Note: Descriptions are shown in the official language in which they were submitted.
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IMPROVED POLYMER-GRAFTED COTTON FIBERS AND PRODUCTS
The present invention relates to the field of graft polymer coatings,
especially
as applied to cotton and cotton polyester fibers and fabrics, for properties
of crocking, color-
fastness, shrinkage, abrasion-resistance, stain-resistance, and hand. In
certain embodiments
the invention also relates to adding stretch recovery to cotton and cotton
polyester fibers and
fabrics.
Fabrics used in children's apparel should have characteristics such as
softness, excellent colorability, color fastness, and acceptable crocking.
Furthermore, it is
advantageous that the apparel be somewhat stain-resistant. Many consumers
prefer cotton,
both because it is a natural fiber and because it is typically soft. Fabrics
used in children's
apparel and in similar applications, however, typically exhibit inferior
performance in terms
of crocking, abrasion resistance, color fastness, stain resistance, and
shrinkage.
Cost is an important factor in children's clothes. The material processing
and dying processes used in the manufacture of children's apparel is different
than those
used for applications such as adult apparel. For example, children's apparel
may be printed
with a combination of pigments and an adhesive gum, in contrast to the more
expensive
reactive dyes used in adult clothing. A fixing agent is typically used to
improve fastness
because the colorant pigments do not readily migrate into cellulose fibers or
fix onto them.
Soft polymeric adhesive binders or resins are used as fixing agents. Other
useful fixing
agents include alum, caseins, starches, acrylics, rosin sizes, polyvinyl
alcohols, and cationic
colorant fixatives. They improve durability by encapsulating and binding
pigment to fiber
surfaces. Binders and resins only modestly improve durability because they are
a surface
treatment and generally have only moderate fastness. Binders or resins also
stiffen
textile-like aesthetics while often having a negative impact on liquid
distribution and
absorbency properties.
Crocking is a transfer of color from the surface of a colored fabric to an
adjacent area of the same fabric or to another surface principally by rubbing
action.
Crockfastness is color fastness to rubbing. Deeper shades of color require
excess pigment
and binder or resin that tend to rub off or crock. To obtain a navy blue color
with
acceptable crocking using this dying process results in an unacceptably stiff
garment.
Improving crockfastness/colorfastness of dyed textile fabrics has been an
ongoing problem
in the textile industry.
Current techniques to improve one or more characteristics, for example
crocking, results in diminished performance at least in terms of hand and also
usually in
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terms of shrinkage. Furthermore, the treatments exhibit poor fastness to the
fabric during
washings.
It is known to graft certain chemicals on to cotton fiber. U.S. Pat. No.
2,789,030 discusses a method of modifying a cellulose fabrics with acrylate
monomers,
modified by glyoxals. U.S. Pat. No. 3,989,454 teaches grafting acrylate,
especially ethyl
acrylate monomers, onto cotton and mercerized cotton using high energy gamma
radiation
as an initiator and a water/methanol as the solvent. U.S. Pat. No. 4,901,389
teaches a
grafting reaction for a fiber material where free radicals are formed, and
then adding
fluorinated monomers, particularly fluorinated acrylates, which are grafted.
The graft is
beneficially aided by adding a graftable derivative of morpholine, i.e., the
morpholinoethyl
acrylate. U.S. Pat. No. 4,737,156 discloses use of cationic cellulose graft
copolymers for
improving dye fastness to a dyed textile substrate by post dye application
(top up). U.S.
Patent No. 4,524,093 discloses a latex coating composition of an emulsion of
acrylate
monomers and a glyoxal curing resin.
One method to improve the hand is to treat the fabric with a softener. The
use of silicones for softening fabrics, i.e., providing lubrication between
fibers and yams so
they move over one another more easily, has been well known for quite some
time. In
addition, the use of organomodified silicones for textile treatments has also
been well
documented over the years (See U.S. Pat. Nos. 4,620,878; 4,705,704; 4,800,026;
4,824,877;
4,824,890; and 5,173,201. Silicones of this type are typically delivered to
textiles in the form
of an aqueous emulsion.
Other silicone fluids, for example polydimethylsiloxanes, provide additional
benefits such as improved fabric feel. Examples of these preemulsified
silicones are 60%
emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning Corporation
under the
trade name DOW CORNING 1157 (TM) Fluid and 50% emulsion of
polydimethylsiloxane
(10,000 cs) sold by General Electric Company under the trade name General
Electric SM
2140 (TM) Silicones. Such compositions are usually added to either the wash or
rinse water
of a laundering operation. They are typically aqueous based, water dispersible
microemulsions which contain from about 0.1 % to about 15% of the
microemulsified
functional silicones. The compositions are diluted in the wash or rinse.
U.S. Patent No. 5,616,758 describes cationic silicone compositions that can
be employed as a lubricant for fibers such as polyester, nylon, acrylic,
aramides, cotton,
wool, and blends thereof. The use of silicone compounds in the treatment of
synthetic
fibers is known in the art. See, for example, the discussion of epoxy
silicones in U.S. Patent
No. 2,947,771. Such silicone compounds are effective in both providing
increased lubricity
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of the fiber and improved softness for fabrics made from these fibers.
However, epoxy
silicones suffer from the disadvantage that they only possess a limited
durability when
employed with synthetic fibers.
The art has also looked to certain aminosilicones in the treatment of fibers.
Because these silicones possess no net charge, they cannot effectively cling,
generally by
electrical attraction to cellulosic or proteinaceous materials. In fact, when
used in
connection with conventional polyester fiber/cotton blends, the aminosilicones
will cling
only to the polyesters within the blends. In an attempt to overcome these
problems, it is
known to use cationic compounds which adhere to the cellulosic materials.
Certain
cationic compounds such as certain specific cationic polyorganodisiloxanes
(see, for
example, U.S. Patent No. 4,472,566) and quaternary nitrogen derivatives of
organosiloxanes
(such as those discussed within U.S. Patent No. 4,185,087) are known in the
art. Other
suitable fabric softening compounds are the nonquaternary amides and the
nonquaternary
amines. A commonly cited material is the reaction product of higher fatty
acids with
hydroxy alkyl alkylene diamines. See U.S. Pat. Nos. 4,460,485; 4,421,792; and
4,327,133.
U.S. Patent No. 2,952,892 describes a method of modifying cellulosic fibers
with a composition including acrylic prepolymers and silicone resins such as
alkyl
polysiloxanes. U.S. Patent No. 5,951,719 discloses a method of treating a
cellulose fabric
with a composition containing acrylates, glyoxals, and silicone textile
softeners to improve
color-fastness on dyed cotton.
U.S. Pat. No. 5,741,548 teaches a process of chemically bonding a polymeric
coating, that is, acrylic prepolymers, urethane prepolymers, and acrylic
urethanes, to many
fibers, including cellulosic cotton. This patent describes the use of graft
initiators such as iron
salts and peroxides such as urea peroxide. The purpose of the graft is to
provide a surface
capable of binding ink jet printing for high resolution imaging.
U.S. Pat. No. 5,552,472 teaches a solution for forming a grafted substance
containing an initiator, a catalyst, a water-dispersible prepolymer, and a
monomer. The graft
controls fabric porosity, and is useful for controlling the permeability of
air bags. One
composition contains a graft initiator, for example a metal ion; a catalyst,
for example
peroxide, peracid, or perbenzoate; a grafting prepolymer, for example water-
dispersible
urethanes; and a monomer, for example acrylic.
U.S. Pat. No. 5,763,557 teaches a polymeric composition which is applied by
chemical grafting that
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involves the use of monomers/prepolymers, catalyst, graft initiator and other
ingredients of
the composition. The coating is beneficially applied to reemay and satin
acetate fabric
allows to undergo graft polymerization thereby forming a polymeric film which
is
chemically bonded to the fabric substrate with strong adhesion. The preferred
composition
contains a graft initiator, for example a metal ion; a catalyst, for example a
peroxide; a
grafting prepolymer, for example urethane and/or acrylic; a monomer, for
example acrylic;
and a sodium salt of AMPS monomer.
U.S. Pat. No. 6,165,919 teaches a process whereby cellulosic materials such
as cotton fabrics and paper are crosslinked with a composition comprising (A)
polymers of
ethylenically unsaturated polycarboxylic acid monomers or salts thereof, the
monomers
having one or more dicarboxylic groups wherein the carboxyl groups are on
adjacent carbon
atoms; (B) saturated alpha-hydroxypolycarboxylic acids or salts thereof; and
(C) one or
more curing catalysts, and heated to produce esterification and crosslinking
of the celluose
by reaction of the cellulosic hydroxyl groups with carboxyl groups in the
reaction product of
(A) and (B).
Treatments of paper with formaldehyde-based reagents, such as
dimethyloldihydroxylethyleneurea, urea-formaldehyde, and melamine-
formaldehyde, have
been used as wet strength agents to impart these valuable characteristics on
cellulosic fiber.
However, formaldehyde is an irritant and a known carcinogen. In addition,
cellulosic
fabrics treated with formaldehyde-based reagents suffer severe strength loss.
As a result
there are stringent limits on the formaldehyde-production from textile
garments.
Glyoxylated polyacrylamide-diallyldimethyl ammonium chloride copolymer resins
are also
known for use as dry strength and temporary wet strength resins for paper.
The art teaches many formulations for increasing color-fastness, improving
hand, and reducing shrinkage. What is needed is an inexpensive composition and
process
whereby fabric, especially for cotton and cotton-poly blends, can be readily
treated to reduce
crocking, increase color fastness, reduce shrinkage, wherein such treatment
does not
adversely affect the hand. Preferably, the treatment can endure at least 20
washing cycles
with little degradation in performance. Preferably, the treatment that can be
applied without
adding special processing steps to the fabric. The treatment beneficially is
in a single stable
composition with a shelf life of at least two months. The compositions of the
present
invention solve these needs.
The present invention is directed toward compositions and methods to
improve stain resistance, color fastness, crock-fastness, shrinkage, and
abrasion resistance
of textile fibers while not adversely affecting the hand of the textile
products. The
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compositions are formulations that include specific mixtures of monomers (as
used herein
these are prepolymers), prepolymers, catalysts, initiators, crosslinkers, and
silicone softeners
in specific formulations. The composition, when applied to a textile,
preferably a cotton
textile, develops a graft polymerization, thereby forming a polymeric film
over at least a
portion of the fibers that is covalently bonded to the fibers.
The composition can be applied to fibers, cloth, textiles, and the like by
dipping, spraying, rollercoating, and the like. The composition is
beneficially polymerized
during conventional heating and drying processes.
One embodiment of the invention relates to a solution for forming a grafted
substrate comprising a graft initiator for activating sites on a substrate
having active
hydrogens; a first component which includes a functional group for reaction
with an
activated site on the substrate for grafting the first component thereto and
for forming an
active site on the first component; and a second component which includes a
functional
group for reacting with an activated site on the substrate or the first
component and for
forming an active site on the second component. The first and second
components are
grafted onto the substrate when contacted by the solution to form a grafted
substrate; and
one of the first and second components comprises a structure which imparts
increased
softness and stain resistance to the grafted substrate, and the other of the
first and second
components increases the flexibility of the graft.
In one embodiment, the invention involves treating cotton or cotton-polymer
fibers, for example cotton/polyester, with a stable liquid composition
comprising activators,
catalysts, and at least 5%, more preferably at least 7%, of polymerizable
softeners, as well
as a sufficient quantity of selected monomers or prepolymers to adhere the
softener to the
fabric by polymerizing polymers that incorporate the softeners and that are
grafted to the
substrate fibers.
In another embodiment, the invention relates to stable formulations of
treating compositions. The formulations comprise activators, catalysts, and at
least 5%,
more preferably at least 7%, of polymerizable softeners, as well as sufficient
selected
monomers to adhere the softener to the fabric by polymerizing polymers that
incorporate the
softeners. By stable it is meant that the composition remains fluid, and has
less than about
5%, preferably less than about 2%, of the prepolymers therein self polymerize,
that is, form
insoluble/nonsuspendable polymers within the composition during storage at a
temperature
between about 60 F and about 90 F over a period of at least 2 months. The
fluid contains
activators and catalysts, but these are not active at an appreciable rate
until the fluid id
exposed to elevated temperatures during a drying and activating process.
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In another embodiment, the invention relates to stable concentrates, which
can be diluted with water or other solvent to form a stable formulations
described above.
Preferred softeners are an aqueous emulsion of silicone oil for cotton fibers,
and modified or unmodified organopolysiloxanes for cotton/polyester fibers. In
the special
case of a printed cotton, which contains pigments adhering to the cotton
fibers by means of
a gum or other adherent, the preferred softener is a combination of modified
or unmodified
organopolysiloxanes, high density polyethylene, and polyamide.
The terms fiber, yarn, filament, staple and fabric are well known to those
skilled in the textile art. Also, the finishing and treatment operations
referred to are well
known. However, as used herein, the term "fiber" refers individual fibers,
yarns, staple, and
filaments, and also to fabrics, both woven and nonwoven, and to articles made
from fibers
and/or fabrics.
It is known in the art that both natural and synthetic fibers are utilized in
the
formation of fabric material. The cellulosic textile fibers come from natural
sources such as
cotton, flax, esparto grass, milkweed, straw, jute hemp, and bagasse. The
compositions of
the invention are useful for all natural fibers. Blends, such as
cotton/polyester blends, are
well known to those skilled in the textile art.
The terms "colorfast" and/or "fastness" refer to the extent that color will
fade
or change upon exposure to an agent such as, for example, sunlight, reactive
gases,
chemicals, solvents and the like. Colorfastness or fastness can be measured by
standard test
methods such as, for example, AATCC Test Method 3-1989.
As used herein, the terms "crock" or "crockfast" refers to the extent that
color
may be transferred from the surface of a dyed fabric to another surface by
rubbing. Crock
testing may be carried out utilizing standard test procedures and equipment
such as, for
example, an AATCC Crockmeter Model CM.5, available from Atlas Electric Devices
Co.
Chicago, Ill.
As used herein, the term "dyed cotton" and "dyed cotton/polyester" means
fibers that have been exposed to and have incorporated at least one reactive
dye. Disperse
dyes are are used to dye polyester. As used herein, the term "reactive dye"
means an acid,
basic or mordant dye with an attached reactive group that is capable of
covalent bonding to
a cellulose fiber. While reactive dyes, vat dyes and sulfur dyes appear
desirable for use with
cellulose fibers, application of these dyes requires more than one process
step and is often
hampered by slow line speeds needed to achieve adequate reaction times.
As used herein, the term "printed cotton" and "printed cotton/polyester"
means fibers that have been exposed to a pigment and an adherent that helps
bind the
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pigment to the fibers. One such adherent, also called an adhesive gum, is
carboxylated
butadiene acrylonitrile.
As used herein, the term "catalyst" means a fluid formulation comprising
about 0.O1N to about 1N solution, preferably a 0.1 N solution, of the active
ingredient, for
example a peroxide or metabisulfite, typically by not necessarily dissolved in
water.
Advantageously the catalysts are added to the compositions as a solution.
As used herein, the term "graft initiator" means a fluid formulation
comprising about 0.O1N to about IN solution, preferably a 0.1 N solution, of
the active
ingredient, for example an iron salt, typically by not necessarily dissolved
in water.
Advantageously the graft initiators are added to the compositions as a
solution.
As used herein, the compositions are described by weight percent unless
otherwise indicated.
The invention is applicable to the use of any polymerizable monomers such
as: vinylidene chloride, chloroprene, isoprene, dimethylaminoethyl
methacrylate, styrene,
1,3-butylene dimethyacrylate, hydroxyethyl methacrylate, isobutylvinyl ether,
acrylonitrile,
acrylamide, N-vinyl pyridine, glycidyl methacrylate; N-vinyl caprolactam, N-
vinyl
pyrrolidone, N-vinyl carbazole, acrylic acid, methacrylic acid, ethyl
acrylate, ethyl
methacrylate, itaconic acid, isobutylmethacrylate, methyl acrylate, sodium
styrene sulfonate,
sodium vinyl ether, divinylether of ethylene glycol, divinyl ether of
butanediol, vinyl
toluene, vinyl acetate, octadecyl vinyl ether, as well as mixtures and
prepolymers thereof.
However, certain combinations of monomers and prepolymers have been found to
produce
fabric with exceptionally good characteristics, including stain resistance,
crockfastness, and
hand.
Further, the components of the compositions, including acrylic, elastomeric
latex, urethane, silicon oil, polyamide, urethane acrylate, polyethylene
glycol diacrylate,
high density polyethylene, and sodium vinyl sulfonate, refer to compositions
of monomers
and/or prepolymers, and more particularly to formulations of monomers and
prepolymers as
they are commercially available. As used herein, the term "prepolymer"
encompasses
monomers, oligmers, short chain pseudo-stable polymeric chains which can be
normally
incorporated into a polymerizing polymer, and formulations which may react
with other
compounds to form a polymerizable monomer or oligomer.
As used herein, the term "acrylic prepolymer" refers to low molecular weight
polymer chains of 6000 m.w. or less and preferably from about 200 to 1200 m.w.
Monomers especially suited to the practice of the present invention include
acrylic
monomers including hydroxyl, carboxyl, epoxy, amino, hydride and glycidyl
functional
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groups, i.e., hydroxy ethyl or propyl methacrylate, dimethyl and diethyl amino
ethyl
acrylates and methacrylate, methyl, ethyl, butyl, and other alkyl acrylates
and methacrylates,
glycidyl methacrylate, or mixtures thereof. Any of the foregoing monomers can
be used
alone or in combination in a prepolymer.
Diacrylates and triacrylates are present in at most minor quantities because
they may result in undesirable crosslinking.
For example, preferred acrylic prepolymers include HELASTIC WO-8001
(TM), HELASTIC WO-8041 (TM), and HELASTIC WO-8061, available from the
Wilmington Leather Co., New Castle, DE. These are characterized by soft
tensile strength,
adhesion, and color stability. Others include ECCO-REZ 907 available from
Advanced
Polymer, Saddlebrook, NY. It was found that different acrylic prepolymers gave
different
results, and it the most preferred formulations contain predetermined
quantities of several
acrylic prepolymers.
The glyoxal resin prepolymer is the formulation commercially available as
ECCORE GB 404 (TM), available from Eastern Color & Chemical. More preferred is
RESIN KLF (TM) which is a low-formaldehyde producing glyoxal resin.
Several formulations utilize a polymerizable silicone oil, preferably in the
form of an aqueous emulsion or microemulsion of silicone oil. The silicone oil-
softener is
specified by the quantity of the aqueous silicone oil emulsion needed in the
formulation.
Silicone oils and organopolysiloxanes provide better hand, and also increase
abrasion,
chemical, and stain resistance.
Nonfunctional and functional siloxanes as characterized above may be
monomeric, (low molecular weight), or oligomeric or polymeric (high molecular
weight)
and either linear, branched or cyclic. Examples of polymeric siloxane
compounds include
nonfunctional and organofunctional polysiloxanes including
dimethylpolysiloxanes,
methylhydrogen polysiloxanes, methylalkyl polysiloxanes methylaryl
polysiloxanes,
methylfluoroalkyl polysiloxanes, and organofunctional methylpolysiloxanes such
as
aminoalkylmethyl polysiloxane, cyanoalkylmethyl polysiloxane, haloalkylmethyl
polysiloxane, and vinylmethyl polysiloxane. Examples of monomeric or
oligomeric
siloxanes include MeOSi(Me)2-OMe, Me3SiOMe, Me3Si(OMe)21
Si(OMe)41 Si(OEt)41 MeSi(Me)2-OSi(Me)2-Me, HOOC--(CH2 )3-Si(Me)2-O-Si(Me)2 -
(CH2)3
--COOH. Examples of cyclic siloxane oligomers include
octamethylcyclotetrasiloxane and
decamethylcyclopentasiloxane.
The preferred silicone oil emulsion is SEQUASOFT 69 (TM), available from
Gen Corp., Chester, SC. The preferred high molecular weight silicone is
HELASTIC WO-
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8026 (TM), available from the Wilmington Leather Co., New Castle, DE. The
preferred
modified organopolysiloxane emulsion is APS V-SOFT (TM) available from
Advanced
Polymer, Saddlebrook, NY.
The polyamide prepolymer is a dispersion available as MICROMID 632HPL
(TM) from Union Camp, Jacksonville, FL. The preferred urethane prepolymer is
SR 9035
(TM), the preferred urethane acrylate is SR 9035 (TM), and the preferred
polyethylene
glycol diacrylate prepolymer is SR 344 (TM), each available from Sartomer Co.,
PA.
Another urethane prepolymer emulsion is RESAMINE UMT 171(TM).
The anti-crocking nonionic dispersant is CROCKFAST 2 (TM) available
from Aml Technology, Oxford, NY.
The preferred elastomeric latex prepolymer is HISTRETCH V-43 available
from B.F. Goodrich, Cleveland, OH. These are highly elastic polymers with
memory which
allows them to recover shape after being stretched. The polyethylene
prepolymer emulsion
is available as MYKON HD from Gen. Corp, Chester, Sc.
The carboxylyated butadiene acrylonitrile prepolymer is available from
Reichold Chemicals, Research Triangle, NC.
The graft polymer chains are formed from monomers and prepolymers
containing appropriate polymerizable functionality, e.g., groups such as
hydroxyl, carboxyl,
epoxy, amide, amine, a hydride and so forth. The quantity of triacrylates is
kept low to
reduce unwanted crosslinking.
As used herein, water is typically deionized water. Other components, such
as alcohols, alkyl glycols, and other organic solvents, may be used.
It is a primary object of the present invention to provide fiber and fabric
material having a coating of polymeric material which is chemically, that is,
covalently
bonded to the fabric. This invention is applicable to any suitable fabric
material, including
acetate, polyester, polypropylene fabric, nylon, polyester, fiberglass,
acrylic, cellulose,
polyethylene, polyvinyl chloride, polycarbonate, and the like. The invention
is particularly
applicable to cotton and cotton-containing fabrics.
Cotton is a major textile fiber. Typically, it is made of between about 88%
and 96% cellulose. Cellulose is a natural carbohydrate high polymer, that is,
a
polysaccharide, consisting of anhydrous glucose units joined by an oxygen
linkage forming
essentially linear molecular chains.
This grafting of polymeric material onto fibers is achieved by chemical
bonding of the polymers to the fabric substrate molecules through covalent
bonding.
Grafting of a cotton fabric surface with a polymeric layer can be described as
a process
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comprising activating the cellulose molecule, attaching monomers at the
reactive sites, and
then chain propagation on the attached monomers.
Chemical grafting is believed to involve, as a first step, the activation of
the
substrate, i.e., the fabric to be treated. The free radical initiates the
process of chemically
grafting a polymeric layer onto the fabric surface. The acidic proton from the
monomer or
from the substrate is removed by the graft initiator, thereby forming a
radical. In particular,
the process of chemically grafting a polymeric layer to a cotton fabric
surface comprises
abstraction of the (acidic) hydrogen atom from a hydroxy group of the
cellulose molecule
forming a free radical. The radical then initiates the formation of polymer
chains.
