Note: Descriptions are shown in the official language in which they were submitted.
CA 0222~026 1997-12-18
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, TITT,F
Durable Hydrophilic Polymer Coatings
FIRTn OF T~R INVENTION
This invention relates to certain polymer
compositions and their use to impart a durable hydrophilic
coating to woven and non-woven polyester, polypropylene and
polyethylene fabrics or fibers.
R~CKGROUND OF T~ INV~NTION
Polyester, polypropylene and polyethylene woven
and non-woven fabrics have many applications for which their
hydrophobic characteristics are undesirable. These include
applications where a high ability to transmit water is
desirable, such as for diapers, adult incontinence pads,
agricultural fabrics for landscaping or mulching, and some
filtration devices; applications where wicking away of
moisture is desirable for comfort reasons, such as for
certain clothing and sportswear purposes; and applications
where it is desirable to make the surface of a fiber more
hydrophilic for better adhesion or easier incorporation into
water-borne compositions such as cement mixtures or paper
pulps .
U.S. Patent 4,863,619 of Borcher et al. issued
September 5, 1989, discloses organic materials useful as
vicosity reducing agents in the manufacture of fabric
treatment products, in particular soil release polymers.
Polypropylene or polyethylene is commonly used as
the liner (coverstock) in baby diapers and adult
incontinence pads, and in these applications it is next to
the wearer's skin. By design, moisture must pass through
the polypropylene or polyethylene layer into the absorbent
layer below. Since polypropylene or polyethylene is
naturally hydrophobic, it must be treated to allow the
moisture to pass through quickly and not run off the top of
the diaper or pad.
Sll~l11~TESH~ ULE78)
CA 0222~026 1997-12-18
W097/00351 PCT~S96/10266
In diaper manufacture in the U.S. the above liner
i6 commonly treated with a small amount of a surfactant
wetting agent, such as an alcohol ethoxylate, to improve
moisture transport through the polypropylene or polyethylene
layer. Since the alcohol ethoxylate is usually water
soluble, it dissolves and reduces the surface tension of the
water. This causes the moisture to wet the polypropylene or
polyethylene and pass through more quickly. The use of an
alcohol ethoxylate has two important drawbacks, however.
Since it dissolves off, little r~m~;nq to improve passage of
any second or subsequent exposures to moisture. The
capacity of the absorbent layer is reduced as well, since
its absorptivity is based on capillary action, which is
adversely affected by absorption of the alcohol ethoxylate.
A coating is needed which would allow moisture to
pass through the polypropylene or polyethylene liner
quickly, but that will not readily wash off. The present
invention provides such a coating and a process for its
application.
Polypropylene, polyethylene or polyester are also
commonly used in generation of nonwovens used in protective
garments such as medical, surgical, laboratory and other
garments. Such garments can be uncomfortable due to poor
hand and lack of moisture transport. A coating or treatment
is needed which softens the nonwoven fabrics or fibers and
wicks away moisture to enhance comfort. The present
invention provides such a coating or treatment. Thus the
compositions, methods, fabrics and fibers of the present
invention are useful in clothing applications and other
applications where improved wicking or moisture transport
through a woven or non-woven fabric of polyester,
polypropylene or polyethylene is important.
SUMM~Y OF T~ INV~TION
The present invention comprises the following
compositions:
Sl~ 111 ~ITE SI~EET (R~LE 2B~
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A. a composition comprising an aqueous dispersion
of: 1) a hydrophilic copolyester having repeating segments
of a polyoxyethylene diester and a polyalkylene diester, and
2) a polypropylene oxide polymer capped on one or both ends
with an alkyl or ester group, said polymer having more than
4 propylene oxide units and an average molecular weight of
at least about 300;
B. a mixture comprising 1) an organic solvent, 2)
a hydrophilic copolyester having repeating segments of a
polyoxyethylene diester and a polyalkylene diester, and 3) a
polypropylene oxide polymer capped on one or both ends with
an alkyl or ester group, said polymer having more than 4
propylene oxide units and an average molecular weight of at
least about 300;
lS C. a composition comprising an aqueous dispersion
o~ 1) a hydrophilic copolyester having repeating segments of
a polyoxyethylene diester and a polyalkylene diester, and 2)
a polypropylene glycol having an average molecular weight
greater than 1100; or
D. a composition comprising a mixture of 1) an
organic solvent, 2) a hydrophilic copolyester having
repeating segments of a polyoxyethylene diester and a
polyalkylene diester, and 3) a polypropylene glycol having
an average molecular weight greater than 1100.
The present invention further comprises the above
dispersions or mixtures wherein the hydrophilic copolyester
has been modified by reaction with at least one polyol
containing at least 3 hydroxy groups, or with at least one
polyoxyethylene glycol, or with a mixture thereof, to yield
a copolyester having from 1 to about 40 weight percent of
post reactant repeating units.
The present invention further comprises a method
for imparting a durable hydrophilic coating to polyester,
polypropylene or polyethylene fabric or fiber comprising
application to the surface of the ~abric or fiber of an
SU~fi 111 lJTE SltEET (~ILE 2B)
~ ==
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effective amount of at least one of the inventive
compositions A, B, C or D as described above, or said
compositions containing a hydrophilic copolyester which has
been modified as described above.
The present invention further comprises a method
for imparting a durable hydrophilic coating to polyester,
polypropylene or polyethylene fabric or fiber comprising
application to the surface of the fabric or fiber of an
effective amount of at least one composition selected from:
1) a mixture of an organic solvent and a hydrophilic
copolyester having repeating segments of a polyoxyethylene
diester and a polyalkylene diester; 2) a polypropylene oxide
polymer capped on one or both ends with an alkyl or ester
group, said polymer having more than 4 propylene oxide units
and an average molecular weight of at least about 300, an
aqueous dispersion thereof, or a mixture thereof with an
organic solvent, 3) a polypropylene glycol having an average
molecular weight greater than 1100 an aqueous dispersion
thereof, or a mixture thereof with an organic solvent, 4) an
aqueous dispersion of polyvinyl alcohol and a polypropylene
oxide polymer capped on one or both ends with an alkyl or
ester group, said polymer having more than 4 propylene oxide
units and an average molecular weight of at least about 300,
5) an aqueous dispersion of polyacrylamide and a
polypropylene oxide polymer capped on one or both ends with
an alkyl or ester group, said polymer having more than 4
propylene oxide units and an average molecular weight of at
least about 300, 6) a mixture of polyvinyl alcohol and
polypropylene glycol, said polypropylene glycol having an
average molecular weight greater than 1100, and 7) a mixture
of polyacrylamide and polypropylene glycol, said
polypropylene glycol having an average molecular weight
greater than 1100.
The present invention further comprises a woven or
nonwoven polyester, polyethylene or polypropylene fabric or
SUBSTITUTE SHEET ~ L~
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fiber having applied to its surface an effective amount of
at least one of the inventive compositions A, B, C or D as
described above, or said compositions containing a
hydrophilic copolyester which has been modified as described
above.
