U.S. patent application number 16/760920 was filed with the patent office on 2021-06-10 for methods for use of aqueous polyurethane dispersions and articles made thereby.
This patent application is currently assigned to The LYCRA Company LLC. The applicant listed for this patent is A&AT LLC. Invention is credited to DOUGLAS K. FARMER, TING HE.
Application Number | 20210172114 16/760920 |
Document ID | / |
Family ID | 1000005435905 |
Filed Date | 2021-06-10 |
United States Patent
Application |
20210172114 |
Kind Code |
A1 |
FARMER; DOUGLAS K. ; et
al. |
June 10, 2021 |
METHODS FOR USE OF AQUEOUS POLYURETHANE DISPERSIONS AND ARTICLES
MADE THEREBY
Abstract
Methods for improving localized shaping and/or support
functionalities, shape retention, comfort and/or stay of apparel
and other fabric articles by applying an aqueous polyurethane
dispersion at a selected intensity and/or at one or more selected
locations of the apparel or other fabric article are provided.
Apparel and other fabric articles with improved localized shaping
and/or support functionalities, shape retention comfort and/or stay
prepared in accordance with these methods are also provided.
Inventors: |
FARMER; DOUGLAS K.;
(GREENSBORO, NC) ; HE; TING; (NEWARK, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
A&AT LLC |
Wilmington, |
DE |
US |
|
|
Assignee: |
The LYCRA Company LLC
Wilmington
DE
|
Family ID: |
1000005435905 |
Appl. No.: |
16/760920 |
Filed: |
October 30, 2018 |
PCT Filed: |
October 30, 2018 |
PCT NO: |
PCT/US2018/058109 |
371 Date: |
May 1, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62581240 |
Nov 3, 2017 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D06N 3/0077 20130101;
D06M 15/564 20130101; D06M 2200/50 20130101; D06M 23/16 20130101;
D06M 2200/20 20130101 |
International
Class: |
D06M 23/16 20060101
D06M023/16; D06M 15/564 20060101 D06M015/564; D06N 3/00 20060101
D06N003/00 |
Claims
1. A method for improving localized shaping and/or support
functionalities, shape retention, comfort and/or stay of apparel
and other fabric articles, said method comprising: applying an
aqueous polyurethane dispersion at a selected intensity and/or at
one or more selected locations of the apparel or other fabric
article; and curing aqueous polyurethane dispersion to the apparel
or other fabric article following application of the aqueous
polyurethane dispersion at the selected intensity and/or at one or
more selected locations so that shaping and/or support, shape
retention, comfort and/or stay of apparel and other fabric article
is improved.
2. The method of claim 1 wherein the aqueous polyurethane
dispersion comprises: a prepolymer comprising a glycol, an
isocyanate and a diol compound; and water, a neutralizer, a
surfactant, a defoamer, an antioxidant or a thickener.
3. The method of claim 2 wherein the prepolymer further comprising
1-hexonal.
4. The method of claim 2 wherein the isocyanate is
dicyclohexylmethane diisocyanate.
5. The method of claim 2 wherein the prepolymer contains at least
70% glycol, at least 20% isocyanate and at least 2% diol.
6. The method of claim 3 wherein the prepolymer contains less than
1% 1-hexanol.
7. The method of claim 2 wherein the aqueous polyurethane
dispersion comprises: the prepolymer; and water, a neutralizer, a
surfactant, a defoamer, an antioxidant and a thickener water.
8. The method of claim 2 wherein the aqueous polyurethane
dispersion contains at least 30% glycol, at 10% isocyanate and at
least 1% diol.
9. The method of claim 8 wherein the aqueous polyurethane
dispersion further contains at least 50% water, at least 1%
surfactant and/or thickener and/or less than 1% neutralizer,
antioxidant or defoamer.
10. A fabric article exhibiting improved localized shaping and/or
support functionalities, shape retention, comfort and/or stay
produced in accordance with the methods of claim 1.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to methods for use of aqueous
polyurethane dispersions in improving localized shaping and/or
support functionalities, shape retention, stay and/or comfort of
apparel and other fabric articles.
BACKGROUND OF THE INVENTION
[0002] A shaping garment is designed to temporarily alter the
wearer's body shape to achieve a more fashionable figure. In recent
years, fashion trends have tended to embrace clothing and apparel
designs that increasingly accentuate natural curves of the human
body, and the shape wear has been a growing trend in the market.
The primary application has been in women's apparel, such as inner
wear, lingerie, jeans and woven pants. Many women consumers look
for a comfortable garment that enhances her shape while
highlighting her best features, for example, a shaping jean that
can slim the tummy, tighten the thigh and lift the buttock. Such a
garment improves the appearance and self-esteem of the wearer.
[0003] Current techniques for shaping primarily use different yarn
loop structures with long float stitch, higher denier or high draft
of elastic fiber; or to apply a special silhouette pattern in
strategically selected areas. Other common practice includes
introducing second layers of fabric or pad sewn with base fabric,
or selecting the fabrics with different elasticity and sewing
together in different positions. See for example, U.S. Pat. Nos.