A graft initiator is used to activate the fabric surface and start the
polymerization reaction. The graft initiator is selected to abstract an active
hydrogen from a
substrate filament or yarn to which a graft polymer will be bonded. It is
preferred that the
initiator is a metal ion provided by the ionization of a metal salt. Ferrous
ions derived from
ferrous ammonium sulfate, and other metal ions such as Ag+, Co", and Cu",
derived from
their respective salt solutions, have the capacity of removing active
hydrogens and
concomitantly initiating the growth of polymer chains at the site from where
the active
hydrogen was removed. Silver ions and ferrous and ferric ions are preferred,
though other
metal salts may also be advantageously utilized.
The graft initiator beneficially includes an effective concentration of a
metal
ion selected from Fe+3, Fe+2, Ag+, Co+2, and Cu+2. The quantity need not be
large, since once
a site is activated the propagation continues substantially like an
autocatalytic process at that
site. Between 1 and 1000 ppm, preferably between 10 and 100 ppm, of a graft
initiator is
usually sufficient. When ferrous ammonium sulfate is utilized as a graft
initiator, such salts
are preferably present in the graft composition in an amount of from about
0.001 % to about
0.2% by weight of the composition, more preferably between about 0.01% to
about 0.1% by
weight of the composition. Certain iron salts perform especially well, though
they
contribute to yellowing and for certain applications may be less preferred.
In one embodiment of the present invention chemical grafting of a natural or
polymeric filament or yarn substrate is initiated with the reaction of a graft
initiator with an
"active hydrogen" of the substrate by a metal ion. Other methods of initiating
grafting,
including radiation, high or low pH, plasma treatment, or flaming are includes
in certain
embodiments of the invention, and allow the quantity of graft initiator in the
treatment
compositions to be reduced or eliminated. The initiator can in one alternative
embodiment
be ozone or other known free-radical forming agent. In these cases, however,
the
composition will not be a self-contained single-formulation composition which
can be
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easily applied and cured using equipment and processes in place in yarn and
fabric
manufacturing plants.
An active hydrogen is a hydrogen which is relatively easily removed from
the substrate by the graft initiator. A tertiary carbon, for example,
maintains a weaker
covalent bond with a hydrogen atom than a secondary carbon, and that hydrogen
atom
would be one type of active hydrogen. Other types includes N-H, -OH, -000H, -
COOR-H,
etc. For the cellulose structure, it is believed that the graft initiator
removes the active
hydrogen from a cellulose-CH2OH to form a cellulose-CH2O-. Graft initiators
are able to
remove: an active hydrogen alone, resulting in the formation of a cation
position; an active
hydrogen with one electron resulting in a substrate free radical position; or
an active
hydrogen and both electrons resulting in the formation of an anion position on
the substrate.
Hydrogen abstraction produces an activated position on a substrate which
bonds with a monomer or prepolymer, particularly with a vinyl-based monomer.
The free
radical carbonyl group thereafter reacts with either a first component or a
second component
(e.g. CH2=CH-X), so as to graft the component as a free radical upon the
polyester chain.
The grafted free radical component may now, covalently bond to additional
components of
the same or different species thereby activating additional components to a
free radical state,
or may react with another free radical to terminate the polymerization
process. It
is recognized that not all cellulose-CH2OH on a polysaccharide chain need be
activated.
Propagation continues until terminated by, for example, radical combination.
In order to ionize the metal salts to provide an activating metal ion, the
graft
solution includes a catalyst. As used herein the term catalyst means a
substance which
transforms a used graft initiator into an entity capable of initiating another
graft site. A
wide variety of catalysts may be utilized in the method of the present
invention. Among the
catalysts which can be used include ammonium persulfate, hydrogen peroxide,
tert-butylhydroperoxide, ditert-butyl peroxide, benzoyl peroxide, sodium
metabisulfite,
dicumyl peroxide, lauryl peroxide, tert-butyl perbenzoate and peracetic acid.
Other strong
oxidizer, including periodate, can also be used. Peroxide, peracid, or a
perbenzoate are
preferred catalysts. Water soluble peroxide catalysts of urea peroxide and/or
hydrogen
peroxides are preferred, as are ammonium persulfate and/or potassium
persulfate. Benzoyl
peroxide, peracetic acid or tertiary butyl perbenzoate are also useful.
Certain peroxides,
such as urea peroxide, exhibit good stability during storage and good activity
during use.
The catalyst functions to ionize metal salts such as silver or iron salts
described above so as
to provide silver and iron ion graft initiators.
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The catalyst can be present in any effective quantity. When a peroxide is
utilized to activate the graft initiator, such compounds are preferably
present in the grafting
composition in an amount of from about 0.001 % to about 0.2% by weight of the
composition, more preferably between about 0.01 % to about 0.1 % by weight of
the
composition.
The fabric according to the invention has a grafted polymer layer prepared by
a process that includes treating a fabric surface with a graft initiator
effective to chemically
activate the fabric surface. The chemically activated surface is then (or
simultaneously)
contacted with a reagent that includes the polymerizable monomers and
prepolymers that
reacts with the activated fabric surface to form a polymer layer grafted,
i.e., chemically
bonded, onto the fabric surface.
It is expected that not all of the polymerizable material in the treatment
composition will form grafts onto the substrate fiber. Preferably, at least
about 20%, more
preferably at least about 50%, of the polymerizable material is grafted to the
substrate
fibers. Evidence of grafting is found when the fibers do not lose more than
50% of the
treatment after at least 15 washes with normal detergent.
Of course, the grafted polymers may also be crosslinked to other grafted or
non-grafted polymers. It is preferred that at least some of the polymerizable
prepolymers
have functional side chains, such as hydroxyl groups, carboxyl groups, and
secondary or
tertiary amino groups. The described formulations were selected to provide a
grafted
product that improves the feel, shrinkage, stain resistance, color fastness
and crock fastness
of the treated fiber.
Where possible, the reactions of the invention make use of emulsions or
aqueous solutions to minimize environmental release of organic solvents.
Toward this end,
methods have been developed to solubilize the necessary organic materials in
water and
maintain a stable fluid composition. In addition, the reactions typically
exhaust the organic
reactants, leaving little or no organic waste.
The invention relates to forming grafted polymers onto fibers that comprise
cotton. The method provided by the present invention for the chemical grafting
of the
polymer material onto the fabric surface comprises: (a) treating a fabric
surface with an
effective graft initiator producing a chemically activated fabric surface; (b)
contacting the
activated fabric surface with a reagent comprising a polymerizable monomer or
pre-polymer
to produce a polymer layer grafted fabric surface; and (c) terminating the
chemical grafting
by radical combination or other mechanism after the polymer layer is grafted
onto the fabric
surface.
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Accordingly, the present invention provides a composition and a method for
preparing a fabric surface to provide the properties of improved crocking,
color fastness,
abrasion resistance, stain resistance, and hand, and to also provide a fabric
with reduced
shrinkage. The polymer material is chemically grafted onto the fabric
polysaccharides to
form a durable treatment. The grafted polymers advantageously comprise
silicone-based
softeners and at least two selected prepolymers. Grafting is initiated with a
graft initiator.
Other advantages of the present invention is that the formulation is stable at
room temperature, is available as a concentrate, and in preferred embodiments
has all
necessary components in a single fluid composition. The graft initiators and
catalysts are
activated by heat, for example exposure to about 340 for about one minute. It
is
advantageous in the textile production that the treatment formulation be self-
contained,
though it need not necessarily be so. Activation of the cotton fiber with, for
example, ozone
or irradiation, prior to or concurrent with the wet pickup, is also envisioned
as an
embodiment of the reaction. In such a case, the formulation without the
activator and
catalyst will be more stable to temperature variations.
One important aspect of the invention is providing a stable concentrate for
use in treating the fiber. Stable one-composition concentrates, wherein all of
the ingredients
except a solvent are present, are particularly beneficial. The premixing of
the concentrate
allows for better measurement and control of the resulting treatment
formulation.
Applicants have found that particular ratios of certain treating compounds, as
well as the
concentration of the several treating components, are important. Furthermore,
a concentrate
reduces the cost of shipping and handling the treating chemicals.
The particular monomers and prepolymers used for the invention, and the
amount used, depends in part on the properties of the cotton. The properties
of the cotton
depend on whether or not it has been dyed, pigmented by printing, whether or
not the cotton
has other adjuvants such as a cotton-poly composition as is known in the art,
and so forth.
The absolute quantity of the chemical is less important than the ratios of
ingredients in the composition. Certain compounds that provide crosslinking,
for example
diacrylates, triacrylates, and urethane acrylates, with multiple bonding
locations, is included
in only small quantities, generally less than I% of the polymerizable
composition,
preferably less than 0.4% of the polymerizable composition. Silicon-based
softeners, on the
other hand, provide at least 20%, preferably at least 30%, and in most cases
preferably at
least 40% of the polymerizable material.
DYED COTTON AND UN-DYED COTTON
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As used herein, "dyed cotton" is cotton that has been reacted with reactive
dyes. The dyed cotton therefore needs less protection to maintain anticrocking
and colorfast
properties. Further, the reactive dyes alter the fiber and a specially
tailored treatment
composition provides superior combination of very soft hand, good
crockfastness and color
fastness, and good stain and abrasion resistance.
One aspect of the invention is a method of treating cotton fibers comprising
the first step of providing a stable composition comprising between about 0.4%
and about
5% of a glyoxal prepolymer; between about 0.1% and about 3% of an elastomeric
latex
prepolymer; between about 6% and about 35% of an aqueous silicone oil
emulsion;
between about 0.2% and about 5% of a urethane prepolymer emulsion; between
about
0.002% and about 0.3% of a catalyst; and between about 0.002% and about 0.3%
of a graft
initiator. Advantageously, the above-described formulation further comprises
between
about 0.02% and about 2% of a high molecular weight silicone; between about
0.002% and
about 0.15% of a urethane acrylate prepolymer; between about 0.002% and about
0.15% of
a polyethylene glycol diacrylate; and between about 0.004% and about 2% of a
polyethylene
glycol.
The composition is stable with less than 5% of the prepolymers
self-polymerizing at a temperature of between about 60 F and 90 F during
storage over a
period of at least 2 months. The solids content of the stable composition upon
drying is at
least about 5% by weight.
This formulation in the second step is contacted to the cotton fibers to
pick-up between about 40 grams and about 120 grams of the stable composition
to about
100 grams of cotton fibers. The method of contacting and of controlling the
wet pick-up
can be any method known to the art. The cotton fibers are in the third step
dried by
exposure to a temperature sufficient for at least 20%, preferably at least
50%, more
preferably at least 80%, of the prepolymers and silicone oil to polymerize
into polymers
grafted onto the cotton fiber. It is recognized that some prepolymers may self-
polymerize
during the drying step, and these polymers beneficially may be loosely bound
to the fiber.
This is one form of the prior art - it is known to crosslink treatment
chemicals to
themselves. This treatment loses effectiveness as the treatment chemicals are
removed. A
substantial fraction of the treatment chemicals of the present invention are
grafted to the
fiber, however, and therefore is not prone to be removed by abrasion and
laundering.
One advantage of this process is that coating with treatment chemicals
followed by drying, typically at a temperature of 300 F to 400 F, is
routinely performed,
for example on a tenter frame during stretching.
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In one embodiment, the treatment compositions is a stable single-contact
formulation, wherein the activators and catalysts co-exist in the stable
formulation with the
prepolymers. The formulation can be stored and used at normal ambient
temperature
without congealing or polymerizing.
