the H-agent vapour which penetrated a sample of material clamped in the conventional penetration test cell was swept by a stream of air into an absorption bubbler containing diethyl succinnate, and the amount of H-agent vapour collected therein was determined by the gas chromatographic method of Gibson et al in Journal 10 of Chromatography Vol. 92 (1974) p.p. 162 to 165 TABLE VI
Tests were carried out at a temperature of 30 C and the test material was contaminated with five one milligram drops of H-agent.
Penetration Results of Natural-Rubber and A Natural-Rubber/Butyl-Rubber Laminate (Glove Material) _ -- -Composition Thickness, Total H Collected, ~g mm 4h 7h 16h 23.8 h 32h ¦
_ _ ~ _ _ Natural Rubber 0.48 8963 _ _ _ _ Natural Rubber 0048 _ _ ~ 0 0 0 0 24.5 Butyl Rubber 0.l28 _ _ ~ _ The alternative method mentioned above for applying the butyl rubber coating involves latex dippingO The advantages of latex dipping over solution dipping in rubber glove manufacture are numerous. The use of flammable, toxic solvents and long drying periods makes solution dipping unpopular as does difficulties in vulcanization or curing of the deposited layerO
~r :
" ~J97~LS~
.
laLex clipping on the ,ther hand is relatively simple, less hazarclous and less costly. Removal of water requires less equipment than the solvents used in solution dipping and is a much safer process (fire, toxicity and pressure curing). Moreover, .
- a glove can be produced in a shorter time using a latex system rather than with a solvent system.
-~ The latex dipping method is essentially the same as the -~' solution dipping method, with the exception that the butyl rubber ~ ~`
` coating cornposition is applied in the form of a latex dispersion .. . .
of the butyl rubber composition in water.
- The preferred butyl rubber composition for use in forming the latex dispersion is as follows~
`~. `'.
TABLE Vll A
I'ARTS BY DRY WElG~lT
ButyL rubber latex (selected from butyl, bromobutyl ~lnd chlorobutyl latexes) 100 sulpllur 0.5 to 5.0 zinc dibutylditlliocarbam~te 0.1 to 5.0 ~illC oxide 3 to 8 - dithiocarbamate rubber accelerator 0.1 to 5.0 -~
A cotton knitted fabric glove blank was placed on a porcelain former, flamed to smooth off the surface and dipped into a coagulant bath. This consisted of a 10% acetic acid solution in acetone. The former ~las allowed to dry whilst being rotated for about
2~ minutes at room temperature (24 C). The cotton blank was then ~ ~
dipped into a natural-rubber latex bath made up of a latex (LOTOL ~ ~-~ , - 1185) and allowed to dwell 5 seconds. This was then withdrawn, ~-inverted and aLlowed to dry. The natural rubber film was then scrubbed with an abrasive cleaner using a beaker brush and water and then rinsed and dried. This was then dipped into a bath of ~9~lS~
butyl-rubber latex made up of the following butyl rubber composition and withdrawn at 10 cm per minute and immediately rotated at about 8 rpm at 24C until the film had gelled. The film was then dried in an oven at 66C
for 1 hour in the inverted position. The most preferred butyl rubber latex composition is as follows:
TABLE VII
PARTS BY DRY WEIGHT
- Butyl latex 100 100.00 Sulphur 3.00 Zinc dibutyldithiocarbamate 4O00 Zinc oxide 5O00 Formaldehyde (preservative) 0.10 Mera ~ 255 4O00 Pigments to give Olive drab colour 6.50 MERA ~ 255 - a liquid dithiocarbamate rubber curing acceleratorO
~ The washing ànd dlpplng procedures were repeated until five dip-coats of butyl-rubber latex had been applied although no abrasive cleaner was used on the butyl film. The finished product was then dried at 66C for l hour and cured in a pressure vessel under the following conditions (i) 30 p5i steam in the jacket (131C); (ii) 26 psi air in the curing chamber; (iii) 3 hours duration.
~ The above process enabled applicant to produce a good rubber glove with excellent fleæibility and softness.
