Nonwoven articles

Nonwoven particles having high durability and absorbent characteristics, and their methods of manufacture, are presented. One preferred article is characterized by PA1 (a) a nonwoven web comprised of organic fibers comprised of polymers having a plurality of pendant hydroxyl groups; and PA1 (b) a binder comprising an at least partially crosslinked and at least partially hydrolyzed polymeric resin having a plurality of pendant resin hydroxyl groups, the resin crosslinked by a crosslinking agent, the crosslinking agent selected from the group consisting of organic titanates and amorphous metal oxides, the polymeric resin derived from monomers selected from the group consisting of monomers within the general formula ##STR1## wherein: X is selected from the group consisting of Si(OR.sup.4 OR.sup.5 OR.sup.6) and O(CO)R.sup.7 ; and PA1 R.sup.1 -R.sup.7 inclusive are independently selected from the group consisting of hydrogen and organic radicals having from 1 to about 10 carbon atoms, inclusive, and combinations thereof.

BACKGROUND OF THE INVENTION 
1. Brief Description of the Invention 
The invention is drawn toward absorbent, durable nonwoven articles, such as 
wipes, and methods for their manufacture. 
2. Related Art 
Synthetic wiping articles comprised of a nonwoven web made from polyvinyl 
alcohol (PVA) fibers and subsequently coated with covalently crosslinked 
PVA binder resins are known and have been sold as commercial products for 
many years. Chemically crosslinked PVAs provide distinct advantages in 
their usage in synthetic wipes. They increase and improve the elements of 
a dry wipe, non-linting of the wipe surface, mechanical strength, 
hydrophilic properties, and may also be cured in the presence of pigments 
to generate a colored wiping product. While their use has enjoyed 
considerable success, the currently known PVA binders used in synthetic 
wipes are chemically crosslinked in immersion baths containing potentially 
toxic materials, such as formaldehyde, various dialdehydes, 
methylolamines, and diisocyanates. 
Glass and other fibers are sometimes sized (i.e., coated) with PVA coatings 
insolubilized with polyacrylic acid, or crosslinked with metal complexes, 
such as aluminum, titanium, silicon, or zirconium chelates, and the like. 
U.S. Pat. No. 3,253,715 describes boil proof nonwoven filter media 
comprising a nonwoven fiber substrate and a binder comprising polyvinyl 
alcohol and polyacrylic acid. Although cellulosic fibers suitable for 
filters are described, there is no mention of polyvinyl alcohol fibers 
having utility. The polyvinyl alcohol fibers used in the present invention 
are prone to severe shrinkage under the pH and/or temperature conditions 
described in the '715 patent. In addition, the inventors herein have found 
that ratios of polyacrylic acid to polyvinyl alcohol in binders described 
in the '715 patent result in strong, but extremely rubbery, absorbent 
articles with poor "hand" and dry-wipe properties. 
Natural chamois is a highly absorbent article derived from a goat-like 
antelope, and is commonly used to dry automobiles after washing. The 
absorbent properties of natural chamois have been emulated in several 
"synthetic chamois." Synthetic chamois commercially available may be 
formed from PVA fibers and a PVA binder crosslinked by formaldehyde, which 
undesirable for ecological reasons. Other synthetic chamois are known to 
be made from nonwoven fibers and an originally hydrophobic acrylic latex 
binder which has functional groups to make the binder, and thus the 
article, hydrophilic. These latter are inexpensive, but have very high 
drag property. 
It would be desirous to develop a nonwoven article suitable for use in 
absorbing hydrophilic materials employing hydrophilic binders and fibers, 
without the use of formaldehyde. Such an article would allow the articles 
to exhibit high durability, good hand properties, low drag, and good 
dry-wiping properties (picks up water with no streaking) while maintaining 
absorption and "wet out" properties comparable to known articles. Such 
articles could be produced using ingredients and methods which are not as 
harmful to manufacturing personnel, users or the environment as are 
currently used ingredients. Finally, it would be advantageous if such 
binders could be cured in the presence of pigments to generate colored 
wiping products. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, absorbent nonwoven articles are 
presented which can be produced using binder crosslinking agents which are 
less troublesome to handle, and which afford the inventive articles with 
as good or better absorbency and physical properties than known articles. 
In addition, certain preferred embodiments of the inventive articles may 
be made without the use of any chemical crosslinkers. 
As used herein the term "absorbent" means the articles of the invention are 
hydrophilic (and therefore absorbent of aqueous materials). 
Thus, a first aspect of the invention is an absorbent nonwoven article 
comprising: 
(a) a nonwoven web comprised of organic fibers, the organic fibers 
comprised of polymers having a plurality of pendant fiber hydroxyl groups; 
and 
(b) a binder comprising an at least partially crosslinked and at least 
partially hydrolyzed polymeric resin having a plurality of pendant resin 
hydroxyl groups, the resin crosslinked by a crosslinking agent, the 
crosslinking agent selected from the group consisting of organic titanates 
and amorphous metal oxides, the polymeric resin derived from monomers 
selected from the group consisting of monomers within the general formula 
##STR2## 
wherein: X is selected from the group consisting of Si(OR.sup.4 OR.sup.5 
OR.sup.6) and O(CO)R.sup.7 ; and 
R.sup.1 -R.sup.7 inclusive are independently selected from the group 
consisting of hydrogen and organic radicals having from 1 to about 10 
carbon atoms, inclusive, and combinations thereof. 
Preferably, the binder is bonded to at least a portion of the organic 
fibers through bonds between the pendant fiber hydroxyl groups, a bonding 
agent, and the pendant resin hydroxyl groups, wherein the crosslinking 
agent and bonding agent are independently selected from the group 
consisting of organic titanates and amorphous metal oxides. Also preferred 
articles in accordance with this aspect of the invention are those wherein 
the crosslinking agent and bonding agent are the same compounds, and 
wherein R.sup.4 -R.sup.7 inclusive are methyl (--CH.sub.3). 
Two particularly preferred articles within this aspect of the invention are 
those in which the organic titanate crosslinking and/or bonding agent is 
dihydroxybis(ammonium lactato)titanium or a titanium complex with an 
alpha-hydroxy acid (e.g., lactic acid) and an alditol (e.g., D-glucitol). 
As used herein the terms "bond" and "bonding" are meant to include hydrogen 
bonds, hydrophobic interactions, hydrophilic interactions, ionic bonds, 
and/or covalent bonds. The term "crosslinking" means chemical (covalent or 
ionic) crosslinking. 
Especially preferred binders useful in this and other aspects of the 
invention are aqueous compositions comprising copolymers of vinyl 
trialkoxysilane and vinyl monomers such as vinyl/acetate, at least 
partially hydrolyzed with alkali, and at least partially crosslinked with 
inorganic ions and chelating organic titanates. The inorganic ions (e.g., 
aluminum, zirconium) react or otherwise coordinate with silanol groups, 
while the titanates react with secondary hydroxyl groups on the resin. 
This unique dual curing approach, with possibly different crosslinking 
chain lengths, allows intermolecular bonding between the PVA polymers of 
the binder and, theoretically, between the fiber hydroxyl groups and PVA 
polymers of the binder. 
A second aspect of the invention is drawn toward nonwoven absorbent 
articles similar to those of the first aspect of the invention, wherein 
the crosslinking agent is selected from the group consisting of 
dialdehydes, titanates, and amorphous metal oxides. 
A third aspect of the invention is an absorbent nonwoven article 
comprising: 
(a) a nonwoven web comprised of a plurality of organic fibers comprising 
polymers having a plurality of pendant hydroxyl groups; and 
(b) a binder coating at least a portion of the fibers, the binder 
comprising polyvinyl alcohol insolubilized with an effective amount of a 
polymeric polycarboxylic acid (preferably polyacrylic acid). 
Preferred within this aspect of the invention are those articles wherein 
all of the polymers making up the fibers are at least partially hydrolyzed 
polymerized monomers selected from the group consisting of monomers within 
the general formula 
##STR3## 
with the provisos mentioned above. The nonwoven web may further include a 
minor portion of fibers selected from the group consisting of cotton, 
viscose rayon, cuprammonium rayon, polyesters, polyvinyl alcohol, and 
combinations thereof. 
In contrast to the articles described in the above-mentioned U.S. Pat. No. 
3,253,715, we have found that very low amounts of polymeric polycarboxylic 
acid (in the range of 1 to 5 wt. % as weight of total binder weight) 
afford the best wiping properties while effectively eliminating binder 
washout. Further, we have found that pH (negative logarithm of the 
hydrogen ion concentration in aqueous compositions) ranging from 3 to 3.3 
specified by the above-mentioned '715 patent is suitable for the present 
invention, but pH values up to 4.6 may be utilized, which is much more 
useful for reducing web shrinkage. The articles of this aspect of the 
invention employ a polymeric polycarboxylic acid to insolubilize aqueous 
polyvinyl alcohol, thereby providing absorbent articles with superior 
water absorption, dry-wipe, and improved strength compared to known 
articles. 
A fourth aspect of the invention is an absorbent nonwoven article 
comprising: 
(a) a nonwoven web comprised of organic fibers, the organic fibers 
comprised of polymers having a plurality of pendant hydroxyl groups; and 
(b) a binder coated onto at least a portion of the fibers comprising 
syndiotactic polyvinyl alcohol, the syndiotactic polyvinyl alcohol having 
a syndiotacticity of at least 30%. 
Articles employing the binder system mentioned in part (b) of this aspect 
of the invention employ syndiotactic polyvinyl alcohol (s-PVA) as a major 
(or only) component in the binder. The advantage of this binder is that 
s-PVA may be employed without a chemical crosslinking agent. This is 
because s-PVA tends to form microcrystalline regions. Chemical 
crosslinking through the use of titanates, inorganic ions, and dialdehydes 
may be employed, but they are rendered optional. 
A fifth aspect of the invention is a method of making an absorbent nonwoven 
article, the method comprising: 
(a) forming an open, lofty, three-dimensional nonwoven web comprised of 
organic fibers, the organic fibers comprised of polymers having a 
plurality of pendant hydroxyl groups; 
(b) entangling the fibers of the web using means for entanglement to form 
an entangled fiber web; 
(c) coating a major portion of the fibers of the entangled fiber web with a 
binder precursor composition to form a first coated web having first and 
second major surfaces, the binder precursor composition adapted to form 
the binder of the second aspect of the invention; and 
(d) exposing the first coated web to energy sufficient to at least 
partially cure the binder precursor composition to form a nonwoven bonded 
web of fibers. 