7,950,069, 7,341,500, and 7,945,970, WO2013/154445 A1, U.S. Patent
Application Publication Nos. 2010/0064409A1 and 2011/0214216A1,
GB2477754A and EP 0519135B1. In one design, a rigid panel is added
inside of the jean in front of the belly to help slenderize the
stomach. In another, a piece of padding or sponge is inserted into
trousers to lift and enhance a visual buttock profile of the
wearer. However, all these designs and methods compromise the
wearers' comfort and often are visible from the garment
surface.
[0004] Polyurethanes (including polyurethaneureas) can be used as
adhesives for various substrates, including textile fabrics.
Typically, such polyurethanes are either fully formed non-reactive
polymers or reactive isocyanate-terminated prepolymers. Such
reactive polyurethane adhesives often require extended curing time
to develop adequate bonding strength, which can be a disadvantage
in manufacturing processes. In addition, the isocyanate groups of
the polyurethanes are known to be sensitive to moisture, which
limits the storage stability and reduces the shelf life of the
product incorporating such polyurethanes. Typically, such polymers,
when fully formed, are either dissolved in a solvent (solvent
borne), dispersed in water (water borne), or processed as
thermoplastic solid materials (hot melt). Notably, solvent-based
adhesives face ever-tightening health and environmental legislation
aimed at reducing volatile organic compound (VOC) and hazardous air
pollutant (HAP) emissions. Accordingly, alternatives to
conventional solvent-based products are needed.
[0005] Hot-melt adhesives, although environmentally safe and easily
applied as films, generally have high set and poor recovery when
subject to repeated stretch cycles. Therefore, improvements are
needed.
[0006] Many attempts have been made to develop water borne
polyurethane adhesives to overcome these deficiencies.
[0007] U.S. Pat. No. 5,270,433 discloses an "adhesive composition
comprising a substantially clear and solvent-free, aqueous,
one-component polyurethane dispersion containing the reaction
products of (a) a polyol mixture comprising polypropylene glycol,
(b) a mixture of polyfunctional isocyanates comprising
.alpha..alpha..alpha..sub.1.alpha..sub.1-tetramethyl xylene
diisocyanate (TMXDI), (c) a functional component capable of salt
formation in aqueous solution, and (d) optionally, a
chain-extending agent." The adhesive films from this composition
have low recovery power and poor heat resistance in view of the
unsymmetrical structure and steric hindrance of isocyanate groups
on TMXDI, preventing the formation of strong inter-chain urea
hydrogen bonds in the hard segments of the polymer.
[0008] U.S. Patent Application Publication No. 2004/0014880 A1
discloses an aqueous polyurethane dispersion for adhesive bonding
in wet and dry laminations stated to have superior coatability,
adhesive strength and heat resistance. This dispersion contains a
substantial amount of organic solvent-methyl ethyl ketone
(MEK).
[0009] U.S. Patent Application Publication No. 2003/0220463 A1
discloses a method for making a polyurethane dispersion that is
free of organic solvent such as N-methylpyrrolidone (NMP). However,
the composition is limited to a prepolymer having low free
diisocyanate species, such as methylene bis(4-phenylisocyanate)
(4,4'-MDI). The process to produce such a prepolymer with low free
diisocyanate is complicated (as disclosed in U.S. Pat. No.
5,703,193). Such processing also requires short path distillation
of the free diisocyanate and is thus not economical in producing a
prepolymer for making a polyurethane dispersion.
[0010] U.S. Pat. No. 4,387,181 discloses a stable aqueous
polyurethane dispersion, containing N-methylpyrrolidone (NMP)
solvent, prepared by reaction of carboxylic group-containing
oxime-blocked, isocyanate-terminated prepolymer and polyamine. The
prepolymer is made by reaction of aromatic diisocyanates, such as
4,4'-diphenylmethanediisocyanate (MDI) or toluene diisocyanate
(TDI), with polyether or polyester polyols and a dihydroxy alkanoic
acid. The oxime-blocked isocyanate groups are capable of reacting
with polyamine at 60 to 80.degree. C., within 6 to 18 hours. The
dispersion is stable in storage, and the film formed from the
dispersion has good tensile properties. However, this dispersion
still has organic solvent present and the longer curing time needed
is unsuitable for fabric bonding and lamination in practice.
[0011] U.S. Pat. No. 5,563,208 describes an acetone process to
prepare an essentially solvent-free aqueous polyurethane
dispersion, comprising urethane prepolymers with blocked isocyanate
groups and polyamines within the molecular weight range of 60 to
400 in a molar ratio of blocked isocyanate groups to primary and/or
secondary amino groups of from 1:0.9 to 1:1.5. This dispersion is
stable in storage at room temperatures and gives a heat-resistant
binder in coating. It requires long curing time (up to 30 minutes),
which is still not suitable for fabric bonding and adhesion.
Furthermore, the acetone process requires an additional
distillation step to remove the acetone from the dispersion, which
makes this process less economical.
[0012] U.S. Pat. No. 6,586,523 describes an acetone process for
preparing a self-crosslinking polyurethane dispersion for sizing
agents, comprising a prepolymer with isocyanate groups partially
blocked and partