Slip-coated elastomeric flexible articles and their method of manufacture

In accordance with the present invention, there is provided a flexible article, such as a surgeon's glove, displaying slip properties with respect to damp and dry mammalian tissue without use of powder lubricants. The article is comprised of a substrate layer having an elastomeric material, the layer having a wearer-contacting surface and a damp slip-conferring amount of a lubricant composition applied to the wearer-contacting surface. The lubricant composition is selected from the group consisting of a first composition and a second composition. The first composition comprises an acetylenic diol and at least one compound selected from the group consisting of an organo-modified silicone, an amino-modified silicone, and a cationic surfactant. The second composition comprises a cationic surfactant and at least one compound selected from the group consisting of an organo-modified silicone, an amino-modified silicone, and an acetylenic diol. The elastomer may be natural or synthetic, and is preferably selected from the group consisting of natural rubber, a polyurethane, neoprene, nitrile rubber, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer and combinations thereof. The cationic surfactant is preferably 1-hexadecylpyridinium chloride monohydrate.

TECHNICAL FIELD OF THE INVENTION 
This invention relates to elastomeric flexible articles (e.g., film 
articles), particularly powder-free medical gloves, that exhibit enhanced 
lubricity ("slip") with respect to both dry and damp surfaces, 
particularly skin or other tissue of the wearer, as compared to similar 
articles or films that are not treated as described herein. This invention 
also relates to a process for making such articles. This invention further 
relates to a lubricant composition and a method of treating elastomeric 
flexible articles with a lubricant composition. 
BACKGROUND OF THE INVENTION 
Elastomeric surfaces of articles, in general, exhibit poor lubricity with 
respect to a dry surface, such as dry skin or other mammalian tissue. 
These properties are due to surface friction. Additionally, many 
elastomeric articles or surfaces display poor lubricity with respect to 
damp surfaces. A high coefficient of friction is a distinct disadvantage 
in those applications where an elastomeric surface must slide on another 
surface, such as in the donning of gloves over dry or damp skin. This is 
particularly important in the use of medical gloves, such as examination 
gloves and surgeon's glove. These gloves are relatively close fitting in 
order to provide sensitivity. Further, most surgeons don their gloves 
after scrubbing up and without having fully dried their hands, so that 
their hands may be distinctly damp. Accordingly, the elastomeric materials 
useful in such applications must exhibit enhanced lubricity with respect 
to dry surfaces ("dry slip"), enhanced lubricity with respect to damp 
surfaces ("damp slip"), and the requisite mechanical properties. The prior 
art has attempted various ways to produce powderless gloves which satisfy 
these requirements. 
One prior approach is to halogenate the surface of rubber gloves with 
chlorine or bromine to make it slippery, i.e., reducing tackiness and 
decreasing the coefficient of friction of the rubber gloves. In the case 
of chlorine as the halogen, the prior art discloses the production and use 
of chlorinated water to treat the rubber gloves. Such methods include (1) 
direct injection of chlorine gas into the water mixture, (2) mixing high 
density bleaching powder and aluminum chloride in water, (3) brine 
electrolysis to produce chlorinated water, and (4) acidified bleach. See 
for example U.S. Pat. Nos. 3,411,982 (Kavalir), 3,740,262 (Agostinelli), 
3,992,221 (Homsy, et al.; treating outer surface with chlorine gas), 
4,597,108 (Momose), and 4,851,266 (Momose). However, chlorination produces 
surfaces which have very poor damp slip. 
There are other prior rubber gloves having a slip layer bonded to the inner 
surface of such gloves. Examples of gloves which have an inner layer of 
elastomeric material with particulate lubricant imbedded therein are 
disclosed in U.S. Pat. Nos. 4,070,713 (Stockum), 4,143,109 (Stockum), 
5,284,607 (Chen) and 5,395,666 (Brindle; together with a surfactant, but 
ionic surfactants are not recommended), and which disclose surgeon's 
gloves with various polymeric slip coatings bonded to the inner surface 
thereof are U.S. Pat. Nos. 3,813,695 (Podell, et al.; an inner layer of 
hydrophilic plastic material, e.g., hydrogel polymer), 3,856,561 
(Esemplare, et al.; an inner layer of a copolymer of vinyl or vinylidene 
chloride and an alkyl acrylate), 4,302,852 (Joung), 4,482,577 (Goldstein, 
et al.), 4,499,154 (James, et al.; uses specific hydrogel polymers as the 
inner layer which is then treated with a cationic surfactant or fatty 
amine) and 4,575,476 (Podell, et al.; hydrogel polymer inner layer treated 
with cationic, anionic or nonionic surfactant). The foregoing differ from 
the present invention. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, there is provided a flexible 
article displaying slip properties with respect to damp and dry mammalian 
tissue without use of powder lubricants. The article is comprised of a 
substrate layer having an elastomeric material, the layer having a 
wearer-contacting surface and a damp slip-conferring amount of a lubricant 
composition applied to the wearer-contacting surface. The lubricant 
composition is selected from the group consisting of a first composition 
and a second composition, wherein the first composition comprises an 
acetylenic diol and at least one compound selected from the group 
consisting of an organo-modified silicone, an amino-modified silicone, and 
a cationic surfactant, preferably 1-hexadecylpyridinium chloride 
monohydrate, and wherein the second composition comprises a cationic 
surfactant, preferably 1-hexadecylpyridinium chloride monohydrate, and at 
least one compound selected from the group consisting of an 
organo-modified silicone, an amino-modified silicone, and an acetylenic 
diol. 