Preferred are those methods wherein the before step (c) the entangled fiber 
web is calendered, and those methods wherein after step (c) the first 
coated web is coated on at least one of its first and second major 
surfaces with a second binder precursor composition. Also preferred are 
those methods wherein the exposing step includes drying the second binder 
precursor composition uniformly to form a dried and cured nonwoven web 
having a surface coating, and those methods wherein the dried and cured 
nonwoven web is calendered, thereby smoothing and fusing the surface 
coating. 
A sixth aspect of the invention is another method of making an absorbent 
nonwoven article comprised of a nonwoven web of fibers, at least a portion 
of the fibers having a binder coated thereon, the method comprising: 
(a) forming a nonwoven web comprised of a plurality of organic fibers 
comprising polymers having a plurality of pendant fiber hydroxyl groups, a 
major portion of the polymers comprising polyvinyl alcohol; 
(b) entangling the fibers of the web using means for entanglement to form 
an entangled fiber web; 
(c) coating a major portion of the fibers of the entangled fiber web with a 
binder precursor composition to form a first coated web having first and 
second major surfaces, the binder precursor composition consisting 
essentially of polyvinyl alcohol and an effective amount of a polymeric 
polycarboxylic acid; and 
(d) exposing the first coated web to energy sufficient to insolubilize the 
polyvinyl alcohol resin to form a nonwoven bonded web of fibers. 
Optionally, bonding and crosslinking agents, as discussed herein, may be 
added to the binder precursor composition. 
Finally, a seventh aspect of the invention is another method of making an 
absorbent nonwoven article comprised of a nonwoven web of fibers, at least 
a portion of the fibers having a binder coated thereon, the method 
comprising: 
(a) forming a nonwoven web comprised of organic fibers, the organic fibers 
comprised of polymers having a plurality of pendant hydroxyl groups; 
(b) entangling the fibers of the web using means for entanglement to form 
an entangled fiber web; 
(c) coating a major portion of the fibers of the entangled fiber web with a 
binder precursor composition to form a first coated web having first and 
second major surfaces, the binder precursor composition consisting 
essentially of syndiotactic polyvinyl alcohol having a syndiotacticity of 
at least 30%; and 
(d) exposing the first coated web to energy sufficient to at least 
partially cure the binder precursor composition to form a nonwoven bonded 
web of fibers. 
An important aspect of the invention is that articles of the invention may 
employ inventive binders which allow the articles to exhibit high 
durability, good feel, reduced drag, and good dry wiping properties while 
maintaining comparable water absorption and "wet out" properties to 
existing wipes. In addition, wiping articles of the present invention may 
also be cured in the presence of pigments to generate colored wiping 
products. 
Preferred articles within the invention may also include in the binder 
efficacious amounts of functional additives such as, for example, fillers, 
reinforcements, plasticizers, grinding aids, and/or conventional 
lubricants (of the type typically used in wiping articles) to further 
adjust the absorbance, durability, and/or hand properties. 
The binders useful in the articles of the invention improve on conventional 
formaldehyde crosslinking agents which tend to embrittle the web fibers, 
reducing web strength, softness, and absorption, and which present 
chemical hazards. 
Regarding the methods of the invention, in preferred methods the "exposing" 
step is preferably carried out in a fashion to afford uniform drying 
throughout the thickness of the web. Typically and preferably the exposing 
step is a two stage process wherein the coated web is first dried at a low 
temperature and subsequently exposed to a higher temperature to cure the 
binder precursor. In some embodiments, a third, higher temperature curing 
step is employed. As discussed herein below, to achieve uniformly dried 
and cured articles, both major surfaces of the uncured web are preferably 
exposed to a heat source simultaneously, or both major surfaces are 
sequentially exposed to the heat source. The methods of the invention may 
also encompass perforating and slitting the dried and cured bonded 
nonwoven into various finished products. 
Further aspects and advantages of the invention will become apparent from 
the drawing figures and description of preferred embodiments which follows 
.

DESCRIPTION OF PREFERRED EMBODIMENTS 
1. Articles Employing Chemically Crosslinked PVA Binders 
Embodiments within this aspect of the invention include articles comprising 
a nonwoven web of fibers having coated thereon a binder comprising 
polyvinyl alcohol (preferably silanol modified) crosslinked with inorganic 
ions, chelating organic titanates, or combinations thereof. 
The nonwoven web of fibers may be made from many types of hydrophilic 
fibers, and may include a minor portion of hydrophobic fibers, selected 
from the following fiber types: cellulosic-type fibers, such as PVA 
(including hydrolyzed copolymers of vinyl esters, particularly hydrolyzed 
copolymers of vinyl acetate), cotton, viscose rayon, cuprammonium rayon 
and the like, and thermoplastics such as polyesters, polypropylene, 
polyethylene and the like. The preferred cellulosic-type fibers are rayon 
and polyvinyl alcohol. Webs containing 100% PVA fibers, 100% rayon fibers, 
and blends of PVA fibers and rayon fibers in the wt. % range of 1:100 to 
100:1 are within the invention, and those webs having PVA:rayon within the 
weight range of 30:70 to about 70:30 are particularly preferred in this 
aspect of the invention, since the coated products exhibit good 
hydrophilicity, strength, and hand. 
Some aspects of the nonwoven fiber web are common to all article 
embodiments of the invention. The fibers employed typically and preferably 
have denier ranging from about 0.5 to about 10 (about 0.06 to about 11 
tex), although higher denier fibers may also be employed. Fibers having 
denier from about 0.5 to 3 (0.06 to about 3.33 tex) are particularly 
preferred. ("Denier" means weight in grams of 9000 meters of fiber, 
whereas "tex" means weight in grams per kilometer of fiber.) Fiber stock 
having a length ranging from about 0.5 to about 10 cm is preferably 
employed as a starting material, particularly fiber lengths ranging from 
about 3 to about 8 cm. 
Nonwoven webs of fibers for use in the articles of the invention may be 
made using methods well documented in the nonwoven literature (see for 
example Turbak, A. "Nonwovens: An Advanced Tutorial", Tappi Press, 
Atlanta, Ga., (1989). The uncoated (i.e., before application of any 
binder) web should have a thickness in the range of about 10 to 100 mils 
(0.254 to 2.54 mm), preferably 30 to 70 mils (0.762 to 1.778 mm), more 
preferably 40 to 60 mils (1.02 to 1.524 mm). These preferred thicknesses 
may be achieved either by the carding/crosslapping operation or via fiber 
entanglement (e.g., hydroentanglement, needling, and the like). The basis 
weight of the uncoated web preferably ranges from about 50 g/m.sup.2 up to 
about 250 g/m.sup.2. 
Binders within this aspect of the invention preferably are crosslinked via 
secondary hydroxyl groups on the PVA backbone with chelating organic 
titanates, and optionally with dialdehydes such as glyoxal. The resultant 
binder system will theoretically further react with hydroxyl groups on the 
fibers when cured at elevated temperatures to produce coated webs with 
excellent wiping properties. 
Particularly preferred are "dual" crosslinked binders, wherein an amorphous 
metal oxide coordinates with silanol groups on the PVA backbone and 
titanates and/or glyoxal coordinate with secondary hydroxyl groups on the 
PVA backbone. 
Silanol modified PVA's used in the present invention may be made via the 
copolymerization of any one of a number of ethyleneically unsaturated 
monomers having hydrolyzable groups with an alkoxysilane-substituted 
ethylenenically unsaturated monomer. Examples of the former are vinyl 
acetate, acetoxyethyl acrylate, acetoxyethylmethacrylate, and various 
propyl acrylate and methacrylate esters. Examples of 
alkoxysilane-substituted ethylenenically unsaturated monomers include 
vinyl trialkoxysilanes such as vinyl trimethoxysilane and the like. 
One particularly preferred silanol-modified PVA may be produced from the 
copolymerization of vinyl acetate and vinyl trialkoxysilane, followed by 
the direct hydrolysis of the copolymer in alkaline solution (see below). 
One commercially available product is that known under the trade 
designation "R1130" (Kuraray Chemical KK, Japan). This preferred base 
copolymer contains from about 0.5 to about 1.0 molar % of the silyl groups 
as vinylsilane units, a degree of polymerization of about 1700, and degree 
of hydrolysis of the vinyl acetate units preferably of 99+%. 
The theoretical crosslink density may range from 1 to about 40 mole % based 
on mole of ethyleneically unsaturated monomer. This may be achieved by 
addition of one or more aqueous titanates and, optionally, 
dialdehyde/NH.sub.4 Cl solutions to a polyvinyl alcohol binder resin. 
Though dialdehydes such as glyoxal and several classes of titanium 
complexes have been shown to crosslink aqueous compositions of polyvinyl 
alcohol, we have found that chelating titanates such as 
dihydroxybis(ammonium lactato) titanium (available under the trade 
designation "Tyzor LA" from du Pont) and titanium orthoesters such as 
Tyzor 131 provide excellent crosslinking for wiping articles described in 
this invention. It is desired that crosslinking be avoided until curing 
conditions (i.e., high temperatures) are present. Thus, organic acids, 
such as citric acid, may help to stabilize titanates such as 
dihydroxybis(ammonium lactato) titanium in aqueous compositions until the 
binder precursors are exposed to crosslinking and curing conditions. 
To improve the tensile and tear strength of the inventive articles, and to 
reduce lint on the surface of the articles, it may be desirable to 
entangle (such as by needletacking, hydroentanglement, and the like) the 
uncoated web, or calender the uncoated and/or coated and cured nonwoven 
articles of the invention. Hydroentanglement may be employed in cases 
where fibers are water insoluble. Calendering of the binder coated web at 
temperatures from about 5.degree. to about 40.degree. C. below the melting 
point of the fiber may reduce the likelihood of lint attaching to the 
surface of the inventive articles and provide a smooth surface. Embossing 
of a textured pattern onto the wipe may be performed simultaneously with 
calendering, or in a subsequent step. 
In addition to the above-mentioned components of the articles of this 
invention, it may also be desirable to add colorants (especially 
pigments), softeners (such as ethers and alcohols), fragrances, fillers 
(such as for example silica, alumina, and titanium dioxide particles), and 
bactericidal agents (for example iodine, quaternary ammonium salts, and 
the like) to add values and functions to the wiping articles described 
herein. 
Coating of the binder resin may be accomplished by methods known in the 
art, including roll coating, spray coating, immersion coating, gravure 
coating, or transfer coating. The binder weight as a percentage of the 
total wiping article may be from about 1% to about 95%, preferably from 
about 10% to about 60%, more preferably 20 to 40%. 
2. Articles Employing PVA-PA Blends as Binders 
The absorbent nonwoven articles in accordance with this aspect of the 
invention comprise a nonwoven web of a plurality of organic fibers 
comprising polymers having a plurality of pendant hydroxyl groups, a major 
portion of the polymers being at least partially hydrolyzed polymerized 
monomers selected from the group consisting of monomers within the general 
formula 
##STR4## 
wherein X is O(CO)R.sup.7 the provisos mentioned above. A binder coats at 
least a portion of the fibers, the binder consisting essentially of 
polyvinyl alcohol insolubilized with an effective amount of polyacrylic 
acid. Optionally, chemical crosslinking agents and/or bonding agents may 
also be employed. 
The nonwoven web of fibers is substantially the same as that described in 
Section 1 above. Any fiber type, such as polyesters, polyolefins, 
cellulosics, acrylics, and the like, may be employed, alone or in 
combination. Preferably, the nonwoven web of fibers comprises one or more 
of the following fibers: cotton, viscose rayon, cuprammonium rayon, 
polyvinyl alcohols including hydrolyzed copolymers of vinyl esters, 
particularly hydrolyzed copolymers of vinyl acetate and the like. 
Preferred cellulosic-type fibers are rayon and polyvinyl alcohol. Blends 
of rayon and polyvinyl alcohol fibers in the weight ranges given above in 
Section 1 are preferred. 
The fiber denier and length are also as previously described in Section 1 
above, as well as the preferred ranges for uncoated web thickness and 
weight. 
Coating of the binder resin may accomplished by the previously mentioned 
methods, including roll coating, spray coating, immersion coating, 
transfer coating, gravure coating, and the like. The binder weight as a 
percentage of the total nonwoven article weight for this aspect of the 
invention may range from about 5% to about 95%, preferably from about 10% 
to about 60%, more preferably 20 to 40%. 
Polymeric polycarboxylic acids useful in the invention include polyacrylic 
acid, polymethacrylic acid, copolymers of acrylic acid, methacrylic acid 
or maleic acid containing more than 10% acidic monomer, provided that such 
copolymers or their salts are water soluble the specified pH levels; and 
vinyl methyl ether/maleic anhydride copolymer. 
Polyacrylic acid, the most preferred polymeric polycarboxylic acid useful 
in the present invention preferably has a weight average molecular weight 
ranging from about 60,000 to about 3,000,000. More preferably, the weight 
average molecular weight of polyacrylic acid employed ranges from 300,000 
to about 1,000,000. 
Optionally, small amounts (i.e., less than about 5 wt. % of the total 
weight of binder) of additional monomers (such as, for example, 
functionalized acrylate monomers like hydroxyethylmethacrylate, vinyl 
azlactone monomers, and the like) may be incorporated in the PVA binder 
polymer to reduce binder washout during repeated use. 
As with previously described embodiments, chemical crosslinkers may be 
used. Preferred crosslinkers are titanates, dialdehydes, borates, and the 
like. 
The nonwoven articles of this aspect of the invention may be calendered as 
previously described in Section 1 to reduce lint on the surface of the 
article and provide a smooth surface for printing. Embossing of a textured 
pattern onto the wipe may be performed simultaneously with calendering, or 
in a subsequent step. 
The above-mentioned optional components (colorants, softeners, fragrances, 
fillers) may also be employed in the nonwoven articles of this aspect of 
the invention. 
3. Articles Employing Binders Comprising Syndiotactic PVA 
Triad syndiotacticity, as used herein, means that of a triad of three 
pendant hydroxyl groups, the hydroxyl groups are positioned in an 
alternating pattern from side to side along the polymer chain. This is 
opposed to atactic, which means that the hydroxyl groups are randomly 
arranged, and isotactic, meaning the hydroxyl groups are positioned on the 
same side of the polymer chain. 
Nonwoven absorbent articles within this aspect of the invention comprise a 
nonwoven web of fibers comprised of polymers having a plurality of pendant 
hydroxyl groups. The binder for articles within this aspect of the 
invention comprises polyvinyl alcohol having a syndiotacticity of at least 
30%. Optionally, a chemical crosslinking agent may also be present. 
The nonwoven web of fibers comprises fibers substantially the same as those 
described above as useful for the other articles of the invention. The 
fiber length and denier, and uncoated web thickness and weight are also as 
above-described in Section 1. Coating of the binder resin may be 
accomplished by the above-mentioned methods known in the art including 
roll coating, spray coating, immersion coating, transfer coating, gravure 
coating, and the like. The binder weight as a percentage of the total 
article weight for articles within this aspect of the invention may range 
from about 5% to about 95%, preferably from about 10% to about 60%, more 
preferably 20 to 40%. 
For preparing syndiotactic PVA, vinyl trihaloacetoxy monomers are commonly 
employed, such as, vinyl trifluoroacetate, trifluoroacetoxyethyl acrylate, 
trifluoroacetoxyethyl methacrylate, and the like. 
Polyvinyl trifluoroacetate is a preferred precursor ester for preparation 
of syndiotactic polyvinyl alcohol used in practice of the invention due to 
its high chemical reactivity making conversion to polyvinyl alcohol 
relatively facile. It may be hydrolyzed with alcoholic alkali, but is 
preferably hydrolyzed with methanolic ammonia (see Example 64 below). 
Polyvinyl trifluoroacetate is readily prepared by polymerization of vinyl 
trifluoroacetate. 
Optionally, small amounts (i.e., less than about 5 wt. %) of additional 
monomers may be incorporated in the parent polymer to improve various 
properties of the polyvinyl alcohol derived therefrom. A particularly 
preferred syndiotactic PVA (and used in Examples 65-91 below) is 
poly(vinyl trifluoroacetate-co-[3-allyl-2,2'-dihydroxy-4,4'-dimethoxybenzo 
phenone]) (99.95:0.05 by weight, abbreviated as PVTFA). The triad 
syndiotacticity measured by .sup.1 H NMR was 51%, isotacticity=7%, 
atacticity=42%. 
The syndiotacticity of the polyvinyl alcohol binder employed in this aspect 
of the invention typically and preferably ranges from about 45% to 100% 
syndiotacticity. It is known that increasing syndiotacticity at constant 
degree of polymerization results in increased melting point for the gel. 
(See Matsuzawa, S. et al., "Colloid Poly. Sci. 1981", 259(12), pp. 
1147-1150.) For this reason higher syndiotacticity is preferred since 
mechanical strength and thermal stability are improved, but aqueous 
compositions of polyvinyl alcohol become more viscous and/or thixotropic 
as syndiotacticity increases due to gel formation. For these reasons, and 
owing to methods of preparation, the preferred range of syndiotacticity 
when coated from aqueous compositions preferably ranges from about 25 to 
about 65% syndiotacticity. 
Although detrimental to the flexibility of the nonwoven articles of the 
invention, it may be advantageous to incorporate a small amount (e.g., up 
to about 10 mole %) of a chemical crosslinker such as those mentioned 
above in order to eliminate washout of the binder during use. Preferred 
crosslinkers are the above-mentioned titanates, with dialdehydes and the 
like being suitable but less preferred for ecological reasons. 
The nonwoven articles of this aspect of the invention may be calendered at 
elevated temperature as above-described to reduce lint on the surface of 
the article and provide a smooth surface for printing. Embossing of a 
textured pattern onto the wipe may be performed simultaneously with 
calendering, or in a subsequent step. In addition, the above-mentioned 
colorants, softeners, fragrances, fillers, and the like may be employed. 
4. Particularly Preferred Articles and Methods 
Referring now to the drawing figures, FIG. 1 illustrates a perspective view 
of an absorbent nonwoven article 10 made in accordance with the invention. 
Article 10 has a plurality of fibers 12 at least partially coated with 
binder. 
FIG. 2 is a cross-sectional view of the article of FIG. 1 taken through the 
section 2--2 of FIG. 1. FIG. 2 illustrates a preferred article wherein the 
major surfaces 14 and 16 (illustrated in exaggerated thickness) are 
comprise a combination of calendered and fused organic fibers and binder. 
Surfaces 14 and 16 form a sandwich with nonwoven material 18. 
FIG. 3 illustrates a preferred method of producing the nonwoven articles 
illustrated in FIGS. 1 and 2. Staple fibers are fed via a hopper 20 or 
other means into a carding station 22, such devices being well known and 
not requiring further explanation. A moving conveyer transports a carded 
web from carding station 22, typically to a crosslapper, not shown, which 
forms a layered web having fibers at various angles to machine direction. 
Carded web 26 then typically and preferably passes through a needling 
station 28 to form a needled web 30 which is passed through calender 
station 32. At this point the calendered web 34 is not more than about 60 
mils (1.524 mm) thick. Calendered web 34 then passes through an immersion 
bath 36 where an aqueous binder precursor composition 37 is applied. Web 
34 passes under rollers 38 and emerges as a coated web 40, which then 
passes through a drying station 42 to form a dried web 44. Drying station 
42 typically and preferably exposes the web to a temperature and for a 
residence time which allows substantially all of the water to be removed 
from the binder precursor to form a dried web 44. 
Depending on the composition of the binder precursor, type of crosslinking 
and/or bonding agent used, amount of water present, etc., web 44 may be 
suitable for use without further curing. In some embodiments, it is 
desirable to pass dried web 44 through a final curing station 46, which is 
at a temperature higher than the temperature of drying station 42, to form 
a dried and cured web 48. 
Web 48 may then be passed through another set of calender rollers 50, which 
may used to emboss a pattern, fuse the surfaces, and impart other 
qualities to the article. Web 52 generally has a thickness of no more than 
60 mils (1.524 mm), and a weight ranging from about 50 g/m.sup.2 to about 
250 g/m.sup.2. 
Web 52 may then pass through a second needling station 54 to perforate the 
web for decorative or other purposes, after which the web is slit and 
wound onto take-up roll 56. 
The features of the various aspects of the invention will be better 
understood in reference to the following Test Methods and Examples, 
wherein all parts and percentages are by weight. Names of ingredients in 
quotation marks indicate trade designations. 
TEST METHODS 
Tensile Strength 
Tensile strength measurements were made on 1.times.3 inch (2.54.times.7.62 
cm) wringer damp, die cut samples using an Instron Model "TM", essentially 
in accordance with ASTM test method D-5035. A constant rate of extension 
(CRE) was employed, and jaws were clamp-type. Rate of jaw separation was 
9.3 inches/min. (23.6 cm/min). 
Elmendorf Tear 
Elmendorf tear tests were conducted on 2.5.times.11 inch (6.35.times.27.94 
cm) damp, die-cut, notched (20 mm) samples, essentially in accordance with 
ASTM D-1424, using an Elmendorf Tear Tester model number 60-32, from 
Thwing-Albert Co., with a 3200 gram pendulum. An average of four 
measurements was used. A high value is desired. 