The present invention further comprises a woven or
nonwoven polyester, polyethylene or polypropylene fabric or
fiber having applied to its surface an effective amount of
at least one composition selected from 1) a mixture of an
organic solvent and a hydrophilic copolyester having
repeating segments of a polyoxyethylene diester and a
polyalkylene diester; 2) a polypropylene oxide polymer
capped on one or both ends with an alkyl or ester group,
said polymer having more than 4 propylene oxide units and an
average molecular weight of at least about 300, an aqueous
dispersion thereof, or a mixture thereof with an organic
solvent, 3) a polypropylene glycol having an average
molecular weight greater than 1100, an aqueous dispersion
thereof, or a mixture thereof with an organic solvent 4) an
aqueous dispersion of polyvinyl alcohol and a polypropylene
oxide polymer capped on one or both ends with an alkyl or
ester group, said polymer having more than 4 propylene oxide
units and an average molecular weight of at least about 300,
5) an aqueous dispersion of polyacrylamide and a
polypropylene oxide polymer capped on one or both ends with
an alkyl or ester group, said polymer having more than 4
propylene oxide units and an average molecular weight of at
least about 300, 6) a mixture of polyvinyl alcohol and
polypropylene glycol, said polypropylene glycol having an
average molecular weight greater than 1100, and 7) a mixture
of polyacrylamide and polypropylene glycol, said
polypropylene glycol having an average molecular weight
greater than 1100.
D~TATT~n D~.sCRIPTION OF T~F. INV~NTION
SU~TITUTE SHEET (RU~
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The present invention comprises compositions that
when applied to polyester, polypropylene or polyethylene
fabric or fiber impart a durable hydrophilic coating. The
present invention further comprises methods for imparting a
durable hydrophilic coating to polyester, polypropylene and
polyethylene fabric or fiber comprising application of the
compositions as described above. The present invention
further comprises, in woven or nonwoven form, polyester,
polypropylene, or polyethylene fabric or fiber having such a
coating applied to its surface.
By the term "organic solvent" is meant those
organic solvents incapable of forming three dimensional
networks of strong hydrogen bonds. Examples of suitable
solvents include dibasic esters, esters (for example ethyl
acetate), ketones (for example acetone), ethers (for example
tetrahydrofuran), and tertiary amides (for example
dimethylformamide or dimethylacetamide).
The term "hydrophilic copolyester" is used to mean
a copolyester conta;n;ng both polyoxyethylene diester and
alkylene diester segments. They may be simple copolyesters,
i.e., they may contain only polyoxyethylene diester and
polyalkylene diester segments, the copolyester being derived
from a single polyethylene oxide, diester and glycol.
Polyethylene oxides of various molecular weights, dimethyl
terephthalate and ethylene glycol are the most common raw
materials for these copolymers, mainly because of cost and
availability. Numerous variations on the comonomers used to
prepare these simple hydrophilic copolyesters are possible.
Other alkylene glycols such as propylene and butylene
glycols are suitable for the replacement of all or part of
the ethylene glycol, or they may be incorporated in minor
amounts into the polyethylene oxide employed. Simple ether
glycols such as diethylene glycol, and cycloaliphatic diols
such as 1,4-cyclohexane dimethanol, are also appropriate as
comonomers for the base copolyesters. Among other diesters
SUB~TITUTE SHEEr (RULE 26)
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that may be used to replace all or part of the dimethyl
terephthalate are diesters of aliphatic diacids such as
adipic and sebacic acids, and diesters of aromatic diacids
such as isophthalic and sulfonated isophthalic acids. The
base copolymers may additionally contain one or more of the
other components, e.g., an acidic group, a basic group, an
ionizable salt group, an antioxidant group, a group that
absorbs ultraviolet light, a dyestuff group and polymeric
groups containing a plurality o~ either hydroxy groups or
amido groups, all of which are disclosed by McIntyre et al.
in U.S. Patents 3,416,952; 3,557,039; and 3,619,269.
The hydrophilic copolyesters are prepared by
condensation at relatively high temperatures under reduced
pressures. Temperatures of about 200 to 280~C, or even
higher, and pressure not higher than about 35 mm Hg are
generally employed. Byproduct alcohols and part of the low
molecular weight glycols originally charged are removed by
distillation during the condensation process. As the
process proceeds the viscosity of the copolyester increases.
A preferred hydrophilic copolyester is a polyester
copolymer with repeating segments of ethylene terephthalate
units containing 10-50~ by weight of polyoxyethylene
terephthalate units, derived from a polyoxyethylene glycol
of average molecular weight of from about 300 to about
6,000, and the molar ratio of ethylene terephthalate units
to polyoxyethylene terephthalate units in the polymeric
compound is between 2:1 and 6:1. A more preferred copolymer
is that wherein the polyoxyethylene terephthalate units are
derived from a polyoxyethylene glycol with an average
molecular weight of from about 1,000 to about 4,000. These
copolymers are disclosed in U.S. Patent 3,416,952. Examples
of these copolymers include the commercially available
"ZELCON" 4780 (available from E. I. du Pont de Nemours and
Company, Wilmington, DE) and "MILEASE" T (available from
Imperial Chemical Industries, Limited, London, England);
SU~3STITUTE SI~E~ U~E 2~)
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both have the Chemical Abstracts Service Registry No. 9016-
88-0. Both "ZELCON"4780 and "MILEASE" T are sold in the
aqueous dispersion form containing up to 85~ water. It is
preferable to use the dehydrated polymer to prepare the
dispersions to avoid the incorporation of excess moisture.
The dehydrated polymer is obtained by drying the above-
mentioned commercial dispersions, or can be obtained in the
concentrated form from the manufacturers. An example of the
latter is "ZELCON" PG, the concentrated form of "ZELCON"
5126, and is obtainable from the E. I. du Pont de Nemours
and Company, Wilmington, DE.
In addition, these hydrophilic polyesters may be
further modified after being formed by reaction with one or
more polyols containing three or more hydroxy groups or one
or more polyoxyethylene glycols or a mixture of one or more
of such polyols and one or more of such glycols, as
disclosed in U.S. 5,239,019. The modified copolyesters are
hydrophilic in nature. They consist of polyols containing
three or more hydroxy groups, and polyoxyethylene glycols.
The polyols may also contain other functional groups such
as, e.g., ester and ether groups. Examples of polyols
suitable for modification of the copolyesters include simple
polyols such as glycerin, pentaerythritol and sorbitol, low
molecular weight ether polyols derived from the simple
polyols such as diglycerol and di- and tripentaerythritol,
and polymeric polyols such as the partially hydrolyzed
polyvinyl acetates and partially esterified derivatives of
cellulose. Ethylene oxide adducts of the above polyols are
also suitable. The polyoxyethylene glycols may vary in
molecular weight from about 300 to 6,000 depending on the
intended application. Molecular weights of about 600 to
3,000 are preferred, with 800 to 1600 being most preferred.
Besides their hydroxy and ether segments, they may
optionally contain other functional groups such as amino
groups and quaternized amino groups.
SU~iTlTUTE SHEEr (RU~ E 26)
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The post-reaction of the copolyester with
additional hydrophilic entities is carried out under milder
conditions than those used in synthesizing the base
copolyester. Most are carried out at temperatures of about
150~C or above, at atmospheric pressure, with temperatures of
180 to 200~C being preferred. In some cases vacuum is also
applied, but the overall conditions are less vigorous than
in the preparation of the base copolyesters. Additionally,
when the post-reactant is charged to the heated base
copolymer, a reduction in viscosity may initially occur,
indicating a reduction in the average molecular weight of
the polymer. As the post-reaction proceeds, the viscosity
of the mass may increase. However, the post-reaction step
is not carried out long enough or under sufficiently severe
conditions so as to result in an intractable mass.