In a more preferred embodiment, the cotton fibers are coated with a stable
composition comprising: between about 0.8% and about 3.5% of a glyoxal
prepolymer;
between about 0.2% and about 2% of an elastomeric latex prepolymer; between
about 8%
and about 30% of an aqueous silicone oil emulsion; between about 0.8% and
about 4% of a
urethane prepolymer emulsion; between about 0.006% and about 0.2% of a
catalyst; and
between about 0.006% and about 0.2% of a graft initiator. The stable
composition
advantageously further comprises between about 0.1 % and about 1.5% of a high
molecular
weight silicone; between about 0.004% and about 0.08% of a urethane acrylate
prepolymer;
between about 0.004% and about 0.08% of a polyethylene glycol diacrylate; and
between
about 0.1 % and about 1 % of a polyethylene glycol.
The concentration and the wet pick-up are to some extent trade-offs, but
certain advantages are inherent in the more concentrated formulations,
including less
solvent to evaporate. In one embodiment the contacting picks-up between about
60 grams
and about 100 grams of the stable composition to about 100 grams of cotton
fibers.
The drying temperature is between about 110 F and 440 F, preferably
between about 250 F and 400 F, say about 340 F, and the drying time is
between about
10 seconds and 10 minutes, say about 1 minute. Without being bound by theory,
it is
believed that both the water loss from the drying and also the elevated
temperature
contribute to effective grafting and polymerizing.
One preferred treatment formulation comprises: between about 1% and about
3% of a glyoxal prepolymer; between about 0.4% and about 1.5% of an
elastomeric latex
prepolymer; between about 10% and about 30% of an aqueous silicone oil
emulsion;
between about 1% and about 3.5% of a urethane prepolymer emulsion; between
about 0.2
and about 1% of a high molecular weight silicone; between about 0.01% to about
0.05% of
a urethane acrylate prepolymer; between about 0.01% to about 0.05% of a
polyethylene
glycol diacrylate; between about 0.01% and about 0.05% of a catalyst; between
about
0.01% and about 0.05% of a graft initiator; and between about 0.16% to about
.8% of a
polyethylene glycol. Treatment of cotton, particularly of dyed cotton, with
this formulation
results in fabric that has good hand, a crock factor of about 4 to 4.5 on the
standard scale of
1 (bad) to 5 (excellent). Fabric so treated also has has excellent
colorfastness and low
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shrinkage, for example near about 3.55 to 4%, where untreated cotton may
exhibit
shrinkage of around 8%.
In one embodiment the stable treating composition is provided by admixing
a stable concentrated composition with water or other solvent. This
concentrate includes
between about 2% and about 10% of a glyoxal prepolymer; between about 0.5% and
about
6% of an elastomeric latex prepolymer; between about 30% and about 70% of an
aqueous
silicone oil emulsion; between about 1% and about 10% of a urethane prepolymer
emulsion; between about 0.01% to about 0.6% of a catalyst; and between about
0.01% to
about 0.6% of a graft initiator. A preferred formulation further includes:
between about
0.1% and about 4% of a high molecular weight silicone; between about 0.01% and
about
0.3% of a urethane acrylate prepolymer; between about 0.2% and about 4% of a
polyethylene glycol; and between about 0.01% and about 0.3% of a polyethylene
glycol
diacrylate. The concentrated composition is diluted, for example with water
added at a
weight ratio of from about 2 parts concentrate: 100 parts water to about 100
parts
concentrate: 100 parts water, preferably from about 4 parts concentrate: 100
parts water to
about 50 parts concentrate: 100 parts water, more preferably from about 10
parts
concentrate: 100 parts water to about 25 parts concentrate: 100 parts water.
In one preferred
embodiment, the treating composition is formed by adding one part concentrate
to between
2 and 4 parts water or other solvent. Again, the concentrated solution is
advantageously
stable over normal storage conditions, for example the concentrated
composition is a fluid
with less than 5% of the prepolymers self-polymerizing at a temperature of
between about
60 F and 90 F during storage over a period of at least 2 months. The stable
concentrated
composition typically comprises between about 10% and about 35% solids when
dried.
In one embodiment the stable concentrated composition comprises: between
about 4% and about 7%, for example about 5.6%, of a glyoxal prepolymer;
between about
1% and about 4%, for example about 2.8%, of an elastomeric latex prepolymer;
between
about 40% and about 60%, for example about 56.1%, of an aqueous silicone oil
emulsion;
between about 4% and about 8%, for example about 5.6%, of a urethane
prepolymer
emulsion; between about 0.03% and about 0.2%, for example about 0.06%, of a
catalyst;
and between about 0.03% and about 0.2%, for example about 0.06%, of a graft
initiator.
The formulation advantageously includes between about 0.5% and about 3%, for
example
about 1.63%, of a high molecular weight silicone; between about 0.02% and
about 0.15%,
for example about 5.6%, of a urethane acrylate prepolymer; between about 0.5%
to about
2%, for example about 1%, of a polyethylene glycol (preferably diethylene
glycol); and
between about 0.02% and about 0.15%, for example about 0.06%, of a
polyethylene glycol
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diacrylate. This stable concentrated composition comprises between about 20%
and about
32% solids when dried.
In yet one embodiment the stable concentrated composition comprises:
between about 4% and about 7% of a glyoxal prepolymer; between about 1% and
about 4%
of an elastomeric latex prepolymer; between about 40% and about 60% of an
aqueous
silicone oil emulsion; between about 4% and about 8% of a urethane prepolymer
emulsion;
between about 0.5% and about 3% of a high molecular weight silicone; between
about
0.02% and about 0.15% of a urethane acrylate prepolymer; between about 0.5% to
about
2% of a polyethylene glycol (preferably diethylene glycol); and between about
0.02% and
about 0.15% of a polyethylene glycol diacrylate. In this embodiment the
catalyst and graft
initiator are added separately, or, alternatively, ozone and/or irradiation
and/or another
method of initiating and propagating grafted polymers is used.
In another embodiment the stable concentrated composition comprises:
between about 5% and about 6% of a glyoxal prepolymer; between about 2% and
about 3%
of an elastomeric latex prepolymer; between about 52% and about 60% of an
aqueous
silicone oil emulsion; between about 5% and about 7% of a urethane prepolymer
emulsion;
between about 0.03% to about 0.1% of a catalyst; between about 0.03% to about
0.1% of a
graft initiator; between about 1 % and about 2% of a high molecular weight
silicone;
between about 0.04% to about 0.1 % of a urethane acrylate prepolymer; between
about
0.04% to about 0.1 % of a polyethylene glycol diacrylate; and between about
0.6% to about
1.6% of a polyethylene glycol. This stable concentrated composition comprises
between
about 25% and about 30% solids when dried.
The graft initiator may comprise salts of Fe, Ag, Co, Cu, or mixtures thereof.
These metal salts are advantageously used with a catalyst to rejuvenate the
graft initiator.
The catalyst comprises a strong oxidizer, for example a peroxide, peracid,
perbenzoate, or
mixtures thereof. The glyoxal prepolymer is a low-formaldehyde prepolymer such
that the
polymer forms less than 30 ppm formaldehyde in treated fiber.
If the cotton fiber comprises undyed cotton, the stable treatment
compositions described above advantageously further includes between about
0.4% and
about 8%, preferably between about 0.8% and about 6%, more preferably between
about
1.2% and about 4.5%, of a fluoroalkyl acrylate.
The concentrated stable compositions described above advantageously
further include between about 2% and about 16%, preferably between about 4%
and about
12%, more preferably between about 6% and about 9%, of a fluoroalkyl acrylate.
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The treatment compositions are added to the fibers, for example to the fabric,
by any method and the polymers are then caused to graft to the fibers and also
to crosslink,
typically but not exclusively by the application of heat, for example about
340 F for a
period of about 30 seconds to about 5 minutes. The application may be
effected, for
instance, by padding, saturating, spraying, or the like. For example,
cellulosic fabric may be
immersed in a bath of treating solution. The treatment compositions may be
emulsified
nonionic or ionic materials.
Thicker fabric may require longer heating at higher temperatures. Thicker
fabrics may preferably be oven cured at about 320 F to 375 F for about 1 to
15 minutes.
The invention includes both the treatment compositions and the method of
treatment.
The invention also includes the product of the process of treating cotton
fibers and/or fabrics with the above-described treatment compositions. Fabric
made of
treated cotton advantageously has a shrinkage of less than about 4.5%,
preferably less than
about 4%, a crockfastness of at least 4 on the below-described standard test,
and a good
hand.
DYED COTTON/POLYESTER AND UN-DYED COTTON/POLYESTER
While the compositions described in DYED COTTON AND UN-DYED
COTTON work well for cotton/polyester blends, different formulations provide
even
superior properties for cotton/polyester blends.
One embodiment of the invention relates to a method of treating
cotton/polyester fibers that includes providing a stable fluid composition
comprising,
between about 1.6% and about 18% of acrylic prepolymer, between about 0.1 %
and about
3% of an elastomeric latex prepolymer, between about 6% and about 35% of an
organopolysiloxane emulsion, between about 0.1% and about 3% of a urethane
prepolymer
emulsion, between about 0.002% and about 0.3% of a catalyst, and between about
0.002%
and about 0.3% of a graft initiator. Beneficially, the treatment fluid also
contains between
about 0.002% and about 0.2% of a polyethylene glycol diacrylate.. In another
embodiment
the composition also includes between about 0.002% and about 0.2% of a
surfactant
monomer. Again, it is important that the treatment composition be stable for
at least 2
months at ambient storage conditions. Again, stable means less than 5% of the
prepolymers
self-polymerize at a temperature of between about 60 F and 90 F during
storage over a
period of at least 2 months, and wherein the solids content of the stable
composition upon
drying is at least about 5% by weight.
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This treatment fluid is contacted with the cotton/polyester fibers to pick-up
between about 40 grams and about 120 grams, for example between about 60 grams
and
about 100 grams, of the stable composition to about 100 grams of
cotton/polyester fibers.
The quantity of fluid remaining after contacting the fluid, and any fluid
removal, is known
as the percent wet pickup.
Then, the polymerizable components of the treatment fluid are made to form
grafts onto the cotton/polyester fibers. In one embodiment this polymerization
is achieved
by drying the cotton fibers by exposure to a temperature sufficient for at
least half of the
prepolymers and organopolysiloxane to polymerize into polymers grafted onto
the cotton
fiber. The drying temperature in one embodiment is between about 250 F and
400 F and
the drying time is between about 10 seconds and 10 minutes.
The stable composition in another embodiment includes: between about
3.2% and about 15% of acrylic prepolymer; between about 0.2% and about 2% of
an
elastomeric latex prepolymer; between about 8% and about 30% of an
organopolysiloxane
emulsion; between about 0.2% and about 2% of a urethane prepolymer emulsion;
between
about 0.004% and about 0.1% of a catalyst; and between about 0.004% and about
0.1% of a
graft initiator. The stable composition beneficially further comprises between
about 0.004%
and about 0.1 % of a polyethylene glycol diacrylate; and between about 0.002%
and about
0.2% of a surfactant monomer.
In one preferred embodiment for treating cotton/polyester fibers, the stable
composition comprises: between about 4% and about 12% of acrylic prepolymer;
between
about 0.4% and about 1.5% of an elastomeric latex prepolymer; between about 9%
and
about 26% of an organopolysiloxane emulsion; between about 0.4% and about 1.5%
of a
urethane prepolymer emulsion; between about 0.006% and about 0.05% of a
catalyst;
between about 0.006% and about 0.05% of a graft initiator; between about
0.006% and
about 0.05% of a polyethylene glycol diacrylate; and between about 0.006% and
about
0.05% of a surfactant monomer.
The treatment composition is beneficially provided by a one-composition
fluid concentrate. Such a fluid concentrate may contain between about 8% and
about 35%
of acrylic prepolymer; between about 0.5% and about 6% of an elastomeric latex
prepolymer; between about 30% and about 70% of an organopolysiloxane emulsion;
between about 0.5% and about 6% of a urethane prepolymer emulsion; between
about
0.01% and about 0.4% of a catalyst; between about 0.01% and about 0.4% of a
graft
initiator. The treatment provides a superior product if it also contains
between about 0.01%
and about 0.4% of a polyethylene glycol diacrylate and between about 0.01% and
about
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0.4% of a surfactant monomer. Again, the concentrated composition is stable
with less than
5% of the prepolymers self-polymerizing at a temperature of between about 60
F and 90
F during storage over a period of at least 2 months, and wherein the stable
concentrated
composition comprises between about 10% and about 35% solids when dried.
The fluid concentrate is diluted using the same dilution factors as described
above, that is, water can be added at a weight ratio of from about 2 parts
concentrate: 100
parts water to about 100 parts concentrate: 100 parts water, preferably from
about 4 parts
concentrate: 100 parts water to about 50 parts concentrate: 100 parts water,
more preferably
from about 10 parts concentrate: 100 parts water to about 25 parts
concentrate: 100 parts
water. In one preferred embodiment, the treating composition is formed by
adding one part
concentrate to between 2 and 4 parts water or other solvent.
The stable concentrated composition in one embodiment includes: between
about 16% and about 30% of acrylic prepolymer; between about 1% and about 4%
of an
elastomeric latex prepolymer; between about 38% and about 60% of an
organopolysiloxane
emulsion; between about 1% and about 4% of a urethane prepolymer emulsion;
between
about 0.02% and about 0.2% of a catalyst; between about 0.02% and about 0.2%
of a graft
initiator. The concentrate may also contain between about 0.02% and about 0.2%
of a
polyethylene glycol diacrylate and between about 0.02% and about 0.2% of a
surfactant
monomer.
In another embodiment the stable concentrated composition includes
between about 20% and about 24% of acrylic prepolymer; between about 2% and
about 3%
of an elastomeric latex prepolymer; between about 46% and about 52% of an
organopolysiloxane emulsion; between about 2% and about 3% of a urethane
prepolymer
emulsion; between about 0.03% and about 0.1% of a catalyst; between about
0.03% and
about 0.1% of a polyethylene glycol diacrylate; between about 0.03% and about
0.1% of a
surfactant monomer; and between about 0.03% and about 0.1% of a graft
initiator.
This concentrate beneficially has between about 25% and about 32% solids,
preferably between about 25% and about 30% solids, when dried.
The surfactant monomer can be any surfactant monomer, also called an ionic
monomers. Such a monomer may contain sulfonate groups, such as sodium vinyl
sulfonate,
sodium p-styrenesulfonate, sodium methallyl sulfonate, sodium p-sulfophenyl
methallyl
ether, or sodium 2-methyl-2-acrylamidopropane sulfonate. Such groups are known
to
increase hydrophilicity. Carboxylate-containing comonomers such as itaconic
acid are also
surfactant monomers. The preferred surfactant monomer is surfactant monomer is
sodium
vinyl sulfonate.
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The graft initiator may be one or more salts of Fe, Ag, Co, Cu, or mixtures
thereof, as described before. Similarly, the catalyst may be a peroxide,
peracid,
perbenzoate, or mixtures thereof.
If the cotton/polyester fiber comprises undyed cotton/polyester fiber, the
stable composition beneficially further includes between about 0.4% and about
8% of a
fluoroalkyl acrylate, for example between about 0.8% and about 6% of a
fluoroalkyl
acrylate, preferably between about 1.2% and about 4.5% of a fluoroalkyl
acrylate.
The concentrated stable composition that provides a preferred treated undyed
cotton/polyester fiber further comprises between about 2% and about 16% of a
fluoroalkyl
acrylate, for example between about 4% and about 12% of a fluoroalkyl
acrylate, preferably
between about 6% and about 9% of a fluoroalkyl acrylate.
Again, the invention also relates to the treated product, as well as to
articles,
fabric, yarn, and staple that include treated fibers.
The invention also relates to both the stable treatment fluid and to the
stable
concentrated composition for treating cotton/polyester fibers.
PRINTED COTTON
A method of treating cotton fibers that have been previously printed with dye
includes providing a stable fluid composition comprising: between about 1% and
about
12% of acrylic prepolymer; between about 0.08% and about 2% of an elastomeric
latex
prepolymer; between about 3% and about 25% of an organopolysiloxane emulsion;
between
about 0.08% and about 2% of a urethane prepolymer emulsion; between about 1.4%
and
about 11.5% of a high density polyethylene prepolymer; between about 0.8% and
about 9%
of a polyamide prepolymer between about 0.0004% and about 0.15% of a catalyst;
and
between about 0.0004% and about 0.15% of a graft initiator. Beneficially,
between about
0.08% and about 2% of a non-ionic dispersant; between about 0.0004% and about
0.15% of
a polyethylene glycol diacrylate; and between about 0.0004% and about 0.15% of
a urethane
acrylate are also included. Again, the treatment composition is stable with
less than 5% of
the prepolymers self-polymerizing at a temperature of between about 60 F and
90 F
during storage over a period of at least 2 months. The solids content of the
stable
composition upon drying is at least about 5% by weight.
This treatment fluid is contacted with the printed cotton fibers to pick-up
between about 40 grams and about 120 grams of the stable composition to about
100 grams
of cotton fibers, beneficially between about 60 grams and about 100 grams of
the stable
composition to about 100 grams of printed cotton fibers.
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Finally, the method includes causing the grafted polymers to form. In one
embodiment this occurs as a result of drying the cotton fibers by exposure to
a temperature
sufficient for at least half of the prepolymers and silicone oil to polymerize
into polymers
grafted onto the printed cotton fiber. For example, the drying temperature may
be between
about 250 F and 400 F and the drying time is between about 10 seconds and 10
minutes.
In one embodiment the stable composition comprises: between about 1.6%
and about 10% of acrylic prepolymer; between about 0.2% and about 1.5% of an
elastomeric latex prepolymer; between about 5% and about 23% of an
organopolysiloxane
emulsion; between about 0.2% and about 1.5% of a urethane prepolymer emulsion;
between
about 2% and about 10% of a high density polyethylene prepolymer; between
about 1.4%
and about 7.5% of a polyamide prepolymer between about 0.002% and about 0.1%
of a
catalyst; and between about 0.002% and about 0.1 % of a graft initiator.
Again, the presence
of between about 0.2% and about 1.5% of a non-ionic dispersant; between about
0.002%
and about 0.1% of a polyethylene glycol diacrylate; and between about 0.002%
and about
0.1 % of a urethane acrylate provides a preferred product. The fluid should,
of course, be
stable.
In one embodiment the stable composition for treating printed cotton
includes between about 2.4% and about 8% of acrylic prepolymer; between about
0.3% and
about 1% of an elastomeric latex prepolymer; between about 6% and about 20% of
an
organopolysiloxane emulsion; between about 0.3% and about 1% of a urethane
prepolymer
emulsion; between about 2.6% and about 8.5% of a high density polyethylene
prepolymer;
between about 2% and about 6% of a polyamide prepolymer; between about 0.006%
and
about 0.05% of a catalyst; between about 0.006% and about 0.05% of a graft
initiator;
between about 0.3% and about 1% of a non-ionic dispersant; between about
0.006% and
about 0.05% of a polyethylene glycol diacrylate; and between about 0.006% and
about
0.05% of a urethane acrylate.
In yet another embodiment, the stable composition is provided by admixing a
stable concentrated composition comprising between about 5% and about 24% of
acrylic
prepolymer; between about 0.4% and about 4% of an elastomeric latex
prepolymer;
between about 15% and about 50% of an organopolysiloxane emulsion; between
about
0.4% and about 4% of a urethane prepolymer emulsion; between about 7% and
about 23%
of a high density polyethylene prepolymer; between about 4% and about 18% of a
polyamide prepolymer between about 0.002% and about 0.3% of a catalyst; and
between
about 0.002% and about 0.3% of a graft initiator with water or other solvent.
The
concentrated composition may further comprise between about 0.4% and about 4%
of a
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non-ionic dispersant; between about 0.002% and about 0.3% of a polyethylene
glycol
diacrylate; and between about 0.002% and about 0.3% of a urethane acrylate.
The dilution
of the stable concentrate is the same as was previously described for other
stable
concentrates.
The concentrated composition is stable with less than 5% of the prepolymers
self-polymerizing at a temperature of between about 60 F and 90 F during
storage over a
period of at least 2 months.
The stable concentrated composition comprises between about 10% and
about 35% solids, preferably between about 25% and about 32% solids, when
dried. The
concentrate is advantageously diluted with water prior to use.
The concentrate can be diluted with water added at a weight ratio of from
about 2 parts concentrate: 100 parts water to about 100 parts concentrate: 100
parts water,
preferably from about 4 parts concentrate: 100 parts water to about 50 parts
concentrate: 100
parts water, more preferably from about 10 parts concentrate: 100 parts water
to about 25
parts concentrate: 100 parts water.
In one embodiment the stable concentrated composition comprises: between
about 8% and about 20% of acrylic prepolymer; between about 1% and about 3% of
an
elastomeric latex prepolymer; between about 25% and about 46% of an
organopolysiloxane
emulsion; between about 1% and about 3% of a urethane prepolymer emulsion;
between
about 10% and about 20% of a high density polyethylene prepolymer; between
about 7%
and about 15% of a polyamide prepolymer; between about 0.01% and about 0.2% of
a
catalyst; and between about 0.01% and about 0.2% of a graft initiator. The
concentrate is
further improved by including between about 1% and about 3% of a non-ionic
dispersant;
between about 0.01 % and about 0.2% of a polyethylene glycol diacrylate; and
between
about 0.01% and about 0.2% of a urethane acrylate.
In yet another preferred embodiment, the stable concentrated composition
comprises: between about 12% and about 16% of acrylic prepolymer; between
about 1.5%
and about 2% of an elastomeric latex prepolymer; between about 30% and about
40% of an
organopolysiloxane emulsion; between about 1.5% and about 2% of a urethane
prepolymer
emulsion; between about 13% and about 17% of a high density polyethylene
prepolymer;
between about 10% and about 12% of a polyamide prepolymer; between about 0.03%
and
about 0.1% of a catalyst; between about 0.03% and about 0.1% of a graft
initiator; between
about 1.5% and about 2% of a non-ionic dispersant; between about 0.03% and
about 0.1%
of a polyethylene glycol diacrylate; and between about 0.03% and about 0.1% of
a urethane
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acrylate. This stable concentrated composition comprises between about 25% and
about
30% solids when dried.
Again, the graft initiator advantageously comprises a salt or salts of Fe, Ag,
Co, Cu,
or mixtures thereof. The initiator may include a magnesium salt. The catalyst
comprises a
strong oxidizer, for example a peroxide, peracid, perbenzoate, or mixtures
thereof. Urea
peroxide is most preferred.
Again, the invention also relates to the treated product, as well as to
articles,
fabric, yarn, and staple that include treated fibers.
The invention also relates to both the stable treatment fluid and to the
stable
concentrated composition for treating cotton/polyester fibers.