Absorption 
Absorption measurements were made on 6.times.8 inch (15.24.times.20.32 cm) 
samples which were die-cut in damp conditions. The absorption measurements 
are reported using the following terms: 
(a) Dry Weight=the dried weight of the sample, in grams. 
(b) No Drip Weight=the maximum total weight of the sample and water 
absorbed, in grams. 
(c) With Drip Weight=the total weight of the sample, in grams, after 
dripping for 60 seconds. 
(d) Damp Weight=the weight of the sample after passing through nip rollers. 
(e) Wet Out=the time it takes for a droplet of water placed on the wipe 
surface to be completely absorbed into the sample. 
(f) % Weight (H.sub.2 O) Loss=(No Drip Weight-With Drip Weight)/No Drip 
Weight. 
(g) Grams Water Absorbed per Square foot (grams/929 cm.sup.2)=3.times.(No 
Drip Weight-Dry Weight). 
(h) Grams Water Absorbed per Gram Dry Weight=(No Drip Weight-Dry 
Weight)/Dry Weight. 
(i) MD=machine direction, 
CD=cross direction, 
"abs"=absorbed, and 
"eff"=effective 
(j) effective water absorption=3.times.(no drip weight-damp weight). 
MATERIALS DESCRIPTION 
The materials are used in the examples which follow: 
"R1130" is the trade designation for a copolymer of vinyl silane and vinyl 
acetate containing from about 0.5 to about 1.0 molar % of the silyl groups 
as vinylsilane units, a degree of polymerization of about 1700, and degree 
of hydrolysis of the vinyl acetate units preferably of 99+% (Kuraray 
Chemical KK, Japan). 
"Tyzor LA" is the trade designation for dihydroxybis(ammonium lactato) 
titanium (50 wt. % aqueous solution, available from du Pont Company, Du 
Pont Company), glyoxal (40 wt. % aqueous solution, Aldrich Chemicals) are 
then added to the silanol modified PVA solution at various proportions and 
combinations as described in the examples to follow. 
"Tyzor 131" is the trade designation for a mixture of titanium orthoester 
complexes (20 wt. % aqueous solution, also available from DuPont. 
"Nalco 8676" is the trade designation for a nanoscale, amorphous aluminum 
hydrous oxide colloid (10 wt. % aqueous solution), available from Nalco 
Chemical Company. 
glyoxal is a dialdehyde of formula HCOCOH, available as a 40 wt. % aqueous 
solution from Aldrich Chemicals, Co. 
"Airvol 165" is the trade designation for a 99.5+% hydrolyzed polyvinyl 
alcohol from Air Products and Chemicals, Inc. 
EXAMPLES 
General Procedure I for Preparing Inventive Articles 
Nonwoven webs consisting of a blend of polyvinyl alcohol and rayon fibers 
(45% polyvinyl alcohol fiber having 1.5 denier and a length of 1.5 inch 
(3.81 cm) purchased from Kuraray, Japan, and 55% rayon fiber having 1.5 
denier and a length of 1 and 9/16 inch (3.97 cm) purchased from BASF) were 
made using a web, making machine known under the trade designation 
"Rando-Webber". The resultant web had a nominal basis weight of 11.5 
g/ft.sup.2 (123.8 g/m.sup.2) and an average thickness of 0.052 inch (0.132 
cm). 
Silanol modified polyvinyl alcohol granules ("R1130") were added to 
deionized water in proportions up to 10 wt. % solid in a stirred flask. 
The flask was then heated to 95.degree. C. until reflux condition is 
achieved. The polymeric solution was then kept at reflux for a minimum of 
45 minutes with adequate mixing. The solution was then cooled down to room 
temperature (about 25.degree. C.). The silanol modified PVA solution was 
then diluted to 2.5 wt. % solid. Reactants such as Nalco 8676, Tyzor LA, 
Tyzor 131, and glyoxal were then added to the silanol modified PVA 
solution at various proportions and combinations as described in the 
examples to follow. 
A 12.times.15 inch (30.48.times.38.1 cm) piece of this nonwoven web was 
placed in a pan and saturated with approximately 200 g of an aqueous 
coating solution containing 5.00 g of total polymer. 
Saturated samples were then dried and cured in a flow-through oven at 
various conditions to be described in the examples below. When curing was 
completed, the samples were conditioned for 60 minutes in 
60.degree.-80.degree. F. (140.degree.-176.degree. C.) tap water then 
dried. Samples were then analyzed for hydrophilicity, water retention and 
absorption, tensile strength, tear strength, and dry wiping properties. 
Examples 1-10 and Comparative Example A 
The results of testing on Comparative Example A, a nonwoven wipe originally 
59 mils (0.149 cm) thick, and known under the trade designation 
"Brittex-11" (available from Vileda, a division of Freudenberg Co., 
Germany, and which is a PVA web coated with a PVA binder crosslinked with 
formaldehyde) were as follows: 
Wet Out=3 sec.; 
% Water Loss=12.8; 
Total Water Absorption=137.5 g/ft.sup.2 (1479 g/m.sup.2); 
g of water absorbed/g of wipe=7.9; 
tensile strength (machine direction)=273 lbs/in.sup.2 (1882 KPa); 
tensile strength (cross direction)=203 lbs/in.sup.2 (1399 KPa); 
Elmendorf Tear strength (machine direction and damp)=86; 
Elmendorf Tear strength (cross direction and damp)=100+. 
The test results for the inventive nonwovens of Examples 1-10 are presented 
in Tables 1 and 2. The nonwovens of Examples 1-10 were prepared as 
described in General Procedure I. For each example, 200 g of the polymeric 
solution (2.5 wt. % of R1130) was added with the reactants described below 
along with 0.1 g of Orcabrite Green BN 4009 pigment. The wt. % designated 
below represents the wt. % of active reactant (solid) over the R1130 
polymer. The coated samples were dried at 150.degree. F. (65.5.degree. C.) 
for 2 hrs. then 250.degree. F. (121.1.degree. C.) for 2 hrs. and finally 
cured at 300.degree. F. (148.8.degree. C.) for 10 minutes. All samples had 
excellent dry wiping properties, low drag, and good feel. 
TABLE 1 
__________________________________________________________________________ 
g H2O 
Sample Wet out 
abs/g of 
g H2O 
% H2O 
Ex. # 
Description 
(sec) Dry wipe 
abs/(ft.sup.2) 
Loss 
__________________________________________________________________________ 
1 Uncoated 0 11.37 148.7 
24.78 
nonwoven 
substrate 
COMATIVE 
2 R1130 0 8.90 158.6 
18.55 
3 R1130/0.5 wt. % 
0 8.37 159.7 
17.2 
Nalco 
8676/5 wt. % 
Tyzor 131 
4 R1130/0.5 wt. % 
0 7.46 145.7 
21.2 
Nalco 8676/ 
15 wt. % 
Tyzor 131 
5 R1130/0.5 wt. % 
0 8.42 150.3 
15.95 
Nalco 
8676/5 wt. % 
Tyzor LA 
6 R1130/0.5 wt. % 
0 7.79 155.9 
16.73 
Nalco 
8676/15 wt. % 
Tyzor LA 
7 R1130/5 wt. % 
0 8.26 145.5 
15.71 
Tyzor 131 
8 R1130/15 wt. % 
0 7.83 150.4 
17.11 
Tyzor 131 
9 R1130/5 wt. % 
0 8.52 151.1 
16.47 
Tyzor LA 
10 R1130/15 wt. % 
0 8.06 136.6 
12.93 
Tyzor LA 
__________________________________________________________________________ 
TABLE 2 
______________________________________ 
Tensile Strength 
Elmendorf 
(KPa) Tear 
Ex.# Sample Description 
MD CD MD CD 
______________________________________ 
1 Uncoated nonwoven 
1289 641 74.7 56.3 
substrate 
COMATIVE 
2 R1120 2126 2011 85.5 93.0 
3 R1130/0.5 wt. % 
2555 2012 95.0 88.0 
Nalco 8676/5 wt. % 
Tyzor 131 
4 R1130/0.5 wt. % 
2770 2032 86.3 100 
Nalco 8676/15 wt. % 
Tyzor 131 
5 R1130/0.5 wt. % 
2543 2001 76.7 85.0 
Nalco 8676/5 wt. % 
Tyzor LA 
6 R1130/0.5 wt. % 
2802 1921 90.3 100 
Nalco 8676/15 wt. % 
Tyzor LA 
7 R1130/5 wt. % 2481 2155 77.0 84.5 
Tyzor 131 
8 R1130/15 wt. % 2327 2201 90.8 84.0 
Tyzor 131 
9 R1130/5 wt. % 2356 1787 80.3 82.5 
Tyzor LA 
10 R1130/5 wt. % 2769 2090 78.0 87.5 
Tyzor LA 
______________________________________ 
Examples 11-20 
The wipes of Example 11-20 were prepared as described in General Procedure 
I, and dried and cured as in Examples 1-10, except that the final 10 
minute cure at 300.degree. F. (121.1.degree. C.) was eliminated. The 
absorbency, tensile strength and tear test results are presented in Tables 
3 and 4. 
It can be seen comparing the data of Tables 3 and 4 with the data of Tables 
1 and 2 that addition of Tyzor LA or Tyzor 131, and the final 
121.1.degree. C. cure, gave immediate wet-out and consistently higher 
tensile strength and Elmendorf tear values. 
TABLE 3 
__________________________________________________________________________ 
g H2O 
Sample Wet out 
abs/g of 
g H2O 
% H2O 
Ex. # 
Description 
(sec) dry Wipe 
abs/(ft.sup.2) 
Loss 
__________________________________________________________________________ 
11 R1130/0.5 wt. % 
28 8.87 152.8 
17.7 
Nalco 8676 
12 R1130/1 wt. % 
60+ 7.80 141.5 
14.09 
Nalco 8676 
13 R1130/1.5 wt. % 
60+ 7.65 141.7 
13.99 
Nalco 8676 
14 R1130/2.0 wt. % 
60+ 7.48 138.7 
14.92 
Nalco 8676 
15 R1130/0.5 wt. % 
0 8.35 160.7 
19.60 
Nalco 8676/1 
wt. % Tyzor LA 
16 R1130/0.5 wt. % 
0 8.49 161.5 
19.70 
Nalco 8676/ 5 
wt. % Tyzor LA 
17 R1130/0.5 wt. % 
0 8.31 155.6 
16.57 
Nalco 8676/ 
10 wt. % Tyzor 
LA 
18 R1130/0.5 wt. % 
0 8.49 164.2 
18.63 
Nalco 8676/ 1 
wt. % Tyzor 
131 
19 R1130/0.5 wt. % 
0 8.12 165.0 
19.69 
Nalco 8676/ 5 
wt. % Tyzor 
131 
20 R1130/0.5 wt. % 
0 8.61 164.8 
21.33 
Nalco 8676/ 
10 wt. % Tyzor 
131 
__________________________________________________________________________ 
TABLE 4 
______________________________________ 
Tensile Strength 
Elmendorf 
(KPa) Tear 
Ex.# Sample Description 
MD CD MD CD 
______________________________________ 
11 R1130/0.5 wt. % 
2218 2022 91.7 85.0 
Nalco 8676 
12 R1130/1 wt. % 2212 1856 88.8 100.0 
Nalco 8676 
13 R1130/1.5 wt. % 
2678 1948 83.3 90.0 
Nalco 8676 
14 R1130/2.0 wt. % 
2961 2164 86.3 100.0 
Nalco 8676 
15 R1130/0.5 wt. % 
2425 1783 78.3 100.0 
Nalco 
8676/1 wt. % 
Tyzor LA 
16 R1130/0.5 wt. % 
2182 2086 74.5 100.0 
Nalco 8676/ 
5 wt. % 
Tyzor LA 
17 R1130/0.5 wt. % 
2379 2130 100.0 95.0 
Nalco 8676/ 
10 wt. % 
Tyzor LA 
18 R1130/0.5 wt. % 
2390 1959 90.3 92.0 
Nalco 8676/ 
1 wt. % 
Tyzor 131 
19 R1130/0.5 wt. % 
2295 1904 85.0 100.0 
Nalco 8676/ 
5 wt. % 
Tyzor 131 
20 R1130/0.5 wt. % 
2419 1837 78.0 100.0 
Nalco 8676/ 
10 wt. % 
Tyzor 131 
______________________________________ 
Examples 21-27 
The inventive nonwovens of Examples 21-27 were prepared as described in 
General Procedure I. For each sample, 200 g of the polymeric solution (2.5 
wt. % of R1130) was mixed with 1.54 g of glyoxal (40 wt. % aqueous 
solution) and 0.25 g of NH.sub.4 Cl and then reacted with the reactants 
described below. The wt. % designated below represents the wt. % of active 
reactant (solid) over the R1130 polymer. The coated samples were dried at 
110.degree. F. (92.2.degree. C.) for 4 hrs. All samples had excellent dry 
wiping properties, low drag, and good feel. The results of the absorbency, 
tensile strength, and tear strength are presented in Tables 5 and 
TABLE 5 
__________________________________________________________________________ 
g H2O 
Sample Wet out 
abs/g of 
g H2O 
% H2O 
Ex. # 
Description 
(sec) Dry wipe 
abs/(ft.sup.2) 
Loss 
__________________________________________________________________________ 
21 NONE: 0 7.40 127.9 
15.27 
COMATIVE 
22 1 wt. % 60+ 8.86 157.1 
24.28 
Nalco 8676 
23 3 wt. % 60+ 9.39 162.9 
26.12 
Nalco 8676 
24 5 wt. % 60+ 8.03 139.3 
23.10 
Nalco 8676 
25 1 wt. % 31 8.25 148.7 
19.70 
A12(SO4)3 
(100% solid) 
26 3 wt. % 16 8.53 153.8 
21.82 
A12(SO4)3(100 
% solid) 
27 5 wt. % 60+ 8.54 147.1 
21.32 
A12(SO4)3(100 
% solid) 
__________________________________________________________________________ 
TABLE 6 
______________________________________ 
Tensile Strength 
Elmendorf 
(KPa) Tear 
Ex.# Sample Description 
MD CD MD CD 
______________________________________ 
21 NONE: 1717 2616 100.0 86.3 
COMATIVE 
22 1 wt. % 1693 2639 94.0 94.3 
Nalco 8676 
23 3 wt. % 2509 1915 -- 91.0 
Nalco 8676 
24 5 wt. % 2248 3230 100.0 90.3 
Nalco 8676 
25 1 wt. % 1880 2202 100.0 82.7 
A12(SO4)3(100 
% solid) 
26 3 wt. % 1813 2273 100.0 85.0 
A12(SO4)3 
(100% solid) 
27 5 wt. % 2449 2030 100.0 96.0 
A12(SO4)3 
(100% Solid) 
______________________________________ 
Examples 28-29 
Examples 28-29 demonstrated the use of nonwoven web containing 100% PVA 
fibers. The nonwoven web was made from 100% PVA fibers which were 1.5 
denier and 1.5 inch long (3.81 cm), purchased from Kuraray, Japan, with a 
basis weight of 7.0 g/ft.sup.2 (75.3 g/m.sup.2) using a carding machine 
known under the trade designation "Rando-Webber." A 12.times.15 inch 
(30.48.times.38.1 cm) sample of this web was coated with a solution 
containing: 130 g of R1130 solution (2.5 wt. % solid), 0.16 g of Nalco 
8676 (10% solid), 1.63 g of Tyzor 131 (20 wt. % in water), and 0.16 g of 
Orcobrite Royal blue pigment #R2008. The coated sample was dried at 
150.degree. F. (65.5.degree. C.) for 2 hrs. then cured at 300.degree. F. 
(148.9.degree. C.) for an additional 15 minutes. The coated sample had a 
rubbery feel. The absorbency and tensile strength data are presented in 
Tables 7 and 
TABLE 7 
__________________________________________________________________________ 
g H2O 
Sample Wet out 
abs/g of 
g H2O 
% H2O 
Ex. # 
Description 
(sec) dry wipe 
abs/(ft.sup.2) 
Loss 
__________________________________________________________________________ 
28 Uncoated 0 12.74 159.3 
30.71 
100% PVA 
fiber web 
COMATIVE 
29 Coated 100% 
7 4.74 81.3 13.32 
PVA fiber 
web 
__________________________________________________________________________ 
TABLE 8 
______________________________________ 
Tensile Strength (KPa) 
Ex. # Sample Description 
MD CD 
______________________________________ 
28 Uncoated 100% PVA fiber 
1751 2042 
web COMATIVE 
29 Coated 100% PVA fiber web 
2752 2352 
______________________________________ 
Examples 30-31 
Examples 30-31 demonstrated the use of a nonwoven web containing a blend of 
PVA and cotton fibers. The nonwoven web was made from 50 wt. % PVA fibers 
which were 1.5 denier and 1.5 inch (3.81 cm) in length, purchased from 
Kuraray, Japan, and 50 wt. % cotton fibers with a resultant basis weight 
of 5.5 g/ft.sup.2 (59.2 g/m.sup.2) using a web making machine known under 
the trade designation "Rando-Webber." A 12.times.15 inch (30.48.times.38.1 
cm) sample of this web was coated with a solution containing: 110 g of 
R1130 solution (2.5 wt. % solid in H.sub.2 O), 0.13 g of Nalco 8676 (10% 
solid in H.sub.2 O), 1.38 g of Tyzor 131 (20% solid in H.sub.2 O), and 
0.14 g of Orcobrite Royal blue pigment #R2008. The coated sample was dried 
at 150.degree. F. (65.5.degree. C.) for 2 hours, then cured at 300.degree. 
F. (148.9.degree. C.) for an additional 15 minutes. The coated sample had 
excellent dry wiping properties, low drag, and good feel. The absorbency 
and tensile strength data are presented in Tables 9 and 
TABLE 9 
__________________________________________________________________________ 
g H2O 
Sample Wet out 
abs/g of 
g H2O 
% H2O 
Ex. # Description (sec) Dry wipe 
abs/(ft) 
Loss 
__________________________________________________________________________ 
30 Uncoated 50/50 
0 22.27 
170.4 
50.16 
blend of 
PVA/Cotton fibers 
web: COMATIVE 
31 Coated 50/50 
4 5.82 57.7 17.41 
blend of 
PVA/Cotton fibers 
web 
__________________________________________________________________________ 
TABLE 10 
______________________________________ 
Tensile Strength (KPa) 
Ex. # Sample Description 
MD CD 
______________________________________ 
30 Uncoated 50/50 blend 
384 411 
of PVA/Cotton fibers 
web: COMATIVE 
31 Coated 50/50 blend of 
3689 2919 
PVA/Cotton fibers web 
______________________________________ 
Example 32 
The nonwoven web used in Example 32 was made from 100% rayon fibers which 
were 3.0 denier and 2.5 inches (6.35 cm) long from Courtaids Chemical 
Company, England, using a carding/crosslap/needletacking process. Its 
basis weight was 16.2 g/ft.sup.2 (174.3 g/m.sup.2). A 15.times.15 inch 
sample of this web (38.1.times.38.1 cm) was coated with a solution 
containing: 250 g of R1130 solution (2.5% solid in H.sub.2 O), 0.31 g of 
Nalco 8676 (10% solid in H.sub.2 O), 3.13 g of Tyzor 131 (20 wt. % in 
H.sub.2 O), and 0.4 g of Orcobrite Royal blue pigment #R2008. The coated 
sample was dried at 150.degree. F. (65.5.degree. C.) for 2 hours and then 
at 250.degree. F. (121.1.degree. C.) for 2 hours, and finally at 
300.degree. F. (148.8.degree. C.) for an additional 10 minutes. The coated 
sample had excellent dry wiping properties, low drag, and soft feel. 
Example 33 
Example 33 demonstrated the preparation of a bactericidal wipe based on 
iodine and the polyvinyl alcohol/polyiodide complex. A solution of 1.2 g 
potassium iodide, 0.64 g iodine crystals, and 50 g of water was prepared. 
This solution was then saturated on a wipe prepared using the procedure of 
Example 5. Initially, a brown color was observed where the sample had been 
treated. The brown color gradually changed to blue color which is a 
characteristic of the polyvinyl alcohol/polyiodide complex. When rinsed 
with water, iodine color and odor were plainly evident. 
General Procedure II for Preparing Inventive Articles 
Nonwoven webs consisting a blend of polyvinyl alcohol and rayon fibers (45% 
polyvinyl alcohol fiber having a denier of 1.5 and a length of 1.5 inch 
(3.81 cm) purchased from Kuraray KK, and 55% rayon fiber having a denier 
of 1.5 and a length of 1 and 9/16 inch (3.97 cm) purchased from BASF) were 
made using a web making machine known under the trade designation 
Rando-Webber. The resultant web had an average dry weight of 12 g/ft.sup.2 
(129 g/m.sup.2) and nominal thickness of 0.056 inch (0.142 cm). 
An aqueous binder precursor solution was prepared for each example 
containing various amounts of Airvol 165 (a 99.8% hydrolyzed polyvinyl 
alcohol with molecular weight 110,000 and degree of polymerization 2500, 
obtained from Air Products) reacted with Tyzor LA and/or Tyzor 131 and 
optionally, glyoxal as described in Examples 34-47 and NH.sub.4 Cl, an 
acid catalyst. The binder precursor solutions also may have contained 
optional crosslinker(s) and pH modifiers as detailed in the Examples. A 
12.times.15 inch (30.48.times.38.1 cm) piece of this nonwoven web was 
placed in a pan and saturated with approximately 200 g of an aqueous 
coating solution containing 5.00 g of total polymer. 
Saturated samples were dried in a flow-through oven at 150.degree. F. 
(65.5.degree. C.), for between 30 minutes and 4 hours, and cured in a 
flow-through oven, preferably for greater than 10 minutes, at temperatures 
greater than 220.degree. F. (104.degree. C.). The samples were flipped 
every 10-30 minutes to aid in even drying conditions. When curing was 
completed, the samples were conditioned for 60 minutes in 
60.degree.-80.degree. F. (15.6.degree.-26.7.degree. C.) tap water then 
dried. Samples were then analyzed for hydrophilicity, water retention and 
absorption, tensile strength, tear strength, and dry wiping properties. 
Examples 34-38 
Examples 34-38 illustrated the advantages of employing a titanate 
crosslinked PVA binder in wiping articles according to the invention. The 
wipes of Examples 34-38 were prepared as described in General Procedure II 
with the compositions described below at an initial coating weight of 5 g 
of polymeric material per 200 g solution and dried slowly at 150.degree. 
F. (65.5.degree. C.), followed by curing at 300.degree. F. (148.9.degree. 
C.). The absorbency, tensile strength, and tear data are presented in 
Tables 11 and 12, respectively. 
TABLE 11 
______________________________________ 
H.sub.2 O 
Wet Abs/Dry 
Ex. Out % H.sub.2 O 
g H.sub.2 O 
wgt. Eff g 
# Description 
(sec.) Loss abs./ft.sup.2 
(g/g) H.sub.2 O/ft.sup.2 
______________________________________ 
34 Airvol 165 
0 20.49 157.62 
8.20 116.22 
without 
Titanate 
35 Airvol 165 
0 17.52 149.55 
7.95 109.86 
with 5% 
Tyzor LA 
36 Airvol 165 
0 13.10 142.83 
7.51 101.49 
with 15% 
Tyzor LA 
37 Airvol 165 
0 18.89 144.96 
7.77 106.56 
with 5% 
Tyzor 131 
38 Airvol 165 
0 15.79 133.47 
7.21 96.06 
with 15% 
Tyzor 131 
______________________________________ 
TABLE 12 
______________________________________ 
Av. Tensile Stress 
(KPa) Elmendorf Tear (Damp) 
Ex. # Description 
Machine Cross Machine Cross 
______________________________________ 
34 Airvol 165 
2489 1999 100+ 88 
without 
Titanate 
35 Airvol 165 
2916 2330 100+ 89 
with 5% 
TYzor LA 
36 Airvol 165 
2985 2489 83 96 
with 15% 
Tyzor LA 
37 Airvol 165 
2930 2296 86 93 
with 5% 
Tyzor 131 
38 Airvol 165 
3103 2530 75 88 
with 15% 
Tyzor 131 
______________________________________ 
Examples 39-45 
Examples 39-45 illustrated the advantages of employing a titanate, and 
optionally, glyoxal crosslinked PVA binder in wiping articles according to 
the invention. The wipes of Examples 39-45 were prepared at an initial 
coating weight of 5 g total PVA, 1.59 g glyoxal, and 0.25 g NH.sub.4 Cl 
per 200 g solution and dried slowly at 150.degree. F. (65.5.degree.). The 
absorbency, tensile strength, and tear data are presented in Tables 13 and 
14, respectively. 
TABLE 13 
__________________________________________________________________________ 
Wet H.sub.2 O Abs/ 
Sample Out % H.sub.2 O 
g H.sub.2 O 
Dry wgt. 
Eff g 
Ex. # 
Description 
(sec.) 
Loss 
abs./ft.sup.2 
(g/g) H2O/ft.sup.2 
__________________________________________________________________________ 
39 Airvol 165 
1 14.47 
125.37 
7.42 88.11 
with 
Glyoxal, 
NH4Cl, w/out 
Titanate 
40 Airvol 165 
1 14.91 
124.62 
7.39 87.81 
with 
Glyoxal, 
NH4Cl, and 
1% Tyzor LA 
41 Airvol 165 
1 14.65 
128.88 
7.34 92.64 
with 
Glyoxal, 
NH4Cl, and 
5% Tyzor LA 
42 Airvol 165 
1 14.75 
130.53 
7.35 93.33 
with 
Glyoxal, 
NH4Cl, and 
10% Tyzor LA 
43 Airvol 165 
1 to 13.83 
121.05 
7.34 84.36 
with 25 
Glyoxal, 
NH4Cl, and 
1% Tyzor 131 
44 Airvol 165 
1 to 15.27 
128.61 
7.48 91.23 
with 
Glyoxal, 
NH4Cl, and 
5% Tyzor 131 
45 Airvol 165 
1 14.58 
121.92 
7.27 83.97 
with 
Glyoxal, 
NH4Cl, and 
10% Tyzor 
131 
__________________________________________________________________________ 
TABLE 14 
__________________________________________________________________________ 
Avg. Tensile 
Elmendorf Tear 
PVA Stress (KPa) 
Damp 
Ex. # 
Description 
Retention 
Machine 
Cross 
Machine 
Cross 
__________________________________________________________________________ 
39 Airvol 165 
80.5 2482 2255 98 100+ 
with 
Glyoxal, 
NH4Cl, w/out 
Titanate 
40 Airvol 165 
83 2709 2193 86 100 
with 
Glyoxal, 
NH4Cl, and 
1% Tyzor LA 
41 Airvol 165 
91.2 2592 2055 86 96 
with 
Glyoxal, 
NH4Cl, and 
5% Tyzor LA 
42 Airvol 165 
91.9 2758 2034 88 95 
with 
Glyoxal, 
NH4Cl, and 
10% Tyzor LA 
43 Airvol 165 
78.2 2696 2455 97 100+ 
with Glyoxal 
NH4Cl, and 
1% Tyzor 113 
44 Airvol 165 
86.1 2772 2392 94 100+ 
with 
Glyoxal, 
NH4Cl, and 
5% Tyzor LA 
45 Airvol 165 
75.1 2558 2310 100+ 100+ 
with 
Glyoxal, 
NH4Cl, and 
10% Tyzor 
131 
__________________________________________________________________________ 
Example 46 
Example 46 demonstrated the ability to color the wiping articles of this 
invention made in accordance with General Procedure II in varying colors 
and shades. A binder binder precursor solution was prepared consisting of 
100 g 5 wt. % Airvol 165, 1.68 g Tyzor LA, 0.03 g, 0.06 g, 0.13 g, 0.25 g, 
or 0.5 g pigment dispersion, and deionized water to achieve a total 
solution weight of 200 g for each run. The binder precursor solution was 
coated onto a 12.times.15 inch (30.48 cm.times.38.1 cm) piece of PVA/rayon 
nonwoven produced as described in General Procedure II, dried at 
120.degree. F. (48.9.degree. C.) for 2 hours, and finally cured for one 
hour at 140.degree. F. (57.0.degree. C.). Upon completion of run, the 
samples were conditioned for 60 minutes in 60.degree.-80.degree. F. 
(140.degree.-176.degree. C.) water and dried. Results are shown below. 
______________________________________ 
Pigment, Amount Results 
______________________________________ 
"Orcobrite Red BN", 
Good color and fastness. 
0.03 to 0.5 g 
"Orcobrite Yellow 
Good color and fastness. 
2GN", 0.03 to 0.5 g 
"Orcobrite Green BN", 
Good color and fastness. 
0.03 to 0.5 g 
"Aqualor Green" Good color, binder washout. 
"Aqualor Blue" Good color, binder washout. 
______________________________________ 
The aqueous pigment dispersions known under the trade designation "Aqualor" 
were obtained from Penn Color (Doylestown, Pa.), while those known under 
the trade designation "Orcobrite" aqueous pigment dispersions were 
obtained from Organic Dyestuffs (Concord, N.C.). Good results were 
obtained with a wide variety of the "Orcobrite" series of pigments. A 
major difference between the "Aqualor" and "Orcobrite" pigment 
dispersions, as supplied, was the substantially higher alkalinity of 
"Aqualor" pigment dispersions, perhaps leading to insufficient cure by the 
titanate crosslinking agent. Generally speaking it was found that the best 
results with regard to coloring were obtained at cure temperatures of 
240.degree.-250.degree. F. (115.6.degree."121.degree. C.), although higher 
temperatures were also useful. 
Example 47 
Example 47 demonstrated the ability to impregnate the synthetic wipes of 
the invention made in accordance with General Procedure II with a number 
of antibacterial, antifungal, and disinfecting solutions for use in the 
health care, business, and/or food service trades. A nonwoven produced in 
accordance with General Procedure II was saturated with an aqueous 
solution containing 1.2 g potassium iodide, 0.64 g solid iodine crystals, 
and 50 g deionized water. 
Initially, a brown color was observed where the sample had been treated. 
The brown color gradually changed to blue, characteristic of the polyvinyl 
alcohol/polyiodide complex. When the article was rinsed with water, the 
iodine color and odor were plainly evident. 
General Procedure III for Preparing Inventive Articles 
A 12 by 15 inch (30.48.times.38.1 cm) piece of polyvinyl alcohol/rayon (45% 
polyvinyl alcohol fiber having a denier of 1.5 and a length of 1.5 inch 
(3.81 cm) purchased from Kuraray KK, and 55% rayon fiber having a denier 
of 1.5 and a length of 19/16 inch purchased from BASF) blended nonwoven 
fiber substrate (thickness=56 mil (0.142 cm), basis weight =11.5 
g/ft.sup.2 (123.8 g/m.sup.2), prepared using a web marking of 
Rando-Webber) was placed in a pan and saturated with 200 g of an aqueous 
binder precursor solution containing 5.00 g total polyvinyl alcohol and 
polyacrylic acid, prepared by mixing a 5% aqueous solution of "Airvol 165" 
with a 2.5% aqueous solution of the polyacrylic acid. "Airvol 165" (a 
99.8% hydrolyzed polyvinyl alcohol, MW=110,000, DP=2500 obtained from Air 
Products) was used in combination with polyacrylic acid (750,000 MW, 
Aldrich Chemical Co.). The binder precursor solution pH was adjusted with 
85% phosphoric acid. The sample and tray were placed in a flow through 
drying oven at 120.degree.-150.degree. F. (48.9.degree.-65.5.degree. C.) 
for 2 hours followed by curing at 300.degree. F. (148.9.degree. C.) as 
specified in Table 15. The samples were flipped over after about 30 
minutes and 60 minutes to aid in maintaining even drying. When curing was 
completed the samples were conditioned for 60 minutes in 
60.degree.-80.degree. F. water then dried. 