The quality iOe. evenness of the coatings and adhesion of the various coatings was found to be improved by scrubbing the surface of each dried coat-ing prior to application of succeeding coatingsO
~0~7~ti4 : ~ ~
(.1oves made wiLh the bu~y~ rubber composition of Table VJI
were worn by military personnel while carrying out tasks in a field triaL to determine performance and durability of the gloves when worn for a 24 hour period by persons engaged in driving and repairing motor vehicles, moving stores and equipment, field telephone maintenance, and lifting and carrying casualty loaded ~ `
stretchers. When tested for 11-agent resistance by applicant's ~ `-penetration ceLl method, the worn gloves showed no penetration of 11-agent during 24 hours of test. -~
13lends of butyl rubber with other polymers were tried and polymers of polyvinylidene chloride, polyvinylacetate, acrylonitrile-rubber latex and other butyl-rubber latexes were made up and evaluated for physical properties as well as improvement of dipping ~;
properties. I-1Owever, no improvements were noted.
1t will be appreciated that although the presently preferred synthetic rubber used in the outer ]ayer is a butyl rubber, applicant also conte1nl)L1tes the use of other synthetic rubbers which have similar properties. lor e.Yample, Viton~-)which is a trademark for a series oE fluo1oelastomers based on the copolymer of vinyliclene fluoride and llexafluoropropylene is contemplated in view of its resistance to a wide variety of toxic corrosive chemicals and solvents, radiation and nonflammability.
Lt will also be appreciated that while this specification -;
has been directed specifically to the manufacture of CW gloves, other items of CW clothing such as mitts, boots, hats, trousers -and smocks may be fabricated using the principles of the present invention. While it is preferred to preform the fabric substrate to the final form of the article of clothing so as to eliminate the problems associated with properly sealing all seams, it is possible 1 to fabricate an article of clothing subsequent to coating of the substrate with tile CW agent resisting materials provided care is taken to seal the sefl1n~ and 1oins.
. ~ L ~ ~.
)97~S~
:Lt i9 also to be note~l that application of the impermeable layers has been described by re~erence to dipping process. It will be appreciated that the impermeable layers may also be applied by other known means such as by spraying, calendering and the like without departing from the scope of this invention.
` ` ,:` `
.
dipped into a natural-rubber latex bath made up of a latex (LOTOL ~ ~-~ , - 1185) and allowed to dwell 5 seconds. This was then withdrawn, ~-inverted and aLlowed to dry. The natural rubber film was then scrubbed with an abrasive cleaner using a beaker brush and water and then rinsed and dried. This was then dipped into a bath of ~9~lS~
butyl-rubber latex made up of the following butyl rubber composition and withdrawn at 10 cm per minute and immediately rotated at about 8 rpm at 24C until the film had gelled. The film was then dried in an oven at 66C
for 1 hour in the inverted position. The most preferred butyl rubber latex composition is as follows:
TABLE VII
PARTS BY DRY WEIGHT
- Butyl latex 100 100.00 Sulphur 3.00 Zinc dibutyldithiocarbamate 4O00 Zinc oxide 5O00 Formaldehyde (preservative) 0.10 Mera ~ 255 4O00 Pigments to give Olive drab colour 6.50 MERA ~ 255 - a liquid dithiocarbamate rubber curing acceleratorO
~ The washing ànd dlpplng procedures were repeated until five dip-coats of butyl-rubber latex had been applied although no abrasive cleaner was used on the butyl film. The finished product was then dried at 66C for l hour and cured in a pressure vessel under the following conditions (i) 30 p5i steam in the jacket (131C); (ii) 26 psi air in the curing chamber; (iii) 3 hours duration.
~ The above process enabled applicant to produce a good rubber glove with excellent fleæibility and softness.
The quality iOe. evenness of the coatings and adhesion of the various coatings was found to be improved by scrubbing the surface of each dried coat-ing prior to application of succeeding coatingsO
~0~7~ti4 : ~ ~
(.1oves made wiLh the bu~y~ rubber composition of Table VJI
were worn by military personnel while carrying out tasks in a field triaL to determine performance and durability of the gloves when worn for a 24 hour period by persons engaged in driving and repairing motor vehicles, moving stores and equipment, field telephone maintenance, and lifting and carrying casualty loaded ~ `
stretchers. When tested for 11-agent resistance by applicant's ~ `-penetration ceLl method, the worn gloves showed no penetration of 11-agent during 24 hours of test. -~
13lends of butyl rubber with other polymers were tried and polymers of polyvinylidene chloride, polyvinylacetate, acrylonitrile-rubber latex and other butyl-rubber latexes were made up and evaluated for physical properties as well as improvement of dipping ~;
properties. I-1Owever, no improvements were noted.
1t will be appreciated that although the presently preferred synthetic rubber used in the outer ]ayer is a butyl rubber, applicant also conte1nl)L1tes the use of other synthetic rubbers which have similar properties. lor e.Yample, Viton~-)which is a trademark for a series oE fluo1oelastomers based on the copolymer of vinyliclene fluoride and llexafluoropropylene is contemplated in view of its resistance to a wide variety of toxic corrosive chemicals and solvents, radiation and nonflammability.
Lt will also be appreciated that while this specification -;
has been directed specifically to the manufacture of CW gloves, other items of CW clothing such as mitts, boots, hats, trousers -and smocks may be fabricated using the principles of the present invention. While it is preferred to preform the fabric substrate to the final form of the article of clothing so as to eliminate the problems associated with properly sealing all seams, it is possible 1 to fabricate an article of clothing subsequent to coating of the substrate with tile CW agent resisting materials provided care is taken to seal the sefl1n~ and 1oins.
. ~ L ~ ~.
)97~S~
:Lt i9 also to be note~l that application of the impermeable layers has been described by re~erence to dipping process. It will be appreciated that the impermeable layers may also be applied by other known means such as by spraying, calendering and the like without departing from the scope of this invention.
` ` ,:` `
.
Claims (36)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A multi-layered article of clothing comprising, in combination, an inner layer of a resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and polychloroprene, and an outer layer of a butyl rubber completely covering and integral with the inner layer, said inner layer having a high affinity for a toxic chemical vapour and being impermeable to said toxic chemical vapour, and said outer butyl rubber layer being sub-stantially impermeable to a toxic chemical liquid and having a low toxic chemical vapour permeability, thereby providing high resistance to toxic chemicals in liquid and vapour form.
2. A article as defined in claim 1, wherein said inner layer is deposi-ted from a latex.
3. An article as defined in claim 2, wherein the latex is selected from the group consisting of natural and polychloroprene rubber latex.
4. An article as defined in claim 1, wherein the outer layer is deposi-ted from a butyl rubber latex.
5. An article as defined in claim 4, wherein the butyl rubber latex is a dispersion in water of a butyl rubber composition consisting of:
PARTS BY DRY WEIGHT
butyl rubber latex 100 sulphur 0.5 to 5.0 zinc dibutyldithiocarbamate 0.1 to 5.0 zinc oxide 3 to 8 dithiocarbamate rubber accelerator 0.1 to 5.0
PARTS BY DRY WEIGHT
butyl rubber latex 100 sulphur 0.5 to 5.0 zinc dibutyldithiocarbamate 0.1 to 5.0 zinc oxide 3 to 8 dithiocarbamate rubber accelerator 0.1 to 5.0
6. An article as defined in claim 4 or 5, wherein the butyl rubber is selected from the group consisting of bromo-butyl rubber and chloro-butyl rubber.
7. An article as defined in claim 1, wherein the outer layer is deposi-ted from a solution of said butyl rubber in a suitable volatile organic solvent.
8. An article as claimed in claim 7, wherein said solution is a solution in xylene of a butyl rubber composition consisting of PARTS BY DRY WEIGHT
butyl rubber 100 zinc oxide 3 to 8 stearic acid 0.1 to 2.0 antioxidant 0.3 to 3.0 coumarone-indene resin 0 to 15.0 magnesium silicate filler 0 to 100 zinc diethyl dithiocarbamate 0.1 to 3.0
butyl rubber 100 zinc oxide 3 to 8 stearic acid 0.1 to 2.0 antioxidant 0.3 to 3.0 coumarone-indene resin 0 to 15.0 magnesium silicate filler 0 to 100 zinc diethyl dithiocarbamate 0.1 to 3.0
9. An article as defined in claim 8, wherein said butyl rubber is selected from bromo-butyl rubber and chloro-butyl rubber.
10. A multi-layered article of clothing comprising, in combination, a moisture absorptive reinforcing substrate, an inner layer of a resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and polychloroprene, which elastomer adheres to but does not penetrate said sub-strate while substantially completely covering said substrate, and an outer layer of a butyl rubber substantially completely covering and integral with said inner layer, said inner layer having a high affinity for a toxic chemical vapour, and being impermeable to said toxic chemical vapour, and said outer butyl rubber layer being substantially impermeable to a toxic chemical liquid and having a low toxic chemical vapour permeability, thereby providing high resistance to toxic chemicals in liquid and vapour form.
11. An article as defined in claim 10, wherein the substrate comprises a resilient fabric having stretch in two directions, precut and formed in the shape of a glove.
12. An article as defined in claim 11, wherein said fabric is a knitted cotton fabric having an interlocked structure.
13. An article as defined in claim 10, wherein said inner layer is deposited from a latex.
14. An article as defined in claim 13, wherein the latex is selected from the group consisting of natural and polychloroprene rubber latex.
15. An article as defined in claim 10, wherein the outer layer is deposi-ted from a butyl rubber latex.
16. An article as defined in claim 15, wherein the butyl rubber latex is a dispersion in water of a butyl rubber composition consisting of PARTS BY DRY WEIGHT
a butyl rubber 100 sulphur 0.5 to 5.0 zinc dibutyldithiocarbamate 0.1 to 5.0 zinc oxide 3 to 8 dithiocarbamate rubber accelerator 0.1 to 5.0
a butyl rubber 100 sulphur 0.5 to 5.0 zinc dibutyldithiocarbamate 0.1 to 5.0 zinc oxide 3 to 8 dithiocarbamate rubber accelerator 0.1 to 5.0
17. An article as defined in claim 10, wherein the outer layer is deposited from a solution of said butyl rubber in a suitable volatile organic solvent, said butyl rubber having the composition PARTS BY DRY WEIGHT
butyl rubber 100 zinc oxide 3 to 8 stearic acid 0.1 to 2.0 antioxidant 0.1 to 3.0 coumarone-indene resin 0 to 15.0 magnesium silicate filler 0 to 100 zinc diethyl dithiocarbamate 0.1 to 3.0
butyl rubber 100 zinc oxide 3 to 8 stearic acid 0.1 to 2.0 antioxidant 0.1 to 3.0 coumarone-indene resin 0 to 15.0 magnesium silicate filler 0 to 100 zinc diethyl dithiocarbamate 0.1 to 3.0
18. An article as defined in claim 17, wherein said butyl rubber is selected from the group consisting of bromo-butyl rubber and chloro-butyl rubber.
19. A method for producing an article of clothing which is resistant to toxic chemicals in liquid and vapour form, comprising the steps of:
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. clipping the coat former into a latex dispersion of resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elastomer coated former;
d. coating the elastomer coated former with a butyl rubber;
e. drying said butyl rubber, and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affinity for a toxic chemical vapour and is impermeable to said toxic chemical vapour, and wherein said butyl rubber coating is substan-tially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour permeability.
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. clipping the coat former into a latex dispersion of resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elastomer coated former;
d. coating the elastomer coated former with a butyl rubber;
e. drying said butyl rubber, and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affinity for a toxic chemical vapour and is impermeable to said toxic chemical vapour, and wherein said butyl rubber coating is substan-tially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour permeability.
20. A method as defined in claim 19, for producing an article of clothing which is resistant to toxic chemicals in liquid and vapour form, comprising the steps of:
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. dipping the coated former into a latex dispersion of resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elastomer coated former;
d. coating said elastomer coated former with a solution of a butyl rubber in a suitable volatile organic solvent;
e. drying the butyl rubber coating so formed; and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affinity for a toxic chemical vapour and is impermeable to said toxic chemical vapour, wherein said butyl rubber coating is substantially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour permeability.
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. dipping the coated former into a latex dispersion of resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elastomer coated former;
d. coating said elastomer coated former with a solution of a butyl rubber in a suitable volatile organic solvent;
e. drying the butyl rubber coating so formed; and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affinity for a toxic chemical vapour and is impermeable to said toxic chemical vapour, wherein said butyl rubber coating is substantially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour permeability.
21. A method as defined in claim 19, for producing an article of cloth-ing which is resistant to toxic chemicals in liquid and vapour form, compris-ing the steps of:
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. dipping the coated former into a latex dispersion of resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elastomer coated former;
d. coating said elastomer coated former with a butyl rubber latex;
e. drying the butyl rubber coating so formed; and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affinity for a toxic chemical vapour and is impermeable to said toxic chemical vapour and said butyl rubber coating is substantially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour permeability.
a. providing a former for said article of clothing;
b. coating said former with a latex coagulating agent;
c. dipping the coated former into a latex dispersion of resilient elastomer selected from the group consisting of natural rubber, polyacrylate, polybutadiene, styrene-butadiene co-polymer, acrylonitrile-butadiene and poly-chloroprene and drying to produce an elastomer coated former;
d. coating said elastomer coated former with a butyl rubber latex;
e. drying the butyl rubber coating so formed; and f. simultaneously curing said elastomer coating and said butyl rubber coating in situ at elevated temperature, wherein said elastomer coating exhibits a high affinity for a toxic chemical vapour and is impermeable to said toxic chemical vapour and said butyl rubber coating is substantially impermeable to a toxic chemical liquid and exhibits low toxic chemical vapour permeability.
22. A method as defined in claim 20, wherein the solvent is xylene.
23. A method for producing an article of clothing as defined in claim 19, 20 or 21, wherein the latex coagulating agent is a bath of acetic acid in methanol.
24. A method for producing an article of clothing as defined in claim 19, 20 or 21, wherein a plurality of coatings of the butyl rubber are applied, with each coating being washed and dried prior to each subsequent coating to promote greater adhesion of said coatings.
25. A method for producing an article of clothing as defined in claim 19, 20 or 21, wherein said butyl rubber is selected from chloro-butyl rubber and bromo-butyl rubber.
26. A method for producing an article of clothing as defined in claim 19, 20 or 21, wherein step c. said latex dispersion is selected from natural rubber latex and chloroprene rubber latex.
27. A method for producing an article of clothing as defined in claim 19, 20 or 21, wherein there is provided a moisture absorptive reinforcing substrate immediately covering the former before any subsequent coatings are applied.
28. A method as defined in claim 20, wherein said butyl rubber solution is a solution in xylene of a butyl rubber composition consisting of PARTS BY DRY WEIGHT
butyl rubber 100 zinc oxide 3 to 8 stearic acid 0.1 to 2.0 antioxidant 0.1 to 3.0 coumarone-indene resin 0 to 15.0 magnesium silicate filler 0 to 100 zinc diethyl dithiocarbamate 0.1 to 3.0
butyl rubber 100 zinc oxide 3 to 8 stearic acid 0.1 to 2.0 antioxidant 0.1 to 3.0 coumarone-indene resin 0 to 15.0 magnesium silicate filler 0 to 100 zinc diethyl dithiocarbamate 0.1 to 3.0
29. A method as defined in claim 21, wherein said butyl rubber latex is a dispersion in water of a butyl rubber composition consisting of PARTS BY DRY WEIGHT
butyl rubber latex 100 sulphur 0.5 to 5.0 zinc dibutyldithiocarbamate 0.1 to 5.0 zinc oxide 3 to 8 dithiocarbama?e rubber accelerator 0.1 to 5.0
butyl rubber latex 100 sulphur 0.5 to 5.0 zinc dibutyldithiocarbamate 0.1 to 5.0 zinc oxide 3 to 8 dithiocarbama?e rubber accelerator 0.1 to 5.0
30. An article as defined in claim 1, 16 or 17, wherein the thickness of said butyl rubber layer is about 0.03 inches,
31. In a method for producing, an article of clothing which is resistant to toxic chemicals in liquid and vapour form including the sequential steps of:
a. providing a former for said article of clothing;
b. coating said former with a natural rubber or chloroprene latex rubber-coagulating agent;
c. coating the coated former with a natural rubber or chloroprene rubber latex dispersion and drying said latex coating, and d. curing the thus applied rubber coating; the improvement of producing an article of clothing which is resistant to toxic chemicals in liquid and vapor form including, prior to said curing step d. the additional steps of:
(i) applying to the rubber coated former of step c. at least one coating of a butyl rubber;
(ii) drying said butyl rubber, and thereafter (iii) simultaneously curing said rubber coating and said butyl coating in situ at an elevated temperature, the resulting article having a rubber coating thereon exhibiting a high affin-ity for toxic chemical vapors and is impermeable to said toxic chemical vapors, said butyl rubber coating being substantially impermeable to toxic chemical liquids and exhibiting low toxic chemical vapor permeability.
a. providing a former for said article of clothing;
b. coating said former with a natural rubber or chloroprene latex rubber-coagulating agent;
c. coating the coated former with a natural rubber or chloroprene rubber latex dispersion and drying said latex coating, and d. curing the thus applied rubber coating; the improvement of producing an article of clothing which is resistant to toxic chemicals in liquid and vapor form including, prior to said curing step d. the additional steps of:
(i) applying to the rubber coated former of step c. at least one coating of a butyl rubber;
(ii) drying said butyl rubber, and thereafter (iii) simultaneously curing said rubber coating and said butyl coating in situ at an elevated temperature, the resulting article having a rubber coating thereon exhibiting a high affin-ity for toxic chemical vapors and is impermeable to said toxic chemical vapors, said butyl rubber coating being substantially impermeable to toxic chemical liquids and exhibiting low toxic chemical vapor permeability.
32. A method for producing an article of clothing as defined in claim 31 wherein said butyl rubber of step (i) is applied From a solution of butyl rubber containing an inorganic plate-like filler impervious to toxic chemicals in a volatile organic solvent.
33. A method for producing an article of clothing as defined in claim 31 wherein said butyl rubber is applied in the form of a latex.
34. A method for producing an article of clothing as defined in claim 31, 32 or 33 wherein step (i) is repeated to apply a plurality of butyl rubber coatings each such coating being washed and dried prior to each subsequent coating to promote greater adhesion of said coatings.
35. A method as defined in claim 19, 20 or 21, wherein dichlorodiethyl-sulphide is the toxic chemical.
36. A method as defined in claim 20, wherein said solution of butyl rubber contains an inorganic plate-like filler impervious to said toxic chemi-cals.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA292,702A CA1097154A (en) | 1977-12-08 | 1977-12-08 | Chemical warfare glove and method of manufacture |
| US05/881,533 US4190685A (en) | 1977-12-08 | 1978-02-27 | Chemical resistant article |
| US05/947,702 US4218779A (en) | 1977-12-08 | 1978-09-29 | Chemical resistant article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA292,702A CA1097154A (en) | 1977-12-08 | 1977-12-08 | Chemical warfare glove and method of manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1097154A true CA1097154A (en) | 1981-03-10 |
Family
ID=4110241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,702A Expired CA1097154A (en) | 1977-12-08 | 1977-12-08 | Chemical warfare glove and method of manufacture |
Country Status (2)
| Country | Link |
|---|---|
| US (2) | US4190685A (en) |
| CA (1) | CA1097154A (en) |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2514234A1 (en) * | 1981-10-08 | 1983-04-15 | Grosjean Claude | Shaped multiply gloves etc. externally impregnated with latex - with an intermediate barrier film or coagulant to block saturation |
| US5070540A (en) * | 1983-03-11 | 1991-12-10 | Bettcher Industries, Inc. | Protective garment |
| US4519098A (en) * | 1983-06-08 | 1985-05-28 | Becton, Dickinson And Company | Wearing apparel and methods for manufacturing of wearing apparel |
| US4526828A (en) * | 1983-06-27 | 1985-07-02 | Pioneer Industrial Products Company | Protective apparel material and method for producing same |
| EP0156295B1 (en) * | 1984-03-28 | 1991-01-16 | Hering-Mitgau, Mane, Dr. | Process for coating mineral materials with elastomers, and product obtained by this process |
| IT1174594B (en) * | 1984-07-09 | 1987-07-01 | Moldip Spa | FLEXIBLE GLOVES RESISTANT TO IPRITE |
| US5284890A (en) * | 1985-01-31 | 1994-02-08 | Her Majesty The Queen As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government | Synthetic rubber composition |
| US4742578A (en) * | 1985-12-02 | 1988-05-10 | Seid Arnold S | Penetration-resistant surgical glove |
| US4779290A (en) * | 1987-03-09 | 1988-10-25 | Wayne State University | Cut resistant surgical gloves |
| US4696065A (en) * | 1987-03-13 | 1987-09-29 | Barbara Elenteny | Peel away multi-layer gloves |
| US5459879A (en) * | 1989-05-22 | 1995-10-24 | Board Of Regents, The University Of Texas System | Protective coverings |
| US5483697A (en) * | 1989-05-22 | 1996-01-16 | Board Of Regents The University Of Texas | Multilayer protective coverings with a sealing solution |
| JP2504631B2 (en) * | 1991-04-30 | 1996-06-05 | 住友ゴム工業株式会社 | Glove manufacturing method |
| US5336555A (en) * | 1991-05-10 | 1994-08-09 | Darras Robert L | Surgical glove comprising carbon fiber whiskers |
| US5441355A (en) * | 1994-05-24 | 1995-08-15 | Arbitrage Imports Incorporated | Scrubber device with waterproof mitt |
| US5564127A (en) * | 1995-04-27 | 1996-10-15 | Manne; Joseph | Puncture proof surgical glove |
| US5741885A (en) * | 1995-08-25 | 1998-04-21 | Baxter International Inc. | Methods for reducing allergenicity of natural rubber latex articles |
| US5691446A (en) * | 1995-08-25 | 1997-11-25 | Dove; Jeffrey S. | Methods for reducing allergenicity of natural rubber latex articles and articles so produced |
| US5632948A (en) * | 1995-12-20 | 1997-05-27 | Megladon Industries | Method of manufacturing hand covering with attached pad |
| US6730380B2 (en) * | 1996-02-20 | 2004-05-04 | Safeskin Corp. | Readily-donned elastomeric articles |
| US5822791A (en) * | 1996-06-24 | 1998-10-20 | Whizard Protective Wear Corp | Protective material and method |
| FR2765777B1 (en) * | 1997-07-11 | 1999-10-29 | Borreani Patrick | PROCESS FOR COATING A TEXTILE SUBSTRATE, IN THE FORM OF A GLOVE IN PARTICULAR |
| US20030075828A1 (en) * | 1998-08-13 | 2003-04-24 | Thomas Jonathan David | Solvent resistant glove |
| US6000061A (en) * | 1998-11-18 | 1999-12-14 | Pt. Irama Dinamika Latex | Glove made from a blend of chloroprene rubber and a carboxylated synthetic butadiene rubber |
| US6391409B1 (en) | 1999-02-12 | 2002-05-21 | Allegiance Corporation | Powder-free nitrile-coated gloves with an intermediate rubber-nitrile layer between the glove and the coating and method of making same |
| US6159532A (en) | 1999-06-16 | 2000-12-12 | Mapa Pioneer Corporation | Method for making polymeric glove with thin, fluoroelastomeric coating |
| DE20008047U1 (en) * | 2000-05-04 | 2000-09-14 | Bluecher Gmbh | Glove for pilots |
| AU2002225909A1 (en) * | 2000-12-06 | 2002-06-18 | Polymer Group, Inc. | Method of forming an imaged compound textile fabric |
| FR2819152B1 (en) * | 2001-01-08 | 2003-03-14 | Hutchinson | PROTECTIVE GLOVE WITH REINFORCED MECHANICAL RESISTANCE AND MANUFACTURING METHOD THEREOF |
| FR2819153B1 (en) * | 2001-01-08 | 2003-04-04 | Hutchinson | HIGH MECHANICAL PERFORMANCE GLOVES, AND HIGH RESISTANCE TO CHEMICALS AND / OR RADIOLYSIS, AND PROCESS FOR PRODUCING THE SAME |
| US6875391B2 (en) * | 2002-06-03 | 2005-04-05 | Kimberly-Clark Worldwide, Inc. | Method of making a glove having improved donning characteristics |
| ES2204335B1 (en) * | 2002-10-15 | 2005-08-01 | Vives Vidal, Vivesa, S.A. | PROCEDURE FOR THE MANUFACTURE OF A BATHROOM AND PRODUCT OBTAINED. |
| US20040122382A1 (en) * | 2002-12-23 | 2004-06-24 | Kimberly-Clark Worldwide, Inc. | Elastomeric articles with beneficial coating on a surface |
| US6772443B2 (en) * | 2002-12-30 | 2004-08-10 | Kimberly-Clark Worldwide, Inc. | Breathable elastomeric glove |
| US20040245670A1 (en) * | 2003-06-03 | 2004-12-09 | Janssen Robert A. | Method of forming a low tack elastomeric article |
| KR101194223B1 (en) * | 2003-07-02 | 2012-10-29 | 앤셀 헬스케어 프로덕츠 엘엘씨 | Textured surface coating for gloves and method of making |
| US20050130521A1 (en) * | 2003-12-10 | 2005-06-16 | Wyner Daniel M. | Protective laminates |
| US9890497B2 (en) | 2004-03-31 | 2018-02-13 | A T G Ceylon (Private) Limited | Anti-perspirant glove |
| GB2400051B (en) * | 2004-03-31 | 2005-03-09 | John Ward Ceylon | Polymeric garment material |
| CA2572394A1 (en) * | 2004-08-16 | 2006-03-02 | Behrouz Vossoughi | Drying glove |
| FR2875384B1 (en) * | 2004-09-23 | 2007-01-05 | Api Seplast Soc Par Actions Si | METHOD FOR PRODUCING A PROTECTIVE GLOVE HAVING HIGH SPECIFIC PERFORMANCE |
| US7378043B2 (en) * | 2005-01-12 | 2008-05-27 | Ansell Healthcare Products Llc | Latex gloves and articles with geometrically defined surface texture providing enhanced grip and method for in-line processing thereof |
| ITMI20050385A1 (en) * | 2005-03-10 | 2006-09-11 | Nextec Srl | PROCEDURE AND SYSTEM FOR WATERPROOFING SEMI-FINISHED FOOTWEAR GLOVES GARMENTS AND CLOTHING ACCESSORIES AND PRODUCTS OBTAINED WITH THIS PROCEDURE OR SYSTEM |
| US20070157363A1 (en) * | 2006-01-10 | 2007-07-12 | Jian Tao | Glove having butyl rubber layer to provide resistance to ketone family chemicals |