PRINTED COTTON/POLYESTER
A treatment composition especially suited for cotton/polyester fibers that
have been previously printed with dye is described herein. The printed
cotton/polyester
fibers are contacted with a stable fluid composition comprising: between about
1% and
about 20% of acrylic prepolymer; between about 0.08% and about 2% of an
elastomeric
latex prepolymer; between about 6% and about 35% of an organopolysiloxane
emulsion;
between about 0.08% and about 2% of a polyamide prepolymer; between about 0.2%
and
about 4% of an adhesive gum, for example a carboxylated butadiene
acrylonitrile
prepolymer; between about 0.001% and about 0.15% of a catalyst; between about
0.001%
and about 0.15% of a graft initiator; and advantageously between about 0.001%
and about
0.15% of a polyethylene glycol diacrylate and between about 0.001% and about
0.15% of a
surfactant monomer. The composition is stable with less than 5% of the
prepolymers
self-polymerizing at a temperature of between about 60 F and 90 F during
storage over a
period of at least 2 months. The solids content of the stable composition upon
drying is at
least about 5% by weight.
The contacting can be by any method, and preferably the printed
cotton/polyester fibers pick-up between about 40 grams and about 120 grams of
the stable
composition to about 100 grams of cotton fibers, preferably between about 60
grams and
about 100 grams of the stable composition to about 100 grams of printed
cotton/polyester
fibers.
Finally, the polymerizable material in the treatment composition is
polymerized onto the printed cotton/polyester fibers to form grafted polymers.
This
forming a grafted polymers may be initiated by drying the printed
cotton/polyester fibers at
a temperature sufficient for at least half of the prepolymers and
organospolysiloxane to
polymerize into polymers grafted onto the printed cotton fiber. The drying
temperature can
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be between about 250 F and 400 F and the drying time can be between about 10
seconds
and 10 minutes.
In one embodiment the stable composition includes: between about 2% and
about 15% of acrylic prepolymer; between about 0.2% and about 1.5% of an
elastomeric
latex prepolymer; between about 8% and about 30% of an organopolysiloxane
emulsion;
between about 0.2% and about 1.5% of a polyamide prepolymer; between about
0.4% and
about 3% of a carboxylated butadiene acrylonitrile prepolymer; between about
0.002% and
about 0.05% of a catalyst; between about 0.002% and about 0.05% of a graft
initiator; and
advantageously between about 0.002% and about 0.05% of a polyethylene glycol
diacrylate
and between about 0.002% and about 0.05% of a surfactant monomer.
The stable composition in one embodiment includes between about 3.6%
and about 12% of acrylic prepolymer; between about 0.3% and about 1.25% of an
elastomeric latex prepolymer; between about 9% and about 27% of an
organopolysiloxane
emulsion; between about 0.3% and about 1.25% of a polyamide prepolymer;
between about
0.6% and about 2.5% of a carboxylated butadiene acrylonitrile prepolymer;
between about
0.004% and about 0.03% of a catalyst; between about 0.004% and about 0.03% of
a graft
initiator between about 0.004% and about 0.03% of a polyethylene glycol
diacrylate; and
between about 0.004% and about 0.03% of a surfactant monomer.
In yet another embodiment the stable composition is provided by admixing
between a stable concentrated composition comprising:'between about 5% and
about 40%
of acrylic prepolymer; between about 0.4% and about 4% of an elastomeric latex
prepolymer; between about 30% and about 70% of an organopolysiloxane emulsion;
between about 0.4% and about 4% of a polyamide prepolymer; between about 1%
and
about 8% of a carboxylated butadiene acrylonitrile prepolymer; between about
0.005% and
about 0.3% of a catalyst; and between about 0.005% and about 0.3% of a graft
initiator with
a solvent, for example water. Advantageously, the concentrate also includes
between about
0.005% and about 0.3% of a polyethylene glycol diacrylate and between about
0.005% and
about 0.3% of a surfactant monomer.
The concentrated composition is stable with less than 5% of the prepolymers
self-polymerizing at a temperature of between about 60 F and 90 F during
storage over a
period of at least 2 months.
The stable concentrated composition comprises between about 10% and
about 35% solids when dried, preferably between about 25% and about 32%
solids, more
preferably between about 25% and about 30% solids, when dried.
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In one embodiment the stable concentrated composition includes between
about 10% and about 30% of acrylic prepolymer; between about 1% and about 3%
of an
elastomeric latex prepolymer; between about 40% and about 60% of an
organopolysiloxane
emulsion; between about 1% and about 3% of a polyamide prepolymer; between
about 2%
and about 6% of a carboxylated butadiene acrylonitrile prepolymer; between
about 0.01%
and about 0.1 % of a catalyst; and between about 0.01 % and about 0.1 % of a
graft initiator.
The stable concentrated composition advantageously also includes between about
0.01%
and about 0.1 % of a polyethylene glycol diacrylate and between about 0.01 %
and about
0.1 % of a surfactant monomer.
In a preferred embodiment the stable concentrated composition includes
between about 18% and about 24% of acrylic prepolymer; between about 1.5% and
about
2.5% of an elastomeric latex prepolymer; between about 46% and about 54% of an
organopolysiloxane emulsion; between about 1.5% and about 2.5% of a polyamide
prepolymer; between about 3% and about 5% of a carboxylated butadiene
acrylonitrile
prepolymer; between about 0.02% and about 0.06% of a catalyst; between about
0.02% and
about 0.06% of a graft initiator; between about 0.02% and about 0.06% of a
polyethylene
glycol diacrylate; and between about 0.02% and about 0.06% of a surfactant
monomer.
The method treating the printed cotton/polyester fibers can be performed
when the fibers are in the form of textile.
In one embodiment the graft initiator comprises a salt or salts of Fe, Ag, Co,
Cu, or mixtures thereof. In another embodiment the initiator comprises a salt
of Fe, Mg, or
a mixture thereof. The catalyst comprises a peroxide, peracid, perbenzoate, or
mixtures
thereof.
Again, the invention also relates to the treated product, as well as to
articles,
fabric, yarn, and staple that include treated fibers.
The invention also relates to both the stable treatment fluid and to the
stable
concentrated composition for treating printed cotton/polyester fibers.
COTTON STRETCH COMPONENT
It is sometimes necessary to use cotton fibers in a stretch composition. It
has
been surprisingly found that cotton fiber with a heavy loading of a particular
prepolymer
graft combination exhibits not only excellent stain resistance, good hand, and
excellent
crockfastness, but also exhibits excellent recoverability after stretching. A
commercial
mixture used for this purpose is a mechanical blend of cotton (about 95%) and
SPANDEX
(TM) or LYCRA (TM). While the previously described formulations work well for
treating
cotton fibers intended for this use, a special stable fluid formulation useful
for imparting
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stretchability and recoverability to cotton fibers includes between about 0.8%
and about
15% of acrylic prepolymer; between about 0.4% and about 9% of a high molecular
weight
silicone; between about 6% and about 35% of a silicone oil emulsion; between
about 1.5%
and about 12% of a urethane; between about 0.0004% and about 0.15% of a
catalyst; and
between about 0.0004% and about 0.15% of a graft initiator. Advantageously,
the treatment
composition also includes between about 0.0004% and about 0.15% of a
polyethylene
glycol diacrylate and between about 0.0004% and about 0.15% of a urethane
acrylate
prepolymer.
Unlike other composition treatments, which advantageously have a loading
after grafting and polymerizing of between about 2 and about 6%, the loading
of the cotton
is advantageously between about 3% and about 10%, for example between about 5%
and
about 7%. Such a loading will allow fabric that has been stretched to about
150% of its
original length, held for thirty seconds, and, after allowing the fabric to
relax thirty more
seconds, the fabric will recover to about 95% to about 115%, preferably
between about 97%
to about 108%, of its original size. This can be repeated, with substantially
the same results,
at least 5 and preferably at least 10 times on a treated fabric.
Advantageously the composition is stable with less than 5% of the
prepolymers self-polymerizing at a temperature of between about 60 F and 90
F during
storage over a period of at least 2 months.
The stretchable cotton fibers are contacted with this treatment composition
to pick-up between about 40 grams and about 200 grams of the stable
composition to about
100 grams of cotton fibers, beneficially between about 60 grams and about 140
grams.
Beneficially, the fiber is dry before contacting the treatment composition to
enhance fluid
migration into the fiber structure.
The prepolymers within the treatment fluid are then made to graft and to
polymerize
onto the stretchable cotton fibers, for example by exposure to a temperature
sufficient for at
least half of the prepolymers and silicone oil to polymerize into polymers
grafted onto the
stretchable cotton fibers. A drying temperature of between about 250 F and
400 F for a
drying time of between about 10 seconds and 10 minutes is sufficient for most
fabrics.
In one embodiment the stable composition includes between about 2% and
about 10% of acrylic prepolymer; between about 0.8% and about 7% of a high
molecular
weight silicone; between about 8% and about 30% of a silicone oil emulsion;
between about
1.2% and about 8% of a urethane; between about 0.002% and about 0.1% of a
catalyst;
between about 0.002% and about 0.1 % of a graft initiator; and advantageously
between
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about 0.002% and about 0.1% of a polyethylene glycol diacrylate and between
about
0.002% and about 0.1 % of a urethane acrylate prepolymer.
The stable composition in one preferred embodiment includes between about
2.4% and about 8% of acrylic prepolymer; between about 1.2% and about 5% of a
high
molecular weight silicone; between about 10% and about 27% of a silicone oil
emulsion;
between about 1.6% and about 6% of a urethane; between about 0.006% and about
0.05%
of a catalyst; between about 0.006% and about 0.05% of a graft initiator;
between about
0.006% and about 0.05% of a polyethylene glycol diacrylate; and between about
0.006%
and about 0.05% of a urethane acrylate prepolymer.
The stable composition may be provided by admixing a stable concentrated
fluid composition including between about 4% and about 30% of acrylic
prepolymer;
between about 2% and about 18% of a high molecular weight silicone; between
about 30%
and about 70% of a silicone oil emulsion; between about 3% and about 24% of a
urethane;
between about 0.002% and about 0.3% of a catalyst; between about 0.002% and
about 0.3%
of a graft initiator, and advantageously between about 0.002% and about 0.3%
of a
polyethylene glycol diacrylate and between about 0.002% and about 0.3% of a
urethane
acrylate prepolymer.
Again, this concentrated composition is stable with less than 5% of the
prepolymers self-polymerizing at a temperature of between about 60 F and 90
F during
storage over a period of at least 2 months.
The stable concentrated composition comprises between about 10% and
about 35% solids when dried, preferably between about 25% and about 32% solids
when
dried.
In one embodiment the stable concentrated composition includes between
about 10% and about 20% of acrylic prepolymer; between about 4% and about 14%
of a
high molecular weight silicone; between about 40% and about 60% of a silicone
oil
emulsion; between about 6% and about 16% of a urethane; between about 0.01%
and about
0.2% of a catalyst; between about 0.01% and about 0.2% of a graft initiator;
and
advantageously between about 0.01 % and about 0.2% of a polyethylene glycol
diacrylate;
and between about 0.0 1% and about 0.2% of a urethane acrylate prepolymer.
In one preferred embodiment the stable concentrated composition includes
between about 12% and about 16% of acrylic prepolymer; between about 6% and
about
10% of a high molecular weight silicone; between about 50% and about 55% of a
silicone
oil emulsion; between about 8% and about 12% of a urethane; between about
0.03% and
about 0.1% of a catalyst; between about 0.03% and about 0.1% of a graft
initiator; between
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about 0.03% and about 0.1% of a polyethylene glycol diacrylate; and between
about 0.03%
and about 0.1% of a urethane acrylate prepolymer. This stable concentrated
composition
contains between about 25% and about 30% solids when dried.
The stretchable cotton fibers are beneficially in the form of textile.