Examples 48-62 
Example wipes 48-62 were made in accordance with General Procedure III at 
the conditions specified in Table 15, and subsequently analyzed for wet 
out, absorptivity, tensile strength, tear strength, and dry wiping 
properties. The test results are presented in Tables 16-17. Examples 48-62 
each contained 0.1 g "Orcobrite Yellow 2GN 9000" (a yellow pigment, 
available from Organic Dyestuffs, Corp.). 
TABLE 15 
__________________________________________________________________________ 
% Coating 
Conditioned 
Loss During 
Coat Wt. 
Ex. # 
Description 
Cure Conditions 
Conditioning 
(g/m.sup.2) 
__________________________________________________________________________ 
48 Polyacrylic 
2 HR 120.degree. F. 
4 40.5 
Acid, pH = 3.0, 
(48.9.degree. C.)/ 
COMATIVE 
5 MIN 300.degree. F. 
(148.9.degree. C.) 
49 Airvol 165 2 HR 120.degree. F. 
1 48.4 
(polyvinyl (48.9.degree. C.)/ 
alcohol), 5 MIN 300.degree. F. 
pH = 3.0, (148.9.degree. C.) 
COMATIVE 
50 1 part 2 HR 120.degree. F. 
0 49.5 
Polyacrylic 
(48.9.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
2 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.0 
51 1 part 2 HR 120.degree. F. 
0 48.2 
Polyacrylic 
(48.9.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
3 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.0 
52 1 part 2 HR 120.degree. F. 
0 56.9 
Polyacrylic 
(48.9.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
165 parts Airvol 
(148.9.degree. C.) 
5, pH = 3.0 
53 1 part 2 HR 120.degree. F. 
0 58.5 
Polyacrylic 
(48.9.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
10 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.0 
54 1 part 2 HR 150.degree. F. 
0 52.4 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.5 
55 1 part 2 HR 150.degree. F. 
0 51.6 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 15 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.5 
56 1 part 2 HR 150.degree. F. 
0 55.4 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 25 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.5 
57 0.1 part 2 HR 150.degree. F. 
1 49.5 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.5 
58 0.5 part 2 HR 150.degree. F. 
1 53.5 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, PH = 3.5 
59 1 part 2 HR 150.degree. F. 
0 55.4 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.5 
60 1 part 2 HR 150.degree. F. 
0 49.7 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 4.0 
61 1 part 2 HR 150.degree. F. 
0 52.3 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 4.6 
62 1 part 2 HR 50.degree. F. 
1 48.3 
Polyacrylic 
(65.6.degree. C.)/ 
acid/ 5 MIN 300.degree. F. 
99 parts Airvol 
(148.9.degree. C.) 
165, pH = 3.3 
__________________________________________________________________________ 
TABLE 16 
______________________________________ 
Tensile Tensile 
Strength Strength Elmendorf 
Elmendorf 
Machine Cross Web Tear Test 
Tear Test 
Ex. Direction 
Direction (Machine 
(Cross Web 
% H.sub.2 O 
# (KPa) (KPa) Direction) 
Direction) 
Loss 
______________________________________ 
48 1910 1014 65 73 11 
49 3054 2240 53 90 11 
50 2937 2420 54 100+ 10 
51 3296 2117 74 86 11 
52 2379 1751 87 100+ 11 
53 2779 1813 81 82 13 
54 2772 2737 96 100+ 18 
55 2958 2565 77 100+ 20 
56 2854 2399 79 90 21 
57 2758 2365 91 100+ 16 
58 2523 2324 88 100+ 18 
59 2723 2461 85 100+ 20 
60 2737 2392 89 100+ 22 
61 2785 2358 87 100+ 22 
62 2909 2275 90 100+ 19 
______________________________________ 
TABLE 17 
______________________________________ 
Total H.sub.2 O Abs. 
H.sub.2 O Abs./Dry 
Eff. H.sub.2 O Abs. 
Ex.# (g/ft.sup.2) Wt. (g/g) (g/ft.sup.2) 
______________________________________ 
48 175.7 9.70 105.2 
49 137.7 7.70 98.9 
50 142.7 7.63 101.1 
51 139.4 7.27 94.5 
52 126.2 6.13 84.9 
53 136.3 6.67 96.3 
54 158.7 7.78 114.0 
55 157.0 8.03 111.4 
56 156.0 7.46 111.1 
57 148.6 7.41 105.0 
58 159.7 7.86 115.3 
59 160.9 8.31 116.7 
60 158.7 8.55 116.1 
61 162.1 8.21 118.3 
62 150.8 7.76 108.7 
______________________________________ 
Example 63 
This example demonstrated the preparation of a bactericidal wipe based on 
iodine and a polyvinyl alcohol/polyiodide complex, and made in accordance 
with General Procedure III. A solution of 1.2 g potassium iodide, 0.64 g 
iodine crystals, and 50 g water was prepared. This solution was coated 
onto a sample of 1:2 polyacrylic acid/polyvinyl alcohol wipe prepared as 
in General Procedure III above. Initially, a brown color was observed 
where the sample had been treated. The brown color gradually changed to 
blue characteristic of the polyvinyl alcohol/polyiodide complex. When 
rinsed with water iodine color and odor were plainly evident. 
General Procedure IV for Preparing Inventive Articles 
A 12 by 15 inch (30.48.times.38.1 cm) piece of polyvinyl alcohol/rayon (45% 
polyvinyl alcohol fiber having a denier of 1.5 and a length of 1.5 in 
(3.81 cm) purchased from Kuraray KK, and 55% rayon fiber having a denier 
of 1.5 and a length of 1.56 inch (3.96 cm) purchased from BASF) blended 
nonwoven fiber substrate (thickness=56 mil (0.142 cm), basis weight 11.5 
g/ft.sup.2 (123.8 g/cm.sup.2), prepared using a web making machine known 
under the trade designation "Rando-Webber") was placed in a pan and 
saturated with 200 g of an aqueous binder precursor solution containing 
5.00 g total polyvinyl alcohol. "Airvol 165" (a 99.8% hydrolyzed polyvinyl 
alcohol, MW=110,000, DP=2500 obtained from Air Products) was used in 
combination with syndiotactic polyvinyl alcohol prepared in Example 64 to 
comprise the polyvinyl alcohol content in Examples 65-91. The binder 
precursor solutions may also have contained optional crosslinker(s), and 
pH modifiers depending on the Example. The sample and tray were placed in 
a flow through drying oven at 120.degree.-50.degree. F. 
(48.9.degree.-65.6.degree. C.) for 3 to 4 hours as specified. The samples 
were flipped over after about 30 minutes and 60 minutes to aid in 
maintaining even drying. When curing was completed the samples were 
conditioned for 60 minutes in 60.degree.-80.degree. F. 
(15.6.degree.-26.7.degree. C.) water then dried. Samples were then 
analyzed for wet out, absorptivity, tensile strength, tear strength, and 
dry wiping properties, with the results reported in Tables 18-27. 
Example 64: Preparation of Syndiotactic PVA 
This example illustrated the preparation of syndiotactic polyvinyl alcohol 
employed in Examples 65-91. 
The polyvinyl trifluoroacetate (PVTFA) copolymer described above (300 g) 
was dissolved in 700 g acetone. This solution was slowly added to 1700 g 
of 10% methanolic ammonia that had been cooled in ice to 15.degree. C. 
Despite vigorous mechanical stirring a large ball of solid material formed 
on the stirrer blade making stirring ineffective. After addition was 
complete the ball of material was broken up by hand and the mixture was 
shaken vigorously. The process was repeated twice more (elapsed time was 
about 3 hr). The divided mass was vigorously mechanically stirred for 20 
minutes and allowed to stand at room temperature overnight. 
The supernatant liquid was decanted off leaving a mixture of white powder 
and yellow fibrils. The solids were collected by filtration and spread in 
a tray at 15.6.degree. C. to evaporate residual solvent. The solids were 
collected when constant weight over 2 hr was achieved. The solid was 
chopped in a blender to give 87.3 g of beige powder, 92% yield, referred 
to hereinafter as "Syn". Analysis of this material was carried out using 
IR and .sup.1 H NMR spectroscopy, and Gel Permeation Chromatography. The 
results indicated the likely presence of traces of trifluoroacetate esters 
and salts. The triad syndiotacticity measured by .sup.1 H NMR in 
DMSO-d.sub.6 was 33%, atacticity=50%, isotacticity=17%, The difference 
between the hydrolyzed polymer and the trifluoroacetate precursor polymer 
may be due to acid catalyzed epimerization of hydroxyl groups during 
drying or solution in boiling water. 
Examples 65-70 
Examples 65-70 illustrated the advantages of employing syndiotactic 
polyvinyl alcohol alone or in blends with atactic polyvinyl alcohol in 
wiping articles according to the invention. The articles were prepared at 
an initial coating weight of 5 g total PVA/200 g solution. Curing 
conditions were 4 hr at 48.9.degree. C. 
TABLE 18 
__________________________________________________________________________ 
Tensile 
Tensile 
% Coating 
Strength 
Strength 
Weight Elmendorf 
Elmendorf 
Machine 
Cross 
Loss Tear Tear 
Ex. Direction 
Direction 
During Machine 
Cross 
# Description 
(KPa) 
(KPa) 
Conditioning 
Direction 
Direction 
__________________________________________________________________________ 
65 100% 2061 1131 10.1 63(5) 95(7) 
AIRVOL 
165 
66 99% 2186 1496 8.9 79(2) 100+ 
AIRVOL 
165: 1% 
Syn 
67 95% 2027 1427 8.4 74(7) 89(0) 
AIRVOL 
165: 5% 
Syn 
68 90% 2475 1799 7.8 75(4) 86(7) 
AIRVOL 
165: 10% 
Syn 
69 80% 2109 1510 6.2 100+ 95(4) 
AIRVOL 
165: 20% 
Syn 
70 100% Syn 
2661 1979 5.5 100+ 91(0) 
__________________________________________________________________________ 
TABLE 19 
__________________________________________________________________________ 
Water 
Total Absorption 
Effective 
Water /Dry wt. 
Water 
Ex. Wet Out 
% Water 
Absorption 
of Sample 
Absorption 
# Description 
(sec) 
Loss (g/ft.sup.2) 
(g/g) (g/ft.sup.2) 
__________________________________________________________________________ 
65 100% 0 17.4 134.52 
7.92 99.60 
AIRVOL 
165 
66 99% 0 20.0 150.09 
8.38 112.50 
AIRVOL 
65: 1% 
Syn 
67 95% 0 15.0 136.17 
7.81 99.90 
AIRVOL 
65: 5% 
Syn 
68 90% 0 14.8 130.50 
7.63 95.40 
AIRVOL 
165: 10% 
Syn 
69 80% 0 15.8 131.58 
7.14 94.80 
AIRVOL 
165: 20% 
Syn 
70 100% 2 16.8 143.25 
7.33 106.71 
Syn 
__________________________________________________________________________ 
Examples 71-83 
These examples demonstrated the use of syndiotactic polyvinyl alcohol with 
chemical crosslinkers (Tyzor LA and/or glyoxal) in wiping articles 
according to the invention. Curing conditions were 3.5 hr at 150.degree. 
F. (65.5.degree. C.). Mole % crosslinking amounts for Tyzor LA were based 
on four bonds between titanium and polyvinyl alcohol. Mole % crosslinking 
amounts for glyoxal were based on four bonds between glyoxal and polyvinyl 
alcohol. 
TABLE 20 
__________________________________________________________________________ 
Water 
Total Absorption 
Effective 
Water /Dry wt. 
Water 
Ex. Wet Out 
% Water 
Absorption 
of Sample 
Absorption 
# Description 
(sec) 
Loss (g/ft.sup.2) 
(g/g) (g/ft.sup.2) 
__________________________________________________________________________ 
71 1% Blend of Syn 
0 25.1 129.2 8.65 119.49 
in Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
72 1% Blend of Syn 
0 20.1 137.4 8.12 117.36 
in Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
73 5% Blend of Syn 
0 16.9 134.7 7.71 106.92 
in Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
74 5% Blend of Syn 
0 17.8 135.2 7.62 108.00 
in Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
75 10% Blend of 
0 21.7 128.4 7.96 110.28 
Syn in Airvol 
165 with 20 
mol % Tyzor LA 
crosslinking 
__________________________________________________________________________ 
TABLE 21 
__________________________________________________________________________ 
Water 
Total Absorption 
Effective 
Water /Dry wt. 
Water 
Ex. Wet Out 
% Water 
Absorption 
of Sample 
Absorption 
# Description 
(sec) 
Loss (g/ft.sup.2) 
(g/g) (g/ft.sup.2) 
__________________________________________________________________________ 
76 10% Blend of 
0 18.2 133.8 7.70 108.2 
Syn in Airvol 
165 with 20 
mol % Tyzor LA 
crosslinking 
77 1% Blend of 
0 15.6 137.8 8.42 107.7 
Syn in Airvol 
165 with 40 
mol % Glyoxal 
crosslinking 
78 1% Blend of 
0 17 139.4 8.58 111.4 
Syndiotactic 
in Airvol 165 
with 40 mol % 
Glyoxal 
crosslinking 
79 5% Blend of 
0 15.8 145.4 8.35 114.7 
Syndiotactic 
in Airvol 165 
with 40 mol % 
Glyoxal 
crosslinking 
80 5% Blend of 
0 17.3 139.7 8.80 113.3 
Syndiotactic 
in Airvol 165 
with 40 mol % 
Glyoxal 
crosslinking 
81 10% Blend of 
0 11.2 144.5 8.40 107.1 
Syndiotactic 
in Airvol 165 
with 40 mol % 
Glyoxal 
crosslinking 
82 10% Blend of 
0 16.9 154.8 8.30 122.3 
Syndiotactic 
in Airvol 165 
with 40 mol % 
Glyoxal 
crosslinking 
83 10% Blend of 
0 13.1 141.9 7.46 105.2 
Syndiotactic 
in Airvol 165 
__________________________________________________________________________ 
TABLE 22 
______________________________________ 
Tensile 
Strength Tensile % Coating 
Machine Strength Cross 
Weight Loss 
Direction 
Direction During 
Ex. # 
Description (KPa) (KPa) Conditioning 
______________________________________ 
71 1% Blend of 2158 2082 4.3 
Syn in 
Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
72 1% Blend of 2971 1724 4.2 
Syn in 
Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
73 5% Blend of 2572 2199 4.4 
Syn in 
Airvol 165 
with 20 mol 
5 Tyzor LA 
crosslinking 
74 5% Blend of 2737 1979 4.5 
Syn in 
Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
______________________________________ 
TABLE 23 
______________________________________ 
Tensile 
Strength Tensile % Coating 
Machine Strength Cross 
Weight Loss 
Direction 
Direction During 
Ex. # 
Description (KPa) (KPa) Conditioning 
______________________________________ 
75 10% Blend of 
2475 1944 5.1 
Syn in 
Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
76 10% Blend of 
2910 2240 4.8 
Syn in 
Airvol 165 
with 20 mol % 
Tyzor LA 
crosslinking 
77 1% Blend of 2820 1889 3.3 
Syn in 
Airvol 165 
with 40 mol % 
Glyoxal 
crosslinking 
78 1% Blend of 2351 -- 3.5 
Syndiotactic 
in Airvol 
165 with 40 
mol % Glyoxal 
crosslinking 
79 5% Blend of 2482 2006 3.2 
Syndiotactic 
in Airvol 
165 with 40 
mol % Glyoxal 
crosslinking 
80 5% Blend of 2199 1841 3.5 
Syndiotactic 
in Airvol 
165 with 40 
mol % Glyoxal 
crosslinking 
81 10% Blend of 
2227 1696 3.5 
Syndiotactic 
in Airvol 
165 with 40 
mol % Glyoxal 
crosslinking 
82 10% Blend of 
2379 1786 3.0 
Syndiotactic 
in Airvol 
165 with 40 
mol % glyoxal 
crosslinking 
83 10% Blend of 
2365 1696 1.8 
Syndiotactic 
in Airvol 
165 
______________________________________ 
Examples 84-86 
Examples 84-86 demonstrated the effect of coat weight on wiping parameters 
of articles made in accordance with General Procedure IV. A binder 
precursor solution consisting only of 30% syndiotactic PVA was coated onto 
nonwoven substrates at various coating weights (i.e., 1 g, 2 g, 5 g total 
PVA in coating solution) as indicated in Tables 24 and 25, which also 
present the absorbency and strength test results. 
TABLE 24 
__________________________________________________________________________ 
Tensile 
Tensile 
Strength 
Strength 
% Weight 
Elmendorf 
Elmendorf 
Machine 
Cross Loss Tear Tear 
Ex. Direction 
Direction 
During Machine 
Cross 
# Description 
(KPa) (KPa) Conditioning 
Direction 
Direction 
__________________________________________________________________________ 
84 5 g: 100% Syn 
2661 .+-. 117 
1979 .+-. 69 
5.5 100+ 91 .+-. 0 
85 2 g: 100% Syn 
2006 .+-. 131 
1351 .+-. 34 
3.3 75 .+-. 6 
96 .+-. 2 
86 1 g: 100% Syn 
1441 .+-. 138 
1186 .+-. 89 
2.9 84 .+-. 9 
100+ 
__________________________________________________________________________ 
TABLE 25 
__________________________________________________________________________ 
Water 
Total Absorption 
Effective 
Water /Dry wt. 
Water 
Ex. Wet Out 
% Water 
Absorption 
of Sample 
Absorption 
# Description 
(sec) 
Loss (g/ft.sup.2) 
(g/g) (g/ft.sup.2) 
__________________________________________________________________________ 
84 5 g: 100% Syn 
2 16.8 143.25 
7.33 106.71 
85 2 g: 100% Syn 
0 18.2 146.31 
8.31 116.40 
86 1 g: 100% Syn 
0 20.5 157.68 
10.43 127.62 
__________________________________________________________________________ 
Examples 87-89 
Examples 87-89 demonstrated the results of direct ammonolysis of polyvinyl 
trifluoroacetate after the binder precursor solutions was coated on the 
nonwoven substrate. The absorbency and strength of these articles (Tables 
26 and 27) were superior to those of 30% syndiotactic polyvinyl alcohol 
coated from water described in the preceding examples. One explanation of 
the benefits observed is that acid catalyzed loss of syndiotacticity was 
minimized by use of this method which probably provided greater surface 
area for ammonolysis. 
TABLE 26 
______________________________________ 
Tensile Tensile 
% Weight 
Strength Strength 
Loss 
Machine Cross During 
Direction 
Direction 
Condition- 
Ex. # 
Description (KPa) (KPa) ing 
______________________________________ 
87 16 g 3744 3041 0 
PVTFA/ammonolyzed 
(5 g PVA) 
88 6.5 g 2544 2082 0 
PVTFA/ammonolyzed 
(2 g PVA) 
89 3.2 g 1551 1165 0 
PVTFA/ammonolyzed 
(1 g PVA) 
______________________________________ 
TABLE 27 
__________________________________________________________________________ 
Water 
Total Absorption/ 
Effective 
Water Dry wt Water 
Ex. Wet Out 
% Water 
Absorption 
of Sample 
Absorption 
# Description 
(sec) 
Loss (g/ft.sup.2) 
(g/g) (g/ft.sup.2) 
__________________________________________________________________________ 
87 16 g PVTFA/ 
0 22.5 114.4 5.86 81.5 
ammonolyzed 
(5 g PVA) 
88 6.5 g PVTFA/ 
0 23.0 143.2 7.90 107.6 
ammonolyzed 
(2 g PVA) 
89 3.2 g PVTFA/ 
0 30.1 166.2 9.82 134.1 
ammonolyzed 
(1 g PVA) 
__________________________________________________________________________ 
Example 90 
This example demonstrated the preparation of a bactericidal wipe based on 
iodine and the polyvinyl alcohol/polyiodide complex utilizing General 
Procedure IV. A solution of 1.2 g potassium iodide, 0.64 g iodine 
crystals, and 50 g water was prepared. This solution was coated onto a 
sample of a wipe as prepared in Examples 84-86. Initially, a brown color 
was observed where the sample had been treated. The brown color gradually 
changed to blue characteristic of the polyvinyl alcohol/polyiodide 
complex. When rinsed with water iodine color and odor were plainly 
evident. 
Example 91 
A sample containing 5 g 30% syndiotactic PVA as the only binder component 
in 200 g total solution was prepared and coated as in Examples 84-86 
containing 0.1 g "Orcobrite Blue 2GN" pigment (Organic Dyestuffs Corp., 
Concord, N.C.). The sample was cured at 250.degree. F. (121.degree. C.) 
for 2 hours. The sample discolored slightly and had a strong odor, but was 
colorfast after conditioning in luke-warm water for 2 hours. 
Various modifications and alterations of this invention will become 
apparent to those skilled in the art without departing from the scope of 
the invention, and it should be understood that this invention is not to 
be unduly limited to the illustrated embodiments set forth herein.