Suitable polypropylene oxide polymers for use
herein include a polymer of polypropylene oxide which is
capped on one or both ends with alkyl or ester groups, said
polymer having more than 4 propylene oxide units and an
average molecular weight of at least 300. Suitable butyl
end-capped polypropylene oxide polymers are available from
Union Carbide Chemicals and Plastics Company under the trade
name "UCON" LB series products. These are sold commercially
as water-insoluble lubricants for various specialized
applications and other uses. "UCON" LB-65, LB-385, LB-525,
LB-625, LB-1145 and LB-1715 have average molecular weights
of 340, 1200, 1420, 1550, 2080 and 2490, respectively. Other
suitable end-capped polypropylene polymers are available
under the trade name "ARCOL" R-series, available from the
ARCO Chemical Company, Newtown Square, PA. "ARCOL" R-2085
and R-2150 are propoxylated branched fatty alcohols having
an average molecular weight between 1100 and 1200. R-2150
also contains about 2~ ethylene oxide. "ARCOL" R-2151 is a
propoxylated linear fatty alcohol. Other suitable
polypropylene oxide polymers for use herein include
SUBSTITIJTE SHEET ~UI E 2~)
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W O 97/00351 PCTrUS96/10266
polypropylene glycols having an average molecular weight
greater than 1100. Preferably the polypropylene oxide
polymer is endcapped.
The above-defined compositions of or used in the
present invention optionally contain at least one of a
dispersing agent, surfactant, wetting agent, thickening
agent, antistatic agent, coloring agent, fiber lubricant,
softener, other surface active agent and hydrophilic agent,
other ingredients which impart desirable properties for a
particular application, or a mixture thereof.
The above defined aqueous based compositions of
the present invention preferentially include a wetting or
dispersing agent to aid in dispersion. Still more
preferentially the wetting or dispersing agent is a nonionic
surfactant having ethylene oxide moieties and hydrophobic
portions. Suitable examples of these materials include
ethoxylated alkyl phenols such as some "IGEPAL" nonionic
surfactants sold by Rhone-Poulenc Inc., Cranbury NJ, such as
"IGEPAL" C0-970; lauryl alcohol ethoxylated with about 50
ethylene oxide moieties, such as "ETHAL" LA 50 available
from Ethox Chemicals Inc. Greenville, SC; and branched fatty
alcohol ethoxylates such as ~MERPOL" SE, available from E.
I. du Pont de Nemours and Company, Wilmington, DE. Even
more preferentially the nonionic surfactant is an
ethoxylated branched chain alcohol such as "POLYWET" A or B,
containing a mixture of branched alcohol ethoxylates with
about 2 to 13 ethoxy groups along with a solubilizing agent
such as sodium xylene sulfonate, which is available from
Peach State Labs Inc., Rome, Georgia.
Suitable wetting or dispersing agents or
surfactants also include a cationic surfactant, such as
"ARQUAD" 12/50 (dodecyl trimethylammonium chloride in water)
or 16/50 (hexadecyl trimethylammonium chloride in water),
available from Akzo Nobel Chemicals, Inc. Chicago, IL;
sodium alkylnapthalene sulfonate salts such as "ALKANOL"XC
SUBSTITUTE SHEET (RULE 2~)
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and branched fatty alcohol ethoxylates such as "MERPOL"SE
both available from E. I. du Pont de Nemours and Company,
Wilmington, DE; polyoxyethylated (4) isodecyl alcohol such
as "RHODASURF"DA-530 available from Rhone-Poulenc
Surfactants and Specialties, Cranbury, NJ; and sodium
alkylbenzene sulfonate in water such as "BIOSOFT"D-40
available from Stephan Company, Northfield, IL.
A preferred example of the dispersion composition
of the present invention is a dispersion in water of a
polyoxyethylene terephthalate and polyethylene terephthalate
block copolymer such as "ZELCON" PG, available from E. I. du
Pont de Nemours and Company, Wilmington, DE; a butyl-
endcapped polypropylene oxide such as "UCON"LB-series fluid
polymers available from the Union Carbide Chemicals and
Plastics Company, and "POhYW~T" A or B available from Peach
State Labs, Inc.
The present invention further comprises a method
for imparting a durable hydrophilic coating to polyester,
polypropylene or polyethylene fabric or fiber comprising
application to the surface of the fabric or fiber of an
effective amount of the above-defined inventive
compositions.
Alternatively, the present invention also
comprises a method for imparting a durable hydrophilic
coating to polyester, polypropylene or polyethylene fabric
or fiber comprising application to the surface of the fabric
or fiber of an effective amount of at least one composition
selected from: l) a mixture of an organic solvent and a
hydrophilic copolyester having repeating segments of a
polyoxyethylene diester and a polyalkylene diester, 2) a
polypropylene oxide polymer capped on one or both ends with
~ an alkyl or ester group, said polymer having more than 4
propylene oxide units and an average molecular weight of at
- least about 300, an aqueous dispersion thereof, or a mixture
thereof with an organic solvent, 3) a polypropylene glycol
SUB~;TITUTE SHEET (RULE 2B)
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W O 97/00351 PCTrUS96/10266
having an average molecular weight greater than 1100, an
aqueous dispersion thereof, or a mixture thereof with an
organic solvent, 4) an aqueous dispersion of polyvinyl
alcohol and a polypropylene oxide polymer capped on one or
S both ends with an alkyl or ester group, said polymer having
more than 4 propylene oxide units and an average molecular
weight of at least about 300, 5) an aqueous dispersion of
polyacrylamide and a polypropylene oxide polymer capped on
one or both ends with an alkyl or ester group, said polymer
having more than 4 propylene oxide units and an average
molecular weight of at least about 300, 6) a mixture of
polyvinyl alcohol and polypropylene glycol having an average
molecular weight greater than 1100, and 7) a mixture of
polyacrylamide and polypropylene glycol having an average
molecular weight greater than 1100.
These compositions and the inventive compositions
A, B, C and D previously described may be applied to the
fabric or fiber by any suitable means such as wiping,
painting, dipping, foaming, feeding at the nip of a roller,
spraying, or other means. The composition is typically
applied at a minimum level of at least 0.48~ weight of
solids on fiber, preferably at least 0.7 ~ weight of solids
on fiber, and most preferably 1.25~ or higher weight of
solids on fiber to achieve water wetability and durability.
Application at lower levels will improve hydrophilic
character. After drying or removal of the solvent, a
durable hydrophilic coating remains on the fabric or fiber
surface. This coating causes water placed on the surface to
rapidly wet the fabric and to pass through the fabric layer.
The present invention further comprises a woven or
nonwoven polyester, polyethylene or polypropylene fabric or
fiber having applied to i~s surface any of the above
inventive compositions or treated by any of the above
inventive methods.
SUBSTITUT~ SHEET ~U? E 26)
,
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The inventive compositions and methods impart
durable hydrophilic character to polyester, polypropylene or
polyethylene fabrics or fibers in woven or nonwoven form.
Such durability is measured in the trade by what are called
"insult tests", and repeated exposures to moisture or water
washes are referred to as "insults". In the "insult tests"
described below on polypropylene, the inventive compositions
and the compositions used in the method of the present
invention imparted hydrophilic character with durability.
Preferably, combining a block copolymer of polyoxyethylene
terephthalate and polyethylene terephthalate with butyl-
endcapped poly(propylene oxide) polymers and applying from
an aqueous dispersion with a wetting agent containing a
mixture of a polyoxyethylated branched fatty alcohol and
sodium xylene sulfonate provides a coating having enhanced
durability (up to fifteen or more water washes). A
preferred composition is "ZELCON" PG mixed with 20~ "UCON"
LB-625, and other ~ZELCON" polymer/"UCON" combinations. The
polypropylene oxide monoethers show better performance than
either the polypropylene oxide glycols or the polybutylene
oxide polymers tested.