The graft initiator in one embodiment comprises a salt or salts of Fe, Ag, Co,
Cu, or mixtures thereof. In another embodiment the initiator comprises a salt
or salts of Fe,
Mg, or a mixture thereof.
The catalyst in one embodiment is a peroxide, peracid, perbenzoate,
periodate, or mixtures thereof.
The printing of non-reactive pigments onto cotton and cotton/polyester is
known. One adhesive includes a carboxylated butadiene acrylonitrile, though
many other
adhesive gums are know. We have surprisingly found that by incorporating a
small amount
of crosslinkers, in particular between about 0.01% and 0.3%, preferably
between about
0.02% and about 0.1 %, more preferably between about 0.03 and 0.06, of at
least one
crosslinking prepolymer, crockfastness and colorfastness is improved. A
preferred
composition has both a urethane acrylate and a polyethylene glycol diacrylate
present at the
above concentration ranges in carboxylated butadiene acrylonitrile. It may be
necessary to
incorporate a small amount of water, for example about 0.1 to about 1%, to
stabilize this
polymer composition.
Compatible adjuvants can be added to the compositions herein for their
known purposes. Such adjuvants include, but are not limited to, viscosity
control agents,
perfumes, emulsifiers, preservatives, UV light absorbers, antioxidants,
bactericides,
fungicides, colorants, dyes, fluorescent dyes, brighteners, opacifiers, soil
release agents, and
shrinkage control agents. An example of a useful class of antimicrobial agents
that will
impart antimicrobial activity to the fiber includes polymerizable protonated
amines. An
example of a useful class of flame retardant includes polymerizable vinylidene
chloride. In
addition, an antioxidant, antiozonant or other stabilizer can be added to the
fabric to
increase its resistance to aging, high temperature induced degradation or
discoloration. It is
beneficial to bind the adjuvants to the treated fiber to prolong the useful
life of the
adjuvants. The adjuvants can in certain conditions be copolymerized with the
treatment
composition, or may be exchanged onto receptive monomers incorporated into the
treatment. These adjuvants, if used, are added at their usual levels,
excepting the flame
retardant generally each of up to about 5% by weight of the preferred liquid
composition.
In one embodiment, the adjuvant includes a polymerizable hydrophobic
monomer or prepolymer in a quantity sufficient to substantially increase the
hydrophobicity
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of the treated fiber. In some instances an adjuvant can have more than one
function, for
example a di-alkyl fatty acid amine can impart both antimicrobial properties
as well as
change the hydrophobic character of the fiber. In another embodiment,
hydrophillic
monomers or prepolymers are incorporated in a quantity sufficient to
substantially increase
the hydrophillic character of the treated fiber. Examples include the
aforementioned
surfactant monomers, i.e., sodium p-styrenesulfonate, sodium methallyl
sulfonate, sodium
p-sulfophenyl methallyl ether, sodium 2-methyl-2-acrylamidopropane sulfonate,
as well as
carboxylate-containing monomers such as itaconic acid. It may be beneficial to
treat certain
areas or sides of the fiber or fabric with certain adjuvants and to treat
other areas or sides
with other adjuvants. For example, a bandage advantageously includes
antimicrobial
properties as well as hydrophobic and hydrophillic areas or sides of an area.
The formulations described for each of the cotton and cotton/polyester fibers
above are beneficial because they can be applied with no new equipment or
processing
steps. The method of the present invention contemplates contacting fibers and
yams and
fabrics with a grafting solution at any stage of yam or fabric production.
Thus, the grafting
solution may be applied to staple or filament fibers, yams or formed fabric.
The treatment
composition may be grafted onto filaments during a spin finishing operation
and thereafter
formed into the fabric. In addition, yams may be formed from the grafted
filaments, and
thereafter, the yams are formed into the fabric. Alternatively, the yams may
be formed from
non-grafted filaments, the treatment composition is then grafted onto the
yams, and
thereafter, the yams are formed into the fabric.
It is also possible to beam the yarns and then graft the treatment composition
onto the beamed yam during a slashing operation, or to beam the grafted yams
prior to
forming the fabric. Furthermore, it is possible to repackage the grafted yams
and then
utilize the repackaged yams as wrap or fill yams during formation of the
fabric.
The treatment composition may also be grafted onto staple and the grafted
staple is then spun into yam. The grafted filaments may be cut into staple and
the staple
then spun into yams. The filaments or yams or fabrics may be contacted with a
solution of
the first component by a dipping, spraying, or coating operation.
It is still further contemplated that the fibers or yarns may be contacted
with
graft solution either before or after chemical or mechanical production
operations such as
spin finishing, application of lubricants, or sizing. Furthermore, the graft
solution may be
applied to the yams or fibers after formation of a fabric therefrom. The
fabric may be
contacted with grafting solution either before, during, or after chemical and
mechanical
finishing operations such as the application of fabric softeners or
calendaring operations.
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The presence of the treatment polymers on fabrics can be inferred by certain
tests as described here. Use the 18 inch by 18 inch fabric sample normally
used for
shrinkage testing as the sample for testing. Sample should be marked for
shrinkage in
normal manner, as additional shrinkage data can be obtained during testing for
polymer.
Place in a corner of the 18 inch by 18 inch sample, about one-half teaspoon
each of
Heinz(TM) Tomato Ketchup, Hersey's(TM) Chocolate Syrup, and Welch's (TM) Grape
Juice. Force the contaminants into the fabric, and wipe off excess using a
clean paper
towel. Then launder the fabric using a detergent such as Tide Ultra Clean (TM)
in warm
(105 F) water on a regular cycle. After washing, dry the sample. The three
stains should
be completely (or nearly completely) removed. Rate the stains on a "1-5" scale
with "5"
indicating no color, "4" indicating pale color, "3" indicating some color, "2"
indicating lots
of color and "1" indicating large color. The treated fabric will have a rating
of greater than
3.5, and preferably greater than 4. Untreated cotton has staining values of 1-
2.
The shrinkage of the treated fibers in fabric form will be less than 4.5%,
preferably less than 4%, most preferably less than 3.5%. Untreated fabric has
shrinkage of
7.5 to 9%.
The weight of the loading on the fiber or fabric depends on the desired final
use and cost factors. Applicants have surprisingly found that the properties
of good hand,
colorfastness, resistance to staining, shrinking, and abrasion, increase with
the load of
treatment chemicals grafted thereon. Economic concerns limit the amount to
generally
below about 10% by weight. Excellent fabric characteristics are observed with
a loading of
between about 2% to about 7%, preferably between about 3% and about 5%. The
amount
of loading of treatment should be at least half of the initial treatment after
about 15
washings.
The formulations are prepared by adding a precalculated quantity of a desired
prepolymer in a container and to it add monomers, prepolymers, catalyst, graft
initiator and
other ingredients of the composition. Each ingredient was taken in a
concentration ratio by
weight as indicated in the compositions described herein. The contents were
stirred to a
uniform solution.
Fabrics were manufactured and treated with formulations described below.
The fabric was then tested. Softness ("hand") is the an independent tester's
reasonable
judgment when compared to a 100% cotton fabric. Crocking was tested using the
AATCC
Test Method B with a crock meter, both wet and dry. Grading was based on a "1-
5" scale
with "5" indicating no color transfer, "4" indicating pale color transfer, "3"
indicating some
color transfer, "2" indicating lots of color transfer and "1" indicating large
color transfer.
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Color fastness was tested using the AATCC Test Method 61 11 A. Shrinkage was
tested
using the AATCC Test Method 135-1992-IVA 111. Abrasion resistance was tested
using
the Test Method ASTMD1376 (30 minutes).
Example 1
A formulation was prepared that had the composition shown in Table 1.
This formulation was found to, when diluted at ranges from about 2 parts water
to 1 part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
pickup of about 60% and dried at a temperature of about 340 F, provide a
fabric with good
hand, less than 4% shrinkage, a crockfastness of at least 4, no pilling during
abrasive
resistance testing, and a stain resistance of at least 3.5. The composition
was also found to
be a stable fluid with no visible precipitation after storage at room
temperature for a period
of 3 months or more.
TABLE 1, Formulation for Dyed Cotton Fabric
Parts By Weight
Glyoxal resin prepolymer, Ecco Res GB 404 (TM) 5.6
Urethane prepolymer, Resamin UMT171 (TM) 5.6
High mol. wt. Silicone softener, Helastic WO-8026(TM) 1.63
Silicone softener, Sequasoft 69 (TM) 56.13
Elastomeric Latex, Hystretch V-43 (TM) 2.80
Deionized water 27.0
Diethylene glycol 1.0
Urethane acrylate, SR-9035 (TM) 0.06
Polyethylene glycol diacrylate, SR 344 (TM) 0.06
Urea peroxide (0.1% in DIW) 0.06
Ferrous ammonium sulfate solution (0.1N) 0.06
In another composition, the diethylene glycol was replaced with additional
water
with little degradation of finished fabric properties.
In another composition, the glyoxal resin prepolymer Ecco Res GB 404 (TM) was
replaced with glyoxal resin prepolymer Resin KLF (TM) and the formaldehyde in
the fabric
was reduced below 30 ppm.
Example 2
A formulation was prepared that had the composition shown in Table 2. This
formulation was found to, when diluted at ranges from about 2 parts water to 1
part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
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pickup of about 60% and dried at a temperature of about 340 F, provide a
fabric with good
hand, less than 4% shrinkage, a crockfastness of at least 4, no pilling during
abrasive
resistance testing, and a stain resistance of at least 3.5.
TABLE 2, Formulation For Dyed Cotton/Polyester Fabric
Parts By Weight
Acrylic prepolymer, Helastic 8001 (TM) 4.86
Urethane prepolymer, Resamine UMT 171 (TM) 2.43
Acrylic prepolymer, EccoRez 907 (TM) 2.43
Softener polysiloxane, APS V-soft (TM) 48.7
Acrylic prepolymer, Helastic WD 8061 (TM) 14.61
Elastomer Latex, Histretch V-43 (TM) 2.43
Deionized water 24.3
Polyethylene glycol diacrylate, SR344 (TM) 0.05
Sodium vinyl sulfonate 0.05
Urea peroxide O.1N solution 0.05
Ferrous ammonium sulfate 0.1N solution 0.05
Example 3
A formulation was prepared that had the composition shown in Table 3.
\
TABLE 3, Formulation For Printed Cotton Fabric
Parts By Weight %
Polyamide prepolymer dispersion, Micromid 632MPL (TM) 10.89
Urethane prepolymer emulsion, Resamine UMT 171 (TM) 1.80
Acrylic prepolymer, Helastic WD 8061 (TM) 14.52
Elastomer Latex, Histretch V-43 (TM) 1.80
H. D. Polyethylene prepolymer, Mykon HD (TM) 14.52
Modified organopolysiloxane, APS V-soft (TM) 36.31
Non-ionic dispersant, Crockfast 2 (TM) 1.80
Deionized water 18.2
Urethane acrylate, SR-9035 (TM) 0.04
Polyethylene glycol diacrylate, SR-344 (TM) 0.04
Urea peroxide 0.1N solution 0.04
Ferrous ammonium sulfate 0.1N solution 0.04
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This formulation was found to, when diluted at ranges from about 2 parts
water to 1 part formulation to about 4 parts water to 1 part formulation, and
applied to a
fabric at a wet pickup of about 60% and dried at a temperature of about 340
F, provide a
fabric with good hand, less than 4% shrinkage, a crockfastness of at least 4,
no pilling
during abrasive resistance testing, and a stain resistance of at least 3.5.