In one embodiment, the article is a surgeon's glove. The elastomer may be 
natural or synthetic, and is preferably selected from the group consisting 
of natural rubber, a polyurethane, a homopolymer of a conjugated diene, a 
copolymer of at least two conjugated dienes, a copolymer of at least one 
conjugated diene and at least one vinyl monomer and combinations thereof. 
The conjugated diene may contain hetero atoms, such as conjugated dienes 
which have been halogenated, e.g., chloroprene. Preferred conjugated 
dienes include butadiene, isoprene and chloroprene. Preferred vinyl 
monomers include alkenyl arenes, e.g., styrene, alkylenes, e.g., ethylene 
and propylene, and acrylonitrile. The term "combinations thereof" in 
regard to the elastomer includes physical combinations thereof in a single 
layer and layered combinations thereof, for example, a multi-layered 
elastomeric article having a layer of polyurethane formed over and 
adhering to a layer of natural rubber. 
There is also provided a method of treating an elastomeric flexible 
article. The method comprises: (a) cleaning the article surface by 
washing; (b) chlorinating the article surface; (c) neutralizing the 
article surface and residual chlorine; and (d) treating the article 
surface with a lubricant composition. 
The lubricant composition is selected from a first composition and a second 
composition, wherein the first composition comprises an acetylenic diol 
and at least one compound selected from the group consisting of an 
organo-modified silicone, an amino-modified silicone, and a cationic 
surfactant, preferably 1-hexadecylpyridinium chloride monohydrate (also 
known as cetylpyridinium chloride), and wherein the second composition 
comprises a cationic surfactant, preferably 1-hexadecylpyridinium chloride 
monohydrate, and at least one compound selected from the group consisting 
of an organo-modified silicone, an amino-modified silicone, and an 
acetylenic diol. 
If the article has previously been chlorinated or does not require or 
permit chlorination, steps (b) and (c) may be eliminated. If a powder is 
not used as a mold release when the articles are made, the washing step 
(a) may be eliminated. 
Medical powder-free gloves treated with the lubricant composition provide 
superior lubricity with respect to wet/damp donning in comparison to the 
current chlorinated surgical gloves in the market. 
DETAILED DESCRIPTION OF THE INVENTION 
The invention envisages flexible elastomeric articles including those 
adapted for use in partial or total contact with mammalian tissue, such as 
surgical, examination and dental gloves, condoms, bandages, catheters, 
ureters, sheathes and sheath-type incontinence devices and other film 
articles. Additionally, the damp/dry slip-conferring materials may be 
provided on one or more surfaces of the article including, but not limited 
to, an inner and/or outer surface relative to the wearer, as appropriate 
under the circumstances of the use of each article. 
For purposes of this description, the outer surface of an article and, in 
particular, a glove, is defined as that surface which becomes an external 
surface of the glove in the position of actual use when worn. The inner 
surface is defined as that surface which is adjacent to the skin of the 
wearer when worn. The reverse is true in the case of a catheter or ureter: 
the outer surface is the surface in contact with the wearer's tissue. To 
avoid ambiguity, the term "wearer-contacting surface" will be used herein. 
"Tissue" includes skin or epithelia without limitation. 
The elastomer used in the substrate layer may be a natural or synthetic 
rubber. Without limitation, synthetic rubbers include polyurethane, a 
homopolymer of a conjugated diene, a copolymer of at least two conjugated 
dienes, a copolymer of at least one conjugated diene and at least one 
vinyl monomer, and combinations thereof. 
The conjugated dienes are preferably ones containing from 4 to 8 carbon 
atoms. Examples of such suitable conjugated dienes include: 1,3-butadiene 
(butadiene), 2-methyl-1,3-butadiene (isoprene), 
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), 1,3-hexadiene, 
and the like. The conjugated dienes may contain hetero atoms. Such 
conjugated dienes include those which have been halogenated, for example, 
chloroprene. Mixtures of such conjugated dienes may also be used. The 
preferred conjugated dienes are butadiene, isoprene and chloroprene. 
Any vinyl monomer may be used for copolymerization with at least one 
conjugated diene to prepare synthetic rubbers so long as the resulting 
copolymer is elastomeric. Without limitation, such vinyl monomers include 
alkylenes, alkenyl arenes, and acrylonitrile. The preferred alkylenes are 
ethylene, propylene and butylenes. The preferred alkenyl arenes are 
monoalkenyl arenes. The term "monoalkenyl arene" will be taken to include 
particularly those of the benzene series such as styrene and its analogs 
and homologs including o-methylstyrene, p-methylstyrene, 
p-tert-butylstyrene, 1,3-dimethylstyrene, alpha-methylstyrene and other 
ring alkylated styrenes, particularly ring-methylated styrenes, and other 
monoalkenyl polycyclic aromatic compounds such as vinyl naphthalene, vinyl 
anthracene and the like. The preferred monoalkenyl arenes are monovinyl 
monocyclic arenes such as styrene and alpha-methylstyrene, and styrene is 
particularly preferred. 
The copolymers may be random, tapered or block copolymers. If the 
copolymers are block copolymers, it will be understood that each of the 
blocks thereof may be a homopolymer, a random copolymer or a tapered 
copolymer as long as each block predominates in at least one class of the 
monomers characterizing the block. For example, blocks of alkenyl arenes 
may comprise styrene/alpha-methylstyrene copolymer blocks or 
styrene/butadiene random or tapered copolymer blocks as long as the blocks 
individually predominate in alkenyl arenes. 
Preferred rubbers are natural rubber and synthetic rubbers, including 
polyurethane, neoprene, nitrile rubber, block copolymers of styrene and 
butadiene, particularly a styrene-butadiene-styrene block copolymer, and 
block copolymers of styrene and isoprene, particularly a 
styrene-isoprene-styrene block copolymer. Natural rubber and polyurethane 
are more preferred, with natural rubber being most preferred. Neoprene is 
a homopolymer of the conjugated diene chloroprene. Nitrile rubber is a 
copolymer of the conjugated diene butadiene and the vinyl monomer 
acrylonitrile. 
The block copolymers of alkenyl arenes ("A" blocks) and conjugated diene 
("B" blocks) are preferably network forming, i.e., at least two A blocks 
and at least one B block. The simplest form of such a block copolymer is 
A-B-A, which is a triblock copolymer. In such a synthetic rubber, the A 
blocks are thermodynamically incompatible with the B block(s) resulting in 
a rubber consisting of two phases; a continuous elastomeric phase (B 
blocks) and a basically discontinuous hard, glass-like plastic phase (A 
blocks) called domains. These domains act as physical crosslinks anchoring 
the ends of many block copolymer chains. Since the A-B-A block copolymers 
have two A blocks separated by a B block, domain formation results in 
effectively locking the B blocks and their inherent entanglements in place 
by the A blocks and forming a network structure. Such a phenomenon allows 
the A-B-A rubber to behave like a conventionally vulcanized rubber that 
contains dispersed reactive filler particles. These thermoplastic A-B-A 
rubbers are physically crosslinked by the domains in a network structure 
as opposed to being chemically crosslinked like a conventionally 
vulcanized rubber. As such, these polymers may be handled in thermoplastic 
forming equipment and are soluble in a variety of relatively low cost 
solvents. Additionally, when polymers of this type are used, the 
vulcanization step may be eliminated and, contrary to vulcanized scrap 
rubbers, the scrap from the processing of these thermoplastic elastomers 
can be recycled for further use. 
The block copolymers may be produced by any well known block polymerization 
or copolymerization procedures including the well known sequential 
addition of monomer techniques, incremental addition of monomer technique 
or coupling technique as illustrated in, for example, U.S. Pat. Nos. 
3,251,905; 3,390,207, 3,598,887 and 4,219,627, the disclosures of which 
are incorporated herein by reference. As is well known in the block 
copolymer art, tapered copolymer blocks can be incorporated in the 
multiblock copolymer by copolymerizing a mixture of conjugated diene and 
alkenyl arene monomers utilizing the difference in their copolymerization 
reactivity rates. Various patents describe the preparation of multiblock 
copolymers containing tapered copolymer blocks including U.S. Pat. Nos. 
3,251,905; 3,265,765; 3,639,521 and 4,208,356, the disclosures of which 
are incorporated herein by reference. 
It should be observed that the above-described polymers and copolymers may, 
if desired, be readily prepared by the methods set forth above. However, 
since many of these polymers and copolymers are commercially available, 
for example, KRATON.TM. polymers available from Shell Oil Company, it is 
usually preferred to employ the commercially available polymer as this 
serves to reduce the number of processing steps involved in the overall 
process. 
Typical thicknesses of the elastomeric substrate layer for surgical gloves 
range from about 30 to about 400 microns, preferably from about 100 to 
about 350 microns. Surgical gloves tend to be about 150 microns thick and 
orthopedic gloves tend to be about 300 microns thick. 
To impart damp slip properties to the flexible elastomeric article, which 
is at least substantially powderless and is preferably chlorinated, the 
article is treated with a lubrication composition. There are two suitable 
combinations of components. The first composition comprises (i.e., having 
at least) (1) an acetylenic diol and (2) at least one compound selected 
from the group consisting of an organo-modified silicone, an 
amino-modified silicone, and 1-hexadecylpyridinium chloride monohydrate. 
The second composition comprises (1) 1-hexadecylpyridinium chloride 
monohydrate and (2)at least one compound selected from the group 
consisting of an organo-modified silicone, an amino-modified silicone, and 
an acetylenic diol. The lubricant composition is preferably an aqueous 
solution or dispersion. 
The compound 1-hexadecylpyridinium chloride monohydrate (CAS No. 6004-24-6) 
is a commercially available cationic surfactant. Other suitable cationic 
surfactants include those comprising at least one lipophilic moiety such 
as an alkyl, aralkyl, aryl, or cycloalkyl group containing 6 to 18 carbon 
atoms, and a hydrophilic moiety such as a substituted ammonium group (for 
example, a tetra-alkylammonium, pyridinium, or like group). The 
counter-ion present should be compatible with the tissue of the wearer; it 
could be, for example, chloride or other halide. 
Preferred cationic surfactants are quaternary ammonium compounds having at 
least one C.sub.8 -C.sub.18 hydrocarbyl (alkyl, aryl, aralkyl or 
cycloalkyl) group; a preferred hydrocarbyl group is a hexadecyl group. The 
hydrocarbyl group may be attached to a quaternary nitrogen atom which is 
part of a heterocyclic ring (such as a pyridine, morpholine, or 
imidazoline ring). 
As previously mentioned, a particularly preferred surfactant is 
hexadecylpyridinium chloride. Other suitable cationic surfactants include 
benzalkonium chlorides, hexadecyltrimethylammonium chloride, 
dodecylpyridinium chloride, the corresponding bromides, a 
hydroxyethylheptadecylimidazolium halide, coconut alkyldimethylammonium 
betaine and coco aminopropyl betaine. 
Mixtures of surfactants may also be used. 
The cationic surfactant, e.g., the preferred cetylpyridinium chloride, 
concentration is in the range from about 0.05% to about 2.5% by weight. A 
range from about 0.25% to about 0.75% by weight, for example, 0.5%, 
cetylpyridinium chloride solution is preferred. 
The acetylenic diols useful in the present invention are acetylenic 
tertiary glycols and the ethylene oxide adducts of acetylenic tertiary 
glycols. Preferably, the acetylenic diols used in the practice of the 
invention are structurally represented by the formula: 
##STR1## 
in which R.sub.1 and R.sub.4 are alkyl radicals containing from 3-10 
carbon atoms, and R.sub.2 and R.sub.3 are selected from the group 
consisting of methyl and ethyl, and x and y have a sum in the range of 
0-60, inclusive, where y=x=0 represents the acetylenic tertiary glycols. 
In the preferred case, R.sub.1 and R.sub.4 are alkyl radicals having 3-4 
carbon atoms each and R.sub.2 and R.sub.3 are methyl groups. Further 
examples and synthesis techniques for the manufacture of these acetylenic 
diols are disclosed in U.S. Pat. Nos. 3,268,593 (Carpenter et al.) and 
3,293,191 (Carpenter et al.), which are hereby incorporated by reference. 
Acetylenic diols useful in the present invention preferably have a 
10-carbon chain as a backbone with a carbon-carbon triple bond in the 
middle with a hydroxyl group on the carbon atoms on either side of the 
triple bond. The combination of these groups yields a region of high 
electron density, making the molecule polar. There is also a symmetrical, 
highly branched group on each side of this region supplying the molecule 
with two hydrophobic areas. Overall the molecule has a 
hydrophobic-hydrophilic-hydrophobic structure, making it a good wetting 
agent or surface tension reducer. See J. Schwartz et al., "Acetylenic 
diol-based additives help glove makers meet quality standards," 
Elastomerics, pages 16-18, December 1989. Suitable acetylenic diols 
include the following available from Air Products and Chemicals, Inc., 
Allentown, Pa: Surfynol.RTM. 104 (2,4,7,9-tetramethyl-5-decyn-4,7-diol), 
Surfynol.RTM. 104E (Surfynol.RTM. 104/ethylene glycol, 50/50), 
Surfynol.RTM. 440 (Surfynol.RTM. 104+3.5 moles ethylene oxide), 
Surfynol.RTM. 465 (Surfynol.RTM. 104+10 moles ethylene oxide) and 
Dynol.RTM. 604 (a mixture of ethoxylated acetylenic diols). 
The acetylenic diols are preferably ethoxylated acetylenic diols such as 
Dynol.RTM. 604 and Surfynol.RTM. 400 series available from Air Products 
and Chemical Inc., Allentown, Pa. Dynol.RTM. 604 is preferred because it 
provides better lubricity. The acetylenic diol is used in the form of a 
solution, such as an aqueous solution containing at least 0.01% by weight 
up to, for example, 2% by weight of acetylenic diols. The acetylenic diols 
may be used in a mixture or combination. 
The modified silicones useful in the present invention are hydrophilic, 
nonionic silicones. Examples of such silicones are commercially available 
from OSi Specialties, Inc., Danbury, Conn. are NuWet.RTM. 100, NuWet.RTM. 
300 and NuWet.RTM. 500. NuWet.RTM. 100 is a copolymer described as an 
organo-modified polydimethylsiloxane, more specifically a polyalkylene 
oxide modified polydimethylsiloxane. NuWet.RTM. 300 is also a copolymer 
described as an amino-modified silicone-polyether copolymer. As a result 
of the amino-modification, this material has reportable quantities of an 
alkanolamine. NuWet.RTM. 500 is a blend of an organo-modified 
polydimethylsiloxane (&gt;65%) and an ethoxylated alkyl (&lt;20%). There are 
reportable quantities of ethylene oxide (&lt;20%; upper bound concentration 
per MSD Sheet is 0.0002%). The following Table provides some physical 
properties for these three materials. 
______________________________________ 
Physical 
Property NuWet .RTM. 100 
NuWet .RTM. 300 
NuWet .RTM. 500 
______________________________________ 
Appearance 
Clear Clear-Sl. Clear 
Haze 
Color Lt. Straw Lt. Straw to 
Colorless to 
Tan Lt. Straw 
Nominal 425 3500 400 
Viscosity, cP 
Solubility in 
Soluble Dispersable Dispersable 
Water 
Ionic Nature 
Non-ionic Non-ionic Non-ionic 
% Actives 
100 100 100 
Density 1.06 1.027 1.02 
Flash Point.sup.a 
175.degree. F. 
230.degree. F. 
285.degree. F. 
Freezing Point 
-9.4.degree. F. 
&lt;32.degree. F. 
&lt;32.degree. F. 
Molecular 
Copolymer Copolymer Copolymer 
Weight 
______________________________________ 
.sup.a PenskyMartens closed cup ASTM D93. 
According to OSi's product bulletin, the following non-aqueous diluents 
have been found useful: 
ethylene-propylene oxide polymers (Ucon 50HB 100, Union Carbide) 
methyl soyate (Emery 2235, Henkel) 
methyl oleate (Emerest 2301, Henkel) 
methyl cannolate (Emery 2231, Henkel) 
propylene carbonate (Arco) 
oleyl alcohol (Novol, Croda) 
When preparing aqueous solutions or dispersions with these materials, OSi 
recommends pouring the silicone into the vortex of the total water while 
mixing at a moderate speed (about 300 rpm to about 400 rpm). Mixing is 
continued until a uniform solution or dispersion is obtained. Non-aqueous 
solutions or dispersions are prepared in a similar manner, but mix at 
about 150 rpm to about 200 rpm until a clear mixture is obtained. 
U.S. Pat. Nos. 4,690,955 (Kilgour et al.); 4,769,174 (Kilgour);4,847,398 
(Mehta et al.) and 4,857,583 (Austin et al.), disclose various 
organo-modified polysiloxane copolymers (i.e., organo-modified silicones) 
and methods of making same. Such copolymers contain hydroxyl groups. The 
amino-modification may be performed by first substituting a halide for the 
hydroxyl group. The halide may then be reacted with ammonia or an amine to 
substitute an amino group for the halide. This latter process is called 
ammonolysis of halides. Alternatively, amino-modified polysiloxanes (i.e., 
amino-modified silicones) may be prepared according to U.S. Pat. No. 
3,905,823 (Piskoti), which is hereby incorporated by reference. Therein 
the amino-modified polysiloxanes are prepared by mixing an organo-modified 
polysiloxane (i.e., organo-modified silicone) with amino-functional 
silanes or siloxanes and thereafter equilibrating the mixture in the 
presence of a base catalyst, e.g., alkali metal hydroxides, alkoxides, 
hydrides, alkyls, alkenyls and aryls, and silanoates. 
The modified silicone is generally used in the form of a solution, such as 
an aqueous solution containing at least 0.05% by weight up to, for 
example, 5% by weight of the modified silicone. 
The coating of lubricant composition need not coat the wearer-contacting 
surface completely. It is only necessary that enough lubricant composition 
is applied to enhance damp slip. It is preferred, to the extent that it is 
practicable, to keep the lubricant composition on the wearer-contacting 
surface, in the case of medical or dental gloves, in order to ensure that 
maximum grip is maintained on the outer surface. The lubricant composition 
can be applied as an aqueous solution containing from about 0.2 to about 
2% by weight lubricant composition total. The article can be dipped in 
such solution or the solution can be sprayed or painted on it, preferably 
before it is removed from the form. Alternatively, the lubricant 
composition can be applied after the article is stripped from the form. 
The process for applying the particle-containing coating to the 
wearer-contacting surface of the elastomer substrate depends, in part, on 
the nature of the substrate and on whether the glove or other article is 
formed by dipping a form into an elastomeric polymer latex or into a 
solution of the elastomeric polymer in a suitable solvent. Methods for 
making the elastomeric substrate articles of the present invention are 
well known in the art. 
Where the article is formed from compounded natural rubber latex, the 
deposit on the form is beaded and leached in the normal way and may then 
be dried and vulcanized. It is envisaged that the coating will normally be 
applied by subsequently dipping the deposit on the form into an aqueous 
suspension of the coating material, i.e., the binder and microparticles. 
The deposit and coating may then be heated to dry them and to complete 
vulcanization of the rubber. 
Other substrate polymers in dispersed, e.g., latex, form, including 
polyurethanes, may be treated similarly, although a vulcanizing step will 
not be needed in every case, as can be readily appreciated by those 
skilled in the art. 
It is understood that various optional ingredients may be incorporated in 
these articles as apparent to those skilled in the art. For example, where 
the article is a glove, an antiblock agent may be used which would 
facilitate donning and use. The antiblock agent is preferably a 
low-melting wax (mp. from about 100.degree. C. to about 150.degree. C.) 
such as polyethylene wax added as an aqueous emulsion (e.g., 1-2%) to the 
coating mixture. The particle size of the wax should be preferably less 
than 1 .mu.m to avoid interference with the surface morphology. 
In accordance with the present invention, an embodiment of a continuous 
process for making a powder-free glove comprises in summary form: 
(i) dip-coating a coagulant onto a glove form; 
(ii) dip-coating over the coagulant layer a layer of an elastomer; 
(iii) leaching the elastomer article in the hot water; 
(iv) heat curing the elastomer; 
(v) chlorinating the glove; 
(vi) neutralizing the glove and residual chlorine; 
(vii) rinsing the glove; 
(viii) treating the glove with a lubricant composition; 
(ix) drying the lubricant treated glove; and 
(x) removing the glove from the form, thereby reversing the glove. 
If the elastomer is not to be chlorinated, steps (v)-(vii) can be omitted. 
In accordance with the present invention, another embodiment of the process 
for making a powder-free glove comprises in summary form: 
(a) General process for making powdered gloves by 
(i) dip-coating a coagulant onto a glove form; 
(ii) dip-coating over the coagulant layer a layer of an elastomer; 
(iii) leaching the elastomer article in the hot water; 
(iv) heat curing the elastomer; 
(v) dip-coating a starch slurry onto the cured elastomer; and 
(vi) removing the glove from the form and reversing the glove. 
(b) Off-line chlorination of the powdered glove followed by treatment with 
the lubricant composition. 
(i) inverting and washing the powdered glove; 
(ii) chlorinating the glove; 
(iii) neutralizing the glove and residual chlorine; 
(iv) rinsing the glove; 
(v) treating the glove with a lubricant composition; 
(vi) drying the lubricant treated glove; and 
(vii) inverting and re-drying the glove. 
The application of the lubricant solution provides the chlorinated 
powder-free glove with superior lubricity with respect to wet/damp hand 
donning. The steps of part (a) may be omitted if powdered gloves are 
available. Likewise, if chlorinated gloves are available, steps 
(b)(ii)-(iv) may be omitted. 
In an expanded manner, the steps for one embodiment of the present 
invention are discussed below. First there is a cleaning step to clean for 
example the hand form, typically made of porcelain, to remove residue from 
previous manufacturing iterations. The clean form is then dried to remove 
water residue by conveying the form through a preheated oven to evaporate 
the water. 
The preheated form is then dip-coated in a bath containing a coagulant, a 
powder source and a surfactant. The coagulant preferably contains calcium 
ions to break the protection system of the emulsion, thereby allowing the 
latex to deposit on the form. The powder is preferably a calcium carbonate 
powder which later acts as a release agent. Alternatively, the powder 
source may be omitted by using the lipo compound and surfactant 
combination in the coagulant to aid in stripping the glove according to 
U.S. Pat. No. 4,310,928 to Jourg. The surfactant provides good wetting to 
avoid forming a meniscus and trapping air between the form and deposited 
latex, particularly in the cuff area. An example of such a surfactant is 
an acetylene diol. As noted above, the form has been preheated in the 
drying step and the residual heat dries off the water leaving calcium 
nitrate, calcium carbonate powder and surfactant on the surface of the 
form. 
The coated form is then dipped into a latex containing tank. The latex 
contains for example, natural rubber latex plus stabilizers, antioxidant, 
activators, accelerators, and vulcanizers, and the latter all being in 
powder form. The stabilizers are preferably of the phosphate type 
surfactants. The antioxidants are preferably the phenol type, for example, 
Antioxidant 2246 (2,2'-methylenebis (4-methyl-6-t-butylphenol)) available 
from PMC Specialty Group, Fords, N.J. The activator may be for example 
zinc oxide. The accelerator may be for example dithiocarbamate. The 
vulcanizer is preferably sulphur or a sulphur-containing compound. If 
these materials are used, the stabilizer, antioxidant, activator, 
accelerator and vulcanizer are dispersed into water to avoid crumb 
formation by using a ball mill or an attritor. This dispersion is then 
mixed into the latex. An emulsified wax, which is used as an antiozonant, 
is then added to the latex mixture. The coated form is then dipped into 
the latex composition with the thickness of the latex deposited thereon 
controlled by the duration of the dip (in a single dip situation). This is 
about 5 to about 20 seconds, e.g., about 12 seconds, for a surgical glove; 
and about 20 to about 70 seconds, e.g., about 50 seconds, for an 
orthopedic glove. 