| US20070265408A1 (en) * | 2006-05-11 | 2007-11-15 | Yulex Corporation | Non-synthetic low-protein rubber latex product and method of testing |
| US8247077B2 (en) * | 2008-04-10 | 2012-08-21 | Ansell Protective Solutions Ab | Chemical protective garment with added flash fire protection |
| WO2010007538A1 (en) * | 2008-07-15 | 2010-01-21 | Dipped Products Plc | A supported elastomeric glove with enhanced gripping surface and a method of transferring of patterns on to a dipped elastomeric glove surface |
| US20110145967A1 (en) * | 2009-12-22 | 2011-06-23 | Summit Glove Inc. | Protective glove and method of manufacturing the same |
| US8980373B2 (en) | 2011-05-12 | 2015-03-17 | Dipped Products Plc | Supported elastomeric glove with enhanced gripping surface and a method of transferring of patterns onto a dipped elastomeric glove surface |
| DE102011107443A1 (en) * | 2011-07-08 | 2013-01-10 | Mattias Finzelberg | Protective glove with textile lining |
| US9163156B2 (en) * | 2012-01-17 | 2015-10-20 | Honeywell International Inc. | Butyl rubber conversion to dispersion and butyl rubber dipped glove |
| WO2015077819A1 (en) | 2013-11-26 | 2015-06-04 | Ansell Limited | Effervescent texturing |
| EP3267815B1 (en) | 2015-03-10 | 2020-12-16 | Ansell Limited | Supported glove having an abrasion resistant nitrile coating |
| US10154699B2 (en) * | 2015-09-10 | 2018-12-18 | Ansell Limited | Highly chemical resistant glove |
| CN111171398B (en) * | 2020-01-04 | 2021-10-01 | 山东瑞祥泰劳保用品有限公司 | Preparation method of damping anti-collision rubber gloves |
| CN114426802A (en) * | 2022-02-10 | 2022-05-03 | 北京邦维高科新材料科技股份有限公司 | Method for manufacturing heat-sealable rubber-plastic composite adhesive tape and product thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US732360A (en) * | 1903-04-24 | 1903-06-30 | Clarence A Lindsay | Seamless rubber glove. |
| US1769977A (en) * | 1927-01-04 | 1930-07-08 | Goodyear S India Rubber Glove | Rubberized handwear |
| US1955840A (en) * | 1928-10-25 | 1934-04-24 | Dunlop Rubber Co | Method of coating or impregnating fabric with rubber |
| US1989717A (en) * | 1930-10-29 | 1935-02-05 | American Anode Inc | Method of making rubber articles |
| US2304137A (en) * | 1932-12-15 | 1942-12-08 | Patrick J Hurley | Protective glove |
| US2018508A (en) * | 1933-10-04 | 1935-10-22 | Us Rubber Co | Manufacture of rubber articles |
| US2121717A (en) * | 1935-05-11 | 1938-06-21 | E.I.Dupont De Nemours & Co. | Method of coating fabrics and product thereof |
| US2135151A (en) * | 1936-05-23 | 1938-11-01 | Brown Co | Method of multiple-coating or finishing |
| US2311488A (en) * | 1940-04-02 | 1943-02-16 | American Anode Inc | Method of depositing rubber and composition employed therein |
| US2526431A (en) * | 1948-04-07 | 1950-10-17 | Us Rubber Co | Method of making rubber coated fabric articles |
| US2989755A (en) * | 1957-10-18 | 1961-06-27 | Seamless Rubber Co | Surgeons' gloves and method of making the same |
| US3110035A (en) * | 1959-11-17 | 1963-11-12 | Robert C Lahue | Surgical glove |
| US3268355A (en) * | 1962-06-07 | 1966-08-23 | Best Mfg Corp | Method of producing vinyl coated fabric glove |
| US3337876A (en) * | 1965-07-06 | 1967-08-29 | Armstrong Edmond | Constant-volume underwater exposure suit |
| US4070713A (en) * | 1976-03-17 | 1978-01-31 | Arbrook, Inc. | Medical glove and method |
-
1977
- 1977-12-08 CA CA292,702A patent/CA1097154A/en not_active Expired
-
1978
- 1978-02-27 US US05/881,533 patent/US4190685A/en not_active Expired - Lifetime
- 1978-09-29 US US05/947,702 patent/US4218779A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4190685A (en) | 1980-02-26 |
| US4218779A (en) | 1980-08-26 |
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