Example 4
A formulation was prepared that had the composition shown in Table 4. This
formulation was found to, when diluted at ranges from about 2 parts water to 1
part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
pickup of about 60% and dried at a temperature of about 340 F, provide a
fabric with good
hand, less than 4% shrinkage, a crockfastness of at least 4, no pilling during
abrasive
resistance testing, and a stain resistance of at least 3.5.
TABLE 4, Formulation For Printed Cotton Polyester Fabric
Parts By Weight %
Acrylic prepolymer, Helastic 8001 (TM) 11.75
Acrylic prepolymer, Helastic WD 8061 (TM) 7.83
Acrylic prepolymer, Helastic 8041 (TM) 1.96
Elastomer Latex, Histretch V-43 (TM) 1.96
Deionized water 19.6
Polyamide prepolymer dispersion, Micromid 632MPL (TM) 1.96
Modified organopolysiloxane, APS V-soft (TM) 50.9
Carboxylated Butadiene acrylonitrile, Tylac 68805 (TM) 3.91
Polyethylene glycol diacrylate, SR-344 (TM) 0.04
Sodium Vinyl Sulfonate 0.04
Urea peroxide 0.1N solution 0.04
Ferrous ammonium sulfate 0.1N solution 0.04
Example 5
A formulation was prepared that had the composition shown in Table 5. This
formulation was found to, when diluted at ranges from about 2 parts water to 1
part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
pickup of about 60% and dried at a temperature of about 340 F, provide a
fabric with good
hand, less than 4% shrinkage, no pilling during abrasive resistance testing,
and a stain
resistance of at least 3.5.
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TABLE 5, Formulation For Cotton Fabric
Parts By Weight %
Glyoxal resin prepolymer, Ecco Res GB 404 (TM) 5.6
Urethane prepolymer, Resamin UMT171 (TM) 5.6
High mol. wt. Silicone softener, Helastic WO-8026(TM) 1.63
Silicone softener, Sequasoft 69 (TM) 56.13
Elastomeric Latex, Hystretch V-43 (TM) 2.80
Fluoroalkyl acrylate copolymer dispersion, Texfluor UPL (TM) 8.0
Deionized water (DIW) 19
Urethane acrylate, SR-9035 (TM) 0.06
Polyethylene glycol diacrylate, SR 344 (TM) 0.06
Urea peroxide (0.1 % in DIW) 0.06
Ferrous ammonium sulfate solution (0.1N) 0.06
Diethylene glycol 1.0
In another composition, the diethylene glycol was replaced with additional
water
with little degradation of finished fabric properties.
In another composition, the glyoxal resin prepolymer Ecco Res GB 404 (TM) was
replaced with glyoxal resin prepolymer Resin KLF (TM) and the formaldehyde in
the fabric
was reduced below 30 ppm.
Example 6
A formulation was prepared that had the composition shown in Table 6. This
formulation was found to, when diluted at ranges from about 2 parts water to 1
part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
pickup of about 60% and dried at a temperature of about 340 F, provide a
fabric with good
hand, less than 4% shrinkage, no pilling during abrasive resistance testing,
and a stain
resistance of at least 3.5.
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TABLE 6, Formulation For Cotton/Polyester Fabric
Parts By Weight
Acrylic prepolymer, Helastic 8001 (TM) 4.86
Urethane prepolymer, Resamine UMT 171 (TM) 2.43
Acrylic prepolymer, EccoRez 907 (TM) 2.43
Softener polysiloxane, APS V-soft (TM) 48.7
Acrylic prepolymer, Helastic WD 8061 (TM) 14.61
Elastomer Latex, Histretch V-43 (TM) 2.43
Fluoroalkyl acrylate copolymer dispersion, Texfluor UPL (TM) 8.0
Deionized water 16.3
Polyethylene glycol diacrylate, SR344 (TM) 0.05
Sodium vinyl sulfonate 0.05
Urea peroxide 0.1N solution 0.05
Ferrous ammonium sulfate 0.1N solution 0.05
Example 7
A formulation was prepared that had the composition shown in Table 7. This
formulation was found to, when diluted at ranges from about 2 parts water to 1
part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
pickup of about 80% and dried at a temperature of about 340 F, provide a
fabric with
excellent stretch and recovery characteristics, as well as good hand, less
than 4% shrinkage,
no pilling during abrasive resistance testing, and a stain resistance of at
least 3.5.
TABLE 7, Formulation For Cotton Fabric
.25 Parts By Weight
Acrylic prepolymer, Helastic 8001 (TM) 13.53
Urethane prepolymer, Resamine UMT 171 (TM) 10.25
High mol. wt. Silicone softener, Helastic WO-8026(TM) 8.12
Silicone softener, Sequasoft 69 (TM) 53.6
Deionized water 14.21
Polyethylene glycol diacrylate, SR344 (TM) 0.06
Urethane acrylate, SR-9035 (TM) 0.06
Urea peroxide 0.1N solution 0.06
Ferrous ammonium sulfate 0.1N solution 0.06
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Example 8
Both treated and untreated fabrics were printed with a dye composition and a
gum,
wherein the gum comprised 99.5% carboxylated butadiene acrylonitrile, 0.04%
urethane
acrylate, and 0.04% polyethylene glycol diacrylate, and a small quantity of
water as a
solvent. The fabrics treated with this composition and dried at a temperature
sufficient to
promote crosslinking, that is, 340 F, were found to have crocking properties
at least about
0.5, and as much as 2, units better on a scale of 1 to 5 that similar fabrics
dyed with just
polyethylene glycol diacrylate and dried at 340 F.
Example 9
A formulation was prepared that had the composition shown in Table 8. This
formulation was found to, when diluted at ranges from about 2 parts water to 1
part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
pickup of about 80% and dried at a temperature of about 340 F, provide a
fabric with fair
stretch and recovery characteristics, as well as good hand, less than 5%
shrinkage, no pilling
during abrasive resistance testing, good wet crockfastness and acceptable dry
crockfastness,
and a stain resistance of at least 3.5.
Table 8
Parts By Weight %
Acrylic prepolymer, Helastic 8001 (TM) 12.9
Deionized water 25.1
Elastomer Latex, Histretch V-43 (TM) 1.29
KF(TM) 28/30% in water 44.08
High mol. wt. Silicone softener, Helastic WO-8026(TM) 3.87
Acrylic prepolymer, Helastic WD 8041 (TM) 2.15
KF 874 (10% in IPA) 1.29
Aurasoft 280 8.6
Sodium vinyl sulfonate 0.04
Urea peroxide (0.1 %) 0.04
Ferrous ammonium sulfate (0.1 %) 0.04
This formulation was tested on cotton navy blotch, and results are in Table 9.
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Table 9
Standard Actual 100% sol. 100% sol. 50% sol. 50% sol.
Specs Finished Jersey Jersey Jersey Jersey
Specs blotch blotch blotch blotch
Print paste Print paste
Burst* 60 92 112 110 105 105
Oz. Wt. 6.5 6.3 7.75 7.6 7.25 7.3
Shrinkage 7x7 5.0x6.0 4.0x5.0 5.0x0 4.0x4.0 4.2x0.6
Stretch - 40 40 42 50 45 45
Recovery 80 97 95 95 95 90
Crock W/D 2.0/3.0 2.0/3.0 5.0/3.5 5.0/3.5 5.0/4.0 4.5/3.5
Pilling 3 2.0 5.0 5.0 5.0 5.0
* Mellens' Burst Test
The Mellen's burst test measures the force needed to press a ball, about 1
inch in diameter, through the fabric, which is a measure of the tensile
strength of the fabric.
As used herein, the tensile strength of the fabric is defined as the force
required to push a
ball through a fabric following the Mellen test procedures. The strength ratio
is the ratio of
the force needed to push the ball through the fabric divided by the force
needed to push the
same ball through similar but untreated fabric. This value is related to sew-
ability and
wear-ability. Typically, resins applied to cotton lower the tensile strength
of a cotton fabric.
Applicants have surprisingly found, as shown above, that treatment of the
fibers of a fabric
increases the strength ratio to 150% (100% being the same strength as
untreated fabric) with
a large loading of polymer. Smaller loadings increase the strength ratio to
115%, and a
preferred loading increases the strength ratio to at least 125%.
Example 10
A formulation was prepared that had the composition shown in Table 10. This
formulation was found to, when diluted at ranges from about 2 parts water to 1
part
formulation to about 4 parts water to 1 part formulation, and applied to a
fabric at a wet
pickup of about 80% and dried at a temperature of about 340 F, provide a
fabric with
excellent stretch and recovery characteristics, as well as good hand, less
than 5.4%
shrinkage, no pilling during abrasive resistance testing, and excellent
crockfastness. The
test data on cotton with a navy blotch is shown in Table 11.
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Table 10
Parts By Weight %
Urethane prepolymer, Resamine UMT 171 (TM) 15.42
Polyamide prepolymer dispersion, Micromid 632MPL (TM) 2.57
Silicone softener, Sequasoft 69 (TM) 43.18
High mol. wt. Silicone softener, Helastic WO-8026(TM) 5.14
Aurasoft 280 (TM) 7.71
Deionized water 25.7
Aurawet 634 (TM) 0.22
Urethane acrylate, SR-9035 (TM) 0.005
Sodium vinyl sulfonate 0.005
Sodium Metabisulfite (0.1 N solution) 0.05
Table 11
Standard Actual 100% sol. 100% sol. 50% sol. 50% sol.
Specs Finished Jersey Jersey Jersey Jersey
Specs blotch blotch blotch blotch
Print paste Print paste
Burst* 60 60 90 92 88 90
Oz. Wt. 6.0 5.9 7.4 7.1 6.5 6.4
Shrinkage 8x8 6.0x6.0 5.4x 1.0 5.Oxl.5 5.Oxl.5 5.2x2.0
Stretch 40 40 35 40 30 38
Recovery 80 90 95 95 95 95
Crock W/D 2.0/3.0 2.0/3.0 4.5/4.0 4.5/3.5 4.5/4.0 4.5/4.0
Pilling 3 3 5.0 5.0 5.0 5.0
* Mellens' Burst Test
Examples 11-13
Three formulations were prepared that had the compositions shown in Table 12,
and
test data are presented on Table 13. This example shows how sensitive the test
results are
to minor formulation changes.
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Table 12
Example 11 12 13
Ingredients, weight percent % % %
Ecco Res GB 404 5.0 6.5 5.6
Urethane prepolymer, Resamine UMT 171 (TM) 4.8 6.8 5.6
High mol. wt. Silicone softener, Helastic WO-8026(TM) 1.4 2.5 1.69
Sequasoft V-43 (TM) 55.0 60.0 56.13
Elastomer Latex, Histretch V-43 (TM) 2.33 3.5 2.80
Water 30.6 20.46 28.0
Urethane acrylate, SR 9035 (TM) 0.04 0.07 0.06
Polyethylene glycol diacrylate SR 344 (TM) 0.05 0.07 0.06
Urea peroxide (0.1%) 0.05 0.055 0.06
Ferrous ammonium 0.04 0.045 0.06
sulfate (0.01)
Table 13
Example 11 12 13
Burst 83 112 92
Oz. wt. 5.64 7.5 6.9
Shrinkage % 7x5 6x5 3.8x3.1
Stretch % 40 30 55
Recovery % 97 98 95
Crock Wet/Dry 5/5 2/4 4/4.5
Pilling 3.5 4 5
Hand Medium soft Soft Very Soft
While it is apparent that the invention herein disclosed is well calculated to
fulfill the objects above stated, it will be appreciated that numerous
modifications and
embodiments may be devised by those skilled in the art, and it is intended
that the appended
claims cover all such modifications and embodiments as fall within the true
spirit and scope
of the present invention.
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