The form now coated with latex is then dipped into a leaching tank in which 
hot water is circulated to leach out all water soluble components for 
example residual calcium nitrates and proteins contained in the natural 
latex. This leaching process may continue for about twelve minutes with 
the tank water being about 120.degree. F. 
The form is then extracted from the leach bath to a bead and print station. 
At this station, a bead is formed around the cuff area at the end of the 
glove by mechanically rolling down the top portion or the end portion of 
the glove a predetermined amount. Company logos, size and a traceable date 
of manufacture are then printed onto the exterior of the glove, for 
example by injecting ink into the latex coating on the form. 
The latex coated form is then sent to a curing station where the natural 
rubber in the form coating is vulcanized typically in an oven, thereby 
heat curing the rubber. The curing station initially evaporates any 
remaining water in the latex coating of the form and then proceeds to the 
higher temperature vulcanization. The drying may occur between 190.degree. 
F. to 200.degree. F. with a vulcanization step occurring at temperatures 
for example from about 220.degree. F. to about 240.degree. F. This overall 
process may last about forty to forty-five minutes total. For example, the 
oven may be divided into four different zones with a form being conveyed 
through the zones of increasing temperature. One example is an oven having 
four zones with the first two zones being dedicated to drying and the 
second two zones being primarily the vulcanization step. Each of the zones 
may have a slightly higher temperature, for example, the first zone at 
about 180.degree. F., the second zone at about 200.degree. F., a third 
zone at about 220.degree. F. and a final zone at about 240.degree. F. The 
residence time of the form within a zone in this case is about ten minutes 
or so. The accelerator and vulcanizer contained in the latex coating of 
the form are used to cross-link the natural rubber therein. The vulcanizer 
forms sulphur bridges between different rubber segments and the 
accelerator is used to speed up sulphur bridge formation. 
The form now having a cured rubber glove thereon is then dipped into a 
starch slurry. Conventional powder-containing gloves may be withdrawn and 
packaged at this point. The slurry has starch and silicone to improve 
donning of the conventional glove on a person's hand, for example. The 
starch is preferably epichlorohydin cross-linked starch. The silicone is 
also used to try to prevent blocking during stripping of the glove from 
the form and to help donning of a dry hand. Therefore, the glove will have 
a starch powder on the surface which is loosely attached thereto. Next, 
the glove is stripped from the form which inverts the glove with the 
inside now being out and vice versa. The gloves are then sorted by sizes 
and inspected for suitability. 
The foregoing steps are those which are used in making a prior art 
powder-containing glove to aid in the donning of a user's hand. Rather 
than making these gloves, such prior art gloves may be obtained and then 
treated in the following manner. 
These powdered gloves are then inverted again inside out and accordingly is 
in the orientation the glove was in prior to stripping from the form. 
The inverted glove is then washed to remove the powder and starch from the 
glove. The wash is performed with ambient temperature tap water and may be 
repeated as necessary. 
The washed gloves are then chlorinated. If a continuous process is used, 
the cured gloves leaving the curing station and optionally still on the 
form are then chlorinated and the intervening steps omitted. The 
chlorination, or more generally halogenation, may be performed in any 
suitable manner known to those skilled in the art. Such methods include 
(1) direct injection of chlorine gas into the water mixture, (2) mixing 
high density bleaching powder and aluminum chloride in water, (3) brine 
electrolysis to produce chlorinated water, and (4) acidified bleach. See 
for example U.S. Pat. Nos. 3,411,982 (Kavalir), 3,740,262 (Agostinelli), 
3,992,221 (Homsy, et al.; however, it is modified to treat the 
wearer-contacting surface rather than or in addition to treating outer 
surface with chlorine gas), 4,597,108 (Momose), and 4,851,266 (Momose). 
One preferred method is to inject chlorine gas into a water stream and 
then feed the chlorinated water into a chlorinator (a closed vessel) 
containing the washed gloves. The concentration of chlorine can be 
monitored and controlled to control the degree of chlorination. The 
chlorine concentration is typically at least about 500 ppm, preferably 
from about 500 ppm to about 1,200 ppm, e.g., about 800 ppm. The time 
duration of the chlorination step may also be controlled to control the 
degree of chlorination. The time duration may range from about 3 to about 
20 minutes, e.g., 7 minutes. The gloves being in a collapsed state will 
chlorinate to a greater extent on the wearer-contacting surface, i.e., the 
donning side of the glove, with a lesser amount on the non-donning side of 
the glove. 
In another preferred method, the gloves may be chlorinated by placing them 
into a chlorinator, including a front-loaded industrial washer, containing 
a water bath which contains bleach which is subsequently acidified to a pH 
of 2 to about 3. The chlorine concentration ranges from about 0.05 to 
about 0.3 wt. %, e.g., about 0.1 wt. %. The time duration ranges from 
about 3 to about 25 minutes. Again, the donning side of the glove will 
have a greater amount of chlorination than the non-donning side of the 
glove. For a greater degree of chlorination on the non-donning side of the 
glove, the gloves would have to be reinverted and the chlorination step 
repeated. 
The acidified bleach is then neutralized preferably with ammonium hydroxide 
or with sodium thiosulfate. This step neutralizes the acidified water 
contained in the chlorinator and quenches excess chlorine to ammonium 
chloride, if ammonium hydroxide is used. 
Still within the industrial washer, the chlorinated gloves are then rinsed 
with tap water at about ambient temperature. This rinse cycle may be 
repeated as necessary. Once all water is removed from the front-load 
washer, the gloves are tumbled to drain excess water. 
A lubricant solution is then added into the chlorinator containing gloves 
which are then tumbled for about five minutes. This coats the donning side 
with the lubricant solution. The lubricant solution is drained from the 
chlorinator and may be reused. If reused, the lubricant solution is 
preferably reused once more. 
The coated gloves are then put into a drier and dried for about ten to 
fifteen minutes at about 110.degree. F. to dry the donning surface. The 
gloves are then reinverted and the non-donning side dried for about 
twenty-five minutes at about 120.degree. F. 
The foregoing shows a sequence of events in the manufacture of gloves 
according to the present invention. If powdered gloves are available or 
chlorinated gloves are available, some of the preceding steps may be 
eliminated and the process started at the appropriate step in the process.

EXAMPLES 
In the following examples and comparative examples, the following 
additional product designations are used: 
NeoRez.RTM. XR-9624 is an aliphatic polyurethane aqueous dispersion 
available from Zeneca Resins (formerly from ICI Resins), Wilmington, Mass. 
Vedoc.RTM. VP180 is a polyester based polyurethane powder. 
Example I 
The powdered glove is manufactured with the general process described in 
the Detailed Description of the Invention section. 
Off-line chlorination of the powdered glove to produce a powder-free glove 
is performed in the following sequence: 
(1) invert and wash the powdered glove; 
(2) chlorinate the washed glove; 
(3) neutralize the glove and residual chlorine; 
(4) rinse the chlorinated and neutralized glove; 
(5) extract to remove excess water from the glove; 
(6) the chlorinated glove is then treated with the following lubricant 
formulation: 
______________________________________ 
Parts by Weight 
______________________________________ 
Water 99.25 
Cetylpyridinium Chloride 
0.50 
NuWet .RTM. 300 0.25 
______________________________________ 
(7) after lubricant treatment, the lubricant treated glove is dried; 
(8) invert and re-dry the lubricant treated glove. The finished glove is 
found to have no loose powder and superior lubricity with respect to 
wet/damp hand donning. 
Example II 
In accordance with the general procedure of Example I, a glove is formed 
utilizing the following lubricant formulation: 
______________________________________ 
Parts by Weight 
______________________________________ 
Water 99.25 
NuWet .RTM. 500 
0.50 
Dynol .RTM. 604 
0.25 
______________________________________ 
The finished glove is found to have no loose powder and superior lubricity 
with respect to wet/damp hand donning. 
Example III 
In accordance with the general procedure of Example I, a glove is produced 
utilizing the following lubricant formulation: 
______________________________________ 
Parts by Weight 
______________________________________ 
Water 99.25 
Cetylpyridinium Chloride 
0.50 
NuWet .RTM. 500 0.25 
______________________________________ 
The finished glove is found to have no loose powder and superior lubricity 
with respect to wet/damp hand donning. 
Example IV 
A layer of natural rubber latex is applied to an average thickness of 150 
micrometer onto a glove form which then is dipped into the following 
anti-blocking coating formulation: 
______________________________________ 
Parts by Weight 
______________________________________ 
NeoRez XR-9624 285.71 
Deionized Water 
84.62 
Vedoc .RTM. VP 180 
18.00 
______________________________________ 
A layer of the formulation is deposited over the layer of natural rubber 
latex. The layers are then cured and dipped in a starch slurry. The glove 
is stripped from the form in a manner that reverses the glove. A method of 
making a polymer coated glove suitable for use in connection with this 
invention is disclosed in U.S. Pat. No. 5,284,607. 
Off-line chlorination and lubricant treatment of the above glove is 
performed in accordance with the general procedure of Example I. 
The finished glove is found to have no loose powder and superior lubricity 
with respect to wet/damp hand donning. 
The present invention has been described primarily with respect to 
surgeon's gloves. As earlier noted, the present invention is also 
applicable to other skin- or tissue-contacting flexible elastomeric 
articles, such as condoms, gloves used by doctors and veterinary surgeons 
for examination purposes (such gloves often being donned with dry hands), 
catheters, ureters, sheets, sheaths and sheath-type incontinence device. 
When the present invention is used for articles such as ureters and 
catheters, the outer surface is coated with the lubricant composition 
(this being the wearer-contacting surface); for condoms the inner and/or 
outer surface may be treated with the lubricant composition.