The compositions, methods, fabrics and fibers of
the present invention are useful in diapers, incontinence
pads, agricultural fabrics for landscaping or mulching, and
filtration devices wherein the ability to transmit water
through the fabric is desirable. The present invention is
also useful in clothing and sportswear where wicking away of
moisture is desirable. In particular nonwoven protective
garments treated in accordance with the present invention
are more comfortable. It has also been found that the
compositions of the present invention act as a softener for
polypropylene or polyethylene as well. The compositions of
the present invention are also useful in applications where
~ it is desirable to make a fiber surface more hydrophilic for
TE SHEEr (FtULE 26)
CA 0222~026 1997-12-18
W O 97/00351 PCT~US96/10266
better adhesion or easier incorporation into water-borne
compositions such as cement mixtures or paper pulps.
In the following examples tradenames used are
defined as follows.
"ZELCON" PG polymer is a polyoxyethylene terephthalate
and polyethylene terephthalate block copolymer, which is
generated by dehydrating "ZELCON" 5126.
"ALKANOL" XC is a sodium alkylnapthalene sulfonate
salt. "MERPOL" SH and "MERPOL" SE are branched fatty
alcohol ethoxylates with average molecular weights between
about 350 and 650. "MERPOL" A is an octyl alcohol phosphate
ester mixture.
"AVITEX" DN is a quaternary methylsulfonium poly(oxy-
1,2-ethanediyl) octadecylammonium salt.
"ELVANOL" 90-50 is fully hydrolyzed poly(vinyl
acetate); a 4~ solids aqueous solution at 20 C gives a
viscosity of 12-15 cP as determined by the Hoeppler falling
ball method. "ZELCON" 5126, "ZELCON" PG, "ALKANOL" XC,
"MERPOL" SH, "MERPOL" SE, "MERPOL" A, "AVITEX" DN, and
"ELVANOL" 90-50 are available from the E. I. du Pont de
Nemours and Company.
"MILEASE" T is a polyoxyethylene terephthalate and
polyethylene terephthalate block copolymer. It is available
from the Imperial Chemical Industries Limited, London,
England.
"UCON" LB-series and "UCON" 50-HB series lubricants are
available from the Union Carbide Chemicals and Plastics
Company, South Charleston, West Virginia, USA 25303.
"ARCOL" R-2085 and R-2150 are propoxylated branched
fatty alcohols with molecular weights between 1100 and 1200.
R-2150 also contains about 2~ ethylene oxide. "ARCOL" R-
2151 is a propoxylated linear fatty alcohol. They are
available from the ARCO Chemical Company, Newtown Square,
Pennsylvania, 19073 USA.
SUBSTITUTE SHEET ~RULE 20
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"WITCONOL" APS, F-26-46, and APM are propoxylated fatty
alcohols available from the Witco Corporation, Greenwhich,
Connecticut.
"PLURACOLS"1010 and 2010 are polypropylene glycols with
average molecular weights of 1050 and 2000, respectively,
and are available from BASF Wyandotte Corporation,
Wyandotte, Michigan, 48192 USA.
"POLYWET" A and B are both a mixture of a
polyoxyethylated branched fatty alcohol (isodecyl) and
sodium xylene sulfonate, and they are available from Peach
State Labs, Inc., Rome, Georgia, 30162 USA.
"ARQUAD" 12/50 or 16/50 are each a cationic surfactant,
available from Akzo Nobel Chemicals, Inc., Chicago,
Illinois, 60606 USA. "ARQUAD" 12/50 is a solution of
dodecyl trimethylammonium chloride in water. "ARQUAD" 16/50
is an aqueous solution of hexadecyl trimethylammonium
chloride.
"MONAZOLINE" O, 1-hydroxyethyl-2-oleylimidazoline is a
cationic surfactant, available from Mona Industries, Inc.
Paterson, NJ, 07544 USA.
"RHODASURF" DA-530 is polyoxyethylated (4) isodecyl
alcohol. "IGEPAL" C0-970 is polyoxyethylated (50)
nonylphenol. Both are available from Rhone-Poulenc Inc.
Cranbury, NJ 08512 USA.
"ETHAL" LA-50 is polyoxyethylated (50) lauryl alcohol,
available from the Ethox Chemicals, Inc., Greenville, South
Carolina, 29606 USA.
"BIOSOFT" D-40 is a 40~ aqueous solution of a sodium
alkylbenzene sulfonate, available from the Stepan Company,
Northfield, Illinois 60093 USA.
MPT .F~ 1
A dispersion was prepared using the components
described below.
Ingredients Equivalence Weight
====_======= =========== ======
SU~ 111 ~JTE SHEET (RU~
CA 0222~026 1997-12-18
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16
"ZELCON" PG 8.3 wt~ 22.9 g
"UCON" LB-625 20~ of "ZELCON" PG 4.6 g
"POLYWET" A 13~ of "ZELCON" PG 3.0 g
Distilled water (1/2 ice) 89 wt~ 243.0 g
Total dispersion (total weight) 273.5 g
A round bottom flask was equipped with a stirrer,
thermocouple, nitrogen line and charged with the "ZELCON" PG
polymer. The vessel was swept well with nitrogen, then
heated to 180~C. It was stirred until fully melted. While it
was melting, the "UCON" LB-625 was dispersed in a mixture of
the water and "POLYWET" A in a rapidly stirring blender.
Then the molten "ZELCON" PG polymer was added and the
mixture stirred for 3-5 minutes or until well mixed. After
diluting, if necessary to lower the viscosity, the mixture
was sonicated or homogenized to complete the dispersion
process.
The weight of "ZELCON" PG given above was its
initial weight. After melting, a small amount estimated at 2
to 3 grams clung to the sides of the flask and was lost in
transfer.
MPT,F~.~ 2 - 1 9
The following compositions were prepared using the
procedure of Example 1. All formulations were aqueous;
after the initial dispersion was made to a concentration of
between 5 to 25~ solids, more water was added to dilute the
dispersion for application in the pad bath used for
performance testing. This allowed the ad~ustment of the
desired pickup of material onto the fabric. The pickup of
aqueous solution by the fabric (wet pickup) was generally in
the range of 66 to 82~ of the weight of the fabric. This
allowed a calculation of the solid material applied to the
fabric. The formula used:
bath solids concentration (~) X wet pickup (~)/100 =
solids applied to fiber (~)
SUBST~TUTE SHEEr (RIJLE 2~)
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T~hle
Ex. Hydrophilic Polypropylene Oxide Surfactant (8)
No. Copolyester Polymer
S === =========== ============== ============
2 "ZELCON" PG: 55.0g "UCON" LB 625: 5.0g "POLYWET" A: 5.0g
3 "ZELCON" PG: 21.2g "UCON" LB-625: 6.3g "POLYWET" A: 3.0g
4 "ZELCON" PG: 22.9g "UCON" LB-625: 4.6g "POLYWET" A: 3.0g
"ZELCON" PG: 25.0g "UCON" LB-625: 2.5g "POLYWET" A: 3.0g
10 6 "ZELCON" PG: 25.0g "UCON" LB-1145: 2.5g"POLYWET" A: 3.0g
7 "ZELCON" PG: 25.0g "UCON" LB-1715: 2.5g"POLYWET" A: 3.0g
8 "ZELCON" PG: 22.9g "UCON" LB 385: 4.6g "POLYWET" A: 3.0g
9 "ZELCON" PG: 45g "UCON" LB-625: 6.8g "POLY~ET" B: 5.3g
10 "ZELCON" PG: 45g "UCON" LB-625: 4.5g "POLYWET" B: 5.3g
15 11 "ZELCON" PG: 45g "UCON" LB-625: 2.3g "POLYWET" B: 5.3g
12 "ZELCON" PG: 45g "UCON" LB-625: 9.0g "POLYWET" B: 5.3g
13 "ZELCON" PG: 45g "UCON" LB-1715: 2.3g"POLYWET" B: 5.3g
14 "ZELCON" PG: 45g "UCON" LB-1145: 2.3g"POLYWET" B: 5.3g
15 "ZELCON" DG: 22.9g Note 1: 4.6g "POLY~ET" A: 3.0g
20 16 "ZELCON" PG: 22.9g Note 2: 4.6g "POLYWET" A: 3.0g
17 "ZELCON" PG: 22.9g Note 3: 4.6g "POLYWET" A: 3.0g
18 "ZELCON" PG: 45g "PLURACOL" 1010: 9.0g"POLYWET" B: 5.3g
19 "ZELCON" PG: 45g "PLUR~COL" 2010: 9.Og"POLYWET" B: 5.3g
25 Note 1: This was "ARCOL" R-2085, a polypropylene oxide
polymer end-capped with a 13-carbon alkyl group.
Note 2: This was "ARCOL" R-2150, a polypropylene oxide
polymer end-capped with a 13-carbon alkyl group, and
containing about 2% ethylene oxide.
30 Note 3: This was "ARCOL" R-2151, a polypropylene oxide
polymer end-capped with 12- to 16-carbon alkyl groups.
The compositions were diluted as described to make
a 200 gram bath, then applied to the test polypropylene
35 fiber. In the tests below, the fiber was a spunbond
polypropylene sheet. After solution application, the fabric
was dried at 235~F (113~C) for 2 minutes and tested. A
variation on a standard water repellency test was used. If
a drop of pure water wet out completely on the fabric, the
40 fabric was rated w/w for "water w~ ". If not, test water
SllBSTITUTE SHFET (RULE 2B)
CA 0222~026 1997-12-18
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solutions with increasing amounts of isopropyl alcohol (IPA)
were used. Webs that resist penetration of pure water, but
absorb a 2~ IPA water solution were given a rating of 1; a
rating of 2 corresponded to 5~ IPA, a rating of 3
corresponded to 10~ IPA , and a rating of 4 corresponded to
20~ IPA. The first solution that wet the fabric was noted,
and the fabric was then assigned that number. Untreated
polypropylene rated a "4" on this test, and lower numbers
than 4 indicated improved wettability.
Treated fabrics that rate w/w were "insulted" to
test durability and then rerated again. The insult test
comprised cutting out a circular piece of the treated
fabric, placing the circle on a glass fritted funnel, and
then sucking 100 mL of distilled water rapidly through the
circle of fabric. The circle was then dried again and
retested for water wetting. The more cycles of "insults"
with full water wetting rem~;n;ng/ the better (these are
rated as "successful" in the table below. A plus (+)
~ollowing a number indicates that the tests were
discontinued before failure occurred.). The results of the
performance testing are listed in Table 2.
Tahle 2
Performance Testing
Example Bath ~ Water Repell~ncy Tests No. of
No. Solids In;t;al After 1stSuccessful
"InRl1lt'- "InRlllts"
2 5.4~ w/w w/w 7
3 3.1~ w/w w/w 7
4 3.0~ w/w w/w 10+
3.0~ w/w 2 0
6 3.0~ w/w w/w 4
7 3.0~ w/w w/w 2
8 1.25~ w/w w/w 3
9 2.5~ w/w w/w 3+
2.5~ w/w w/w 3+
11 2.5~ w/w w/w 3+
12 2.5~ w/w w/w 3+
13 2.5~ w/w w/w 3+
SU~ JTE SHEET (~ULE 2~)
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19
14 2.5~ w/w w/w 3+
1.25~ w/w w/w 13
16 1.25~ w/w w/w 15+
17 1.25~ w/w w/w 15+
18 2.5~ w/w 2 0
19 2.5~ w/w w/w 3+
While the above Example 5 showed poor durability,
other tests with comparable formulations such as Example 10
were satisfactory.
The above tests showed that "PLURACOL" 1010, a
non-endcapped polypropylene glycol with a molecular weight
of 1050, had little durability. "PLURACOL" 2010, with a
molecular weight about 2000, had satisfactory durability
when used with "POLYWET" B. Mixtures of "ZELCON" PG with
"UCON" LB-625 had satisfactory durability with ratios of
"ZELCON" to "UCON" ranging from 5/1 to 20/1. Mixtures of
"ZELCON"PG with "UCON" LB-1715 and "UCON" LB-1145 also had
satisfactory durability with "POLYWET" B.
~MPT.~.~ 20-72
The following compositions were prepared using the
procedures of Example 1 and tested as described in Example
2.
T~RT.~ 3
Ex. Hydrophilic Polypropylene Oxide Surfactant(s)
No. Copolyester Polymer
=== ==========
"ZELCON"PG: 110g "UCON" LB 65: 10g "ARQUAD 12/50: 10g
"IGEPAL"CO-970: 5g
"MERPOL" SE: 10 drops
"POLYWET" A *
35 21 "ZELCON"PG: 110g "UCON" LB 625: 10g "ARQUAD 12/50: 10g
"IGEPAL"CO-970: 5g
"MERPOL" SE: 10 drops
"POLYWET" A *
22 "ZELCON"PG: 110g "UCO~ 50-HB-55: 10g"ARQUAD" 12/50: 10g
"IGEPAL"CO-970: 5g
"MERPOL" SE: 10 drops
"POLYWET" A *
SlJ~;I ~ E SHEET (~ULE 26)
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W O 97/00351 PCTrUS96/10266
* In each case 0.3 g of "POLYWET" A was added to 100 g of
bath after the initial dispersion was added.
The "UCON" 50-HB-55 is an alkyl encapped polymer
containing equal amounts by weight of oxyethylene and
oxypropylene groups.
T~hle 4
Performance Testing
Ex. Bath ~W~ter ReI)ell ~ncy Tests No. of
10 No . .~ol; ~.~ In; t;~1 After 1st Successful
"In~lllt" "In~l~l ts"
3.2~ w/w w/w
21 2.9~ w/w w/w 3
22 2.8~ w/w 3 0
These examples showed the "UCON" LB series worked, that
LB-625 was better than LB-65, but that the "UCON" 50-HB-55 gave
little durability.
~r~PT FS ~3-~7
The following compositions were prepared using the
procedures of Example 1 and tested as described in Example 2.
T~hle 5
Ex. Hydrophilic Polypropylene Oxide Surfactant(s)
25 No. Copolyester Polymer
=== ============== =================== ===5.============
23 "ZELCON"PG: 57g "UCON" LB 625: 11.4g "MERPOL" SE: 3.8g
SOD.XYL.SULF.: 2.6g
24 "ZELCON"PG: 57g "UCON" LB 625: 11.4g "RHODASURF"DA-530: 3.8g SOD.XYL.SULF.: 2.3g
"ZELCON"PG: 57g "UCON" LB 625: 11.4g "MERPOL" SH: 7.6g
SOD.XYL.SULF.: 2.5g
26 "ZELCON"PG: 57g "UCON" LB 625: 11.4g "MERPOL" SH: 3.8g
"MERPOL" SE: l.9g
SOD.XYL.SULF.: 2.3g
27 "ZELCON"PG: 37g "UCON" LB-625: 6.8g "BIOSOFT" D-40: 7.2g
'~RHODASURF~DA-530: 1.2g
Note: SOD.XYL.SULF. is sodium xylene sulfonate, a
40 solubilizing agent.
SUBSTITUTE SHEET ~RUL~
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T~hle 6
Performance Testing
- Ex. Bath ~ Water Repellency Tests No. of
5 No. .~ol;~ ;t;~l After 1st Successful
~ lt" "In~l~lt"
23 1.5~ w/w w/w 4
24 1.5% w/w w/w 6
1.5~ w/w w/w 3
10 26 1.5~ w/w w/w
27 2.5~ w/w w/w 3+
The above tests showed that the inventive
composition has satis~actory durability using a number of
surfactants other than "POLYWET" A or B.
R~P~I\IPT.F..~ ~!8-36
The following compositions were prepared using the procedures of
Example 1 and tested as described in Example 2.
T~hle 7
Ex. Hydrophilic Polypropylene Oxide Surfactant(s)
No. Copolyester Polymer
__= =============== =================== ==============
28 "ZELCON"PG: 55g "UCON" LB 625: 10g LA 50: 5g
"POLYWET" A *
29 "ZELCON"PG: 55g "UCON" LB 625: 15g LA 50: 5g
"POLYWET" A *
"ZELCON"PG: 55g "UCON" LB 1145: 10g LA 50: 5g
"POLYWET" A *
31 "ZELCON"PG: 55g "UCON" LB 1715: 10g LA 50: 5g
"POLYWET" A *
32 "ZELCON" PG: 22.9g Note 1: 4.6g LA 50: 1.5g
"POLYWET" A: 3.0g
33 "ZELCON" PG: 22.9g Note 2: 4.6g LA 50: 1.5g
"POLYWET" A: 3.0g
34 "ZELCON" PG: 22.9g Note 3: 4.6g LA 50: 1.5g
"POLYWET" A: 3.0g
"ZELCON" PG: 22.9g Tridecyl : 4.6g LA 50: 1.5g
Alcohol "POLYWET" A: 3.0g
36 "ZELCON" PG: 22.9g Oleyl : 4.6g LA 50: 1.5g
Alcohol "POLYWET" A: 3.0g
SU~T~TU~E SHE~T ~RULr 26)
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PCT~US96/10266
W O 97/00351
* In these cases, 0.3 g of "POLYWET" A was added to 100 g
of bath after the initial dispersion was added.
Note 1: This was "WITCONOL" APS, a polypropylene oxide
5 polymer with about 11 propylene oxide groups and end-capped J
with an 18-carbon alkyl group.
Note 2: This was "WITCONOL" F26-46, a polypropylene oxide
polymer end-capped with an 18-carbon alkenyl (oleyl) group.
Note 3: This was "WITCONOL" APM, a polypropylene oxide
10 polymer with about 3 propylene oxide groups and end-capped
with a 14-carbon alkyl group.
T~hle 8
Performance Testing
15 Ex. Bath ~ W~ter Repellency Tests No. of
No. .~ol;~ In;t;~l After 1st Successful
"In~lllt" "In.~l~lts"
282.2~ w/w w/w 8
292.4~ w/w w/w 8
302.1~ w/w w/w 7
312.1~ w/w w/w 8
321.25~ w/w 1 0
331.25~ w/w w/w
341.25~ ~1 3 0
351.25~ cl 3 0
361.25~ ~1 >3 0
The above tests showed satisfactory results with a
variety of propylene oxide polymers end-capped with a
variety of alkyl/alkenyl groups, but showed unsatisfactory
results when the number of propylene oxide groups in the
chain was only 3. Results were also unsatisfactory when
tridecyl or oleyl alcohol was substituted for the propylene
oxide polymers.
~MPT.~.~ 37-41
The following compositions were prepared using the
procedure of Example 1 and tested as described in Example 2.
In this series of tests, two different orders of addition of
SUBSTl~UTE SltFET ~F~ULE 2~)
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ingredients were tested. In Table 10,Column A, the order of
addition was the same as in Example 1. In Table 10, Column
B, the hydrophilic copolyester and propylene oxide polymers
were mixed together first and then dispersed in the
surfactant.
T~hle 9
Ex. Hydrophilic Polypropylene Oxide Surfactant(s)
No. Copolyester Polymer
==== ======______== z============
37 Note 1: 55g "UCON" LB 625: lOg LA 50: 5g
"POLYWET" A *
38 Note 2: 55g ~UCON~ LB 625: lOg LA 50: 5g
"POLYWET" A *
39 Note 3: 55g "UCON" LB 625: lOg LA 50: 5g
"POLYWET" A *
Note 4: 55g "UCON" LB 625: 10g LA 50: 5g
"POLYWET" A *
41 Note 5: 55g "UCON" LB 625: 10g LA 50: 5g
"POLYWET" A *
* In each case, O.3 g of "POLYWET" A was added to 100 g of
bath after the initial dispersion was added.
Note 1: This polymer corresponded to "ZELCON" PG except that
10 mole ~ of the dimethyl terephthalate was replaced by 2-
dodecenyl-l-succinic anhydride.
Note 2: This polymer corresponded to "ZELCON" PG except that
2 mole ~ of the dimethyl terephthalate was replaced by 2-
dodecenyl-l-succinic anhydride.
Note 3: This polymer corresponded to "ZELCON" PG except that
the pentaerythritol was replaced by triethanolamine.
Note 4: This polymer corresponded to "ZELCON" PG except that
all of the dimethyl terephthalate was replaced by a mixture
of 95 mole ~ of diethyl sebacate and 5 mole ~ of 2-
dodecenyl-l-succinic anhydride.
Note 5: This polymer was made by post-reaction of "ZELCON~
PG with 10~ by weight of ~AVITEX" DN.
SUBST~TUlE SHEET (RU~E 2B)
CA 0222~026 1997-12-18
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24
T~hle 10
Performance Testing
Ex. Bath ~ W~ter Repell~ncy Tests No. of
5 No. Sol;~ ;t;~l After 1stSuccessful
" In ~1 ] 1 t" "In~ll1ts"
A B
37 2.8~ w/w w/w 5+ 5+
10 38 2.9~ w/w w/w 3 5+
39 3.4~ w/w w/w 3 4
3.0% w/w w/w 2 2
41 3.1~ w/w w/w 4 5+
Results were satisfactory with each of the hydrophilic
copolyesters tested, and with either order o~ addition.
~MPTFS 42-5~
The following compositions were prepared using the
procedures of Examples 1 and 2, and tested as described in
Example 2.
T~hle 11
Ex. Hydrophilic Polypropylene Oxide Sur~actant (8)
No. Polymer Polymer
25 - = ============ =====-===5========= ====~
42 None "UCON" LB 625: 10g "ARQUAD" 12/50: lOy
"IGEPAL" C0-970: 5g
"MERPOL" SE: 5 drops
"POLYWET" A *
30 43 "ZELCON"PG: 110g "UCON" LB 625: 20g "ARQUAD" 12/50: lOg
"IGEPAL" C0-970: 5g
"MERPOL" SE: 10 drops
"POLYWET" A *
44 "ZELCON"PG: llOg "UCON" LB 625: 10g "ARQUAD" 2/50: lOg
"MERPOL" SE: 10 drops
"POLYWET" A *
"ZELCON" PG: 25g None "POLYWET" B: 2.4g
46 Note 1: 34g "UCON" LB-625: 6.3g "POLYWET" B: 1.2g
47 Note 2: 50g "UCON" LB-625: 9.2g "POLYWET" B: 1.7g
40 48 Note 3: 50g "UCON" LB-625: 9.2g "POLYWET" B: 1.7g
49 "ELVANOL" 90-50: 4.2g None "POLYWET" B: 0.6g
50 "ELVANOL" 90-50: 3.1g "UCON" LB-625: 0.6g "POLYWET" B: 0.6g
SU~ 111 LITE SHEET ~RUI E 2~)
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W O 97/00351 PCT~US96/10266
51 Note 4: 4.2g None "POLYWET" B: 0.6g
52 Note 4: 3.lg "UCON" LB-625: 0.61g "POLYWET" B: 0.6g
* In these cases, 0.3 g of "POLYWET" A was added to 100 g
of bath after the initial dispersion was added.
Note l: This polymer corresponded to "ZELCON" PG except that
2 mole ~ of the dimethyl terephthalate was replaced by 2-
dodecenyl-l- 5ucc inic anhydride.
Note 2: This polymer corresponded to "ZELCON" PG except that
10 mole ~ of the dimethyl terephthalate was replaced by 2-
dodecenyl-1-succinic anhydride.
Note 3: This polymer corresponded to "ZELCON" PG except that
25 mole ~ of the dimethyl terephthalate was replaced by 2-
dodecenyl-l-succinic anhydride.
Note 4:Polyacrylamide AF 2545 was used and was 5~ hydrolyzed
and had a molecular weight of approximately 500,000. It was
obtained from Dowell Schlumberger, 6717 S. 61st W. Ave.,
Tulsa, OK 74131, USA.
T~hle 1~
Performance Testing
Ex. Bath ~ Water Repellency Tests No. of
~Q~ .sOl;~ I~;t;~l After 1st ,5llccessfl~1
"I~ Rl ~ lt" "I~l~lts"
42 0.7~ w/w w/w 2
43 3.0~ w/w w/w 5
44 3.0~ w/w w/w 5
1.5~ ~1 3 0
30 46 1.5~ w/w w/w 2
47 1.5~ w/w w/w 2
48 1.5~ 1 0
49 2.0~ <1 1 0
1.9~ w/w w/w 3+
35 51 1.5~ 2 3 0
52 1.5~ w/w w/w 3+
.,
The above series showed that "UCON" LB 625 with
dispersants and "POLYWET" A has some durability, but that
SU~STITU~E SHEET ~RUl E 2~
CA 0222~026 1997-12-18
W O 97/00351 PCT~US96/10266
26
better durability is obtained with the addition of "ZELCON"
PG.
The above tests also showed that "ZELCON" PG is
ineffective without the presence of a polypropylene oxide
5 polymer. "ZELCON" PG in which 2 or 10~ of the dimethyl J
terephthalate was replaced by 2-dodecenyl-1-succinic
anhydride was satisfactory, but a sample where 25~ was
replaced was not satisfactory at the concentration used in
the bath.
"ELVANOL" 90-50 had unsatisfactory performance
when used with "POLYWET" B alone, but had satisfactory
durability when used with "POLYWET" and "UCON" LB-625.
The polyacrylamide AF 2545 had unsatisfactory
performance when used with "POLYWET" B alone, but had
15 satisfactory durability when used with "POLYWET" and "UCON"
LB-625.
~MPT .~..~ 53-56
The following compositions were prepared using the
procedure of Examples 1 and tested as described in Example
2.
T~hle 13
E~. Hydrophilic Polypropylene Oxide Surfactant(s)
No. Copolyester Polymer
25 === ============ =============== =============
53 "ZELCON"PG: 55g "UCON" LB 625: lOg "MONAZOLINE" 0: 5g
"IGEPAL" C0-970: 2.5g
"POLYWET" A *
54 "ZELCON"PG: 55g "UCON" LB 625: lOg "MONAZOLINE" 0: 2.5g
"IGEPAL" C0-970: 2.5g
"POLYWET" A *
"ZELCON"PG: 55g "UCON" LB 625: lOg "IGEPAL" C0-970: 5g
"POLYWET" A *
56 "ZELCON"PG: 55g "UCON" LB 625: lOg LA 50: 5g
"POLYWET" A *
* In each case, O.3 g of "POLYWET" A was added to 100 g of
bath after the initial dispersion was added.
SU13~;TITUTE SffEE~ t ~2r)
CA 0222~026 1997-12-18
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27
T~hle 14
Performance Testing
Ex. Bath ~ W~ter Repellency Tests No. of
No. .~ol;~ In;t;~l After 1st Successful
"I~l~lt" "I~.~lllts"
53 3.2~ w/w w/w 5+
54 3.2~ w/w w/w 5+
2.9~ w/w w/w 4
56 3.2~ w/w w/w 4
These examples showed that "ZELCON" plus "UCON"
gave durable coating whether it was used with a mixed
cationic/nonionic dispersant as in Examples 53 and 54, or
nonionic as in Examples 55 and 56.
~,~MPT .~.~ 57-61
The following compositions were prepared using the
procedure of Examples 1 and tested as described in Example
2.
T~hle 15
Ex. Hydrophilic Polypropylene Oxide Surfactant(s)
No.CopolyesterPolymer
_================= =================== =============
57 "ZELCON"PG: 110g "UCON" LB 385: 10g "ARQUAD"12/50: 10g
"POLYWET" A *
58 "ZELCON"PG: 110g "PLURACOL" 2010: 10g "ARQUAD"12/50: 10g
"POLYWET" A *
59 "ZELCON"PG: 110g "UCON"LB 385: 10g "ARQUAD"16/50: 10g
"POLYWET" A *
60 ~ZELCON~PG: 110g "PLURACOL" 1010: 10g "ARQUAD"16/50: 10g
"POLYWET" A *
61 "ZELCON"PG: 110g ~PLURACOL~' 2010: 10g "ARQUAD"16/50: 10g
"POLYWET" A *
* In each case, 0.3 g of "POLYWET" A was added to 100 g
o~ bath a~ter the initial dispersion was added.
SU13STITUTE SHE~ ~: ' E ~)
CA 0222~026 1997-12-18
W O 97/003~1 PCT~US96/10266
28
T~hle 16
Performance Testing
Ex. Bath ~ W~ter Repel l~ncy Tests No. of
No. Sol;~ t;~l After 1st Successful
S "Tn.ql~lt" "Ir-.qlllts"
57 2.9~ w/w w/w 3
58 2.8~ w/w w/w
59 3.0~ w/w w/w
3.0~ w/w 3 0
10 61 3.1~ w/w w/w
This data showed that polypropylene glycol with an
average molecular weight of 2000 was effective but an
average molecular weight of 1000 was less effective; and
that "UCON" 385 was better in performance than polypropylene
glycol with an average molecular weight of 2000.
E~MPT.~..~ 6~-66
The following compositions were prepared using the
procedures of Examples 1 and 2, and tested as described in
Example 2. In the application tests below, two different
levels of application were tested. In Table 18 Column A,
the treating bath used contained 1.25 ~ solids. In Table 18
Column B, the treating bath used contained 2.5 ~ solids.
T~hle 17
Ex. Hydrophilic Polypropylene Oxide Surfactant(s)
No. Copolyester Polymer
=_= ==========_== ===============_= ===========
30 62 Note 1: 22.9g "UCON" LB-625: 4.6g "POLYWET" A:
3.0g
63 "ZELCON" PG: 22.9g "UCON" LB-625: 4.6g "MERPOL" SE:
3.0g
"MERPOL" A:
35 0.2g
"ALKANOL" XC:
O.2g 64 "ZELCON" PG: 172g "UCON" LB-625: 34.5g "POLYWET" A:
22.5g 65 "ZELCON" PG: 172g "UCON" LB-525: 34.5g "POLYWET"
A: 22.5g 66 "ZELCON" PG: 172g "UCON" LB-385: 34.5g
"POLYWET" A: 22.5g
SUI~STITUTE SHFET (R! !~ E 20
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29
Note 1: This polymer corresponded to "ZELCON" PG except
that 10 mole ~ of the ingredients were replaced by
polyethylene glycol methyl ether (950 molecular weight).
T~hle 18
Performance Testing
Ex. Bath ~ Water Repellency Tests No. of Successful
Sol;t~!: In; t~l After 1st
llt" "I~l]lts"
10 A B A B
62 1.25~ 2.5~ w/w w/w 10+ 15+
63 1.25~ 2.5~ w/w w/w 4 13
64 1.25~ 2.5~ w/w w/w 4 15+
65 1.25~ 2.5~ w/w w/w 10+ 15+
15 66 1.25~ 2.5~ w/w w/w 9 15+
The above table showed the effect of increasing
the loading level in the application bath. Example 63
showed satisfactory results with a surfactant mixture
20 containing non-ionic ("MERPOL" SE and A) and anionic
("ALKANOL" XC) surfactants. Examples 65 and 66 showed
satisfactory results using lower molecular weight (MW)
polypropylene oxide polymers (average MW 1420 and 1200,
respectively, versus "UCON" LB 625 MW of 1550).
~ MPT .F~ 67
The following compositions were prepared using the
procedure of Example 1 and tested as described in Example 2.
T~hle 19
30 Ex. Hydrophilic Polypropylene Oxide Surfactant(s)
No. Copolyester Polymer
~== 5=3=========_ ================= ===============
67 "ZELCON"PG: 514g "UCON" LB 625: 103g "POLYWET" A: 67.3g
The above sample was tested as an agent to speed
the rate of wicking of a spun-laced polyester/wood pulp
composite fabric ("SONTAR~" available from E. I. du Pont de
Nemours & Co., Wilmington, DE) versus a control test in
which no Example 67 composition was used. The lower end of
SlJ~ T~ SHEET (RLELE 26)
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W O 97/003~1 PCT~US96/10266
one inch (2.54cm) wide strips of the test fabric were
immersed in water and the time for the water to climb
vertically along the fabric was measured The results below
are the average of two trials each.
T~hle 20
Solids ~ in Bath Wicking Time: 2.54 cm
Wicking Time: 5.08 cm
(sec.) (sec.)
10 ================ ===================== ====_========
2.0~ 7.28 34.08
6.0~ 6.71 30.60
None 12.64 52.90
15 The above test showed that the inventive
composition nearly doubled the rate of wicking on a
polyester/wood pulp composite fabric.
~MPT .~.~ 68-72
The compositions of examples 68-70 were prepared
using the procedure of Example 1 and then were diluted in
water as described below and padded onto a woven polyester
fabric. Before testing, the polyester fabric was scoured
with hot water (90~C), dried, then further scoured with hot
dichloromethane to remove all finishing chemicals. Examples
71-72 were prepared by dissolution of the listed polymer in
ethyl acetate solvent. Each was then padded onto
polypropylene fabric and allowed to dry at ambient
temperatures before testing.
T~hle 21
Ex. Hydrophilic Polypropylene Surfactants
No. Polymer Ox1~e Polymer or SolvPnt
68 "ZELCON"PG 100g None "IGEPAL CO" 970 10
g
"BIOSOFT"D 40 10 g
69 "ZELCON"PG 45g "UCON"LB-625 9.0g "POLYWET"B 5.3g
None "UCON"LB-625 8 g "POLYWET"B 1.lg
71 None ~UCON"LB-625 3.0g Ethylacetate 297g
72 "ZELCON"PG 3g None Ethylacetate 297g
S~,U3STITUTE S~EET (RUI E 2~
CA 02225026 1997-12-18
PCT~US96/10266
W O 97/00351
T~hle ~
Per~ormance Testing
~ Ex Bath ~W~ter Repell~ncy Test No. of
S ~Q_ .~ol;~;t;~l After 1st Successful
lt" "In.sl]lt"
68 4.25 w/w w/w 3+
69 1.5 w/w w/w 3+
1.5 w/w w/w 3+
.~ol;~q on F~hr;c
71 1.33~ w/w w/w 2+
72 1.33~ 1 1/2 0
The above tests showed that the inventive compositions
were e~fective on different fabrics and effective when
applied from an organic solvent system.
~A~PT.~ 73-78
The following compositions were prepared using the
procedure of Example 1. Examples 73-74 were diluted in
water as described below and padded onto polypropylene
fabric and dried at 235~F for two minutes before testing.
T~hle ~-3
25 Ex. Hydrophilic Polypropylene Sllrf~ct~nt
No. Polym~ Ox;~e polymer
73 "ZELCON"PG 22.9g "UCON" LB-625 4.6g "POLYWET"A
l.lg
74 "ZELCON"PG 22.9g "UCON" LB-625 4.6g "POLYWET"A
30 l.lg
"ZELCON"PG 172g "UCON" LB-625 34.5g "POLYWET"A
22.5g
76 Note 1: 22.9g "UCON" LB-625: 4.6g "POLYWET" A: 3.0g
77 Note 1: 22.9g "UCON" LB-625: 4.6g "POLYWET" A: 3.0g
35 78 Note 1: 22.9g "UCON" LB-625: 4.6g "POLYWET" A: 3.0g
Note 1: This polymer corresponded to "ZELCON" PG except
that 10 mole ~ of the polyethylene glycol was replaced by
polyethylene glycol methyl ether (950 molecular weight).
T~hle ~4
SUBSTITUTE SHEET (RULE 2B)
CA 0222~026 l997-l2-l8
W 097/00351 PCT~US96/10266
Performance Testing
Ex Bath ~ W~ter Repell~ncy Te~t No. of
ol;~l~ In; t;~31 After 1st Successful
~Tnql~lt~ In~lll ts"
73 0.36~ 3 not tested 0
74 0.72~ w/w w/w 2
2.5~ w/w w/w 15+
76 0.36~ <1 not tested 0
77 0.72 w/w w/w 4
0 78 2.5~ w/w w/w 15+
Based on measured wet pickups for this fabric in
the padding operation of approximately 82~, a bath solids
concentration of 0. 36~ corresponds to an application of
0.30~ solids on weight of fabric. This produces a fabric
that has improved hydrophilic character, but is not fully
water wettable. At bath concentrations of 0. 72~
(corresponding to an application level of 0. 59~ solids on
weight of fabric) or higher, a water wettable surface is
obtained. At further increased application levels, more
durability is achieved. The upper limit of application
would be based on practicability.
~MPT.~. 79
The following composition was prepared using the
procedure of Example 1. Example # was diluted in water as
described below and padded onto a flash spun polyethylene
fabric ("TYVEK", a product of E. I. du Pont de Nemours and
Company) and dried at 200~F (93~C) before testing.
T~hle 25
Ex. Hydrophilic Polypropylene Surfactants
No. Pol~Tner Ox;~e Polyrner or sol v~ont
79 " ZELCON" PG 464 g "UCON" LB-625 93g " POLYWET" B 61g
t
SU~ 111 ~JTE SHEET (RIJLE 26)
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~hl e ~6
Per~ormance Testing
Ex Bath %W~ter Repellency Test
No. .~ol;~;t;~l After 1st After 3rd
" In .qll 1 t " " In ~l] l t "
79 3.6~ w/w cl cl
~.
Based on measured wet pickups for this fabric in
the padding operation of 33% to 50~, a bath solids
concentration of 3.6~ corresponded to an application of 1.2
to 1.8~ solids on weight of fabric. This produced a fabric
that was water wettable, but did not wet rapidly. After
further water washes a small amount of material was removed
80 that the fabric was not water wettable, but nevertheless
15 displayed improved hydrophilicity.
TE SHEET (RULE 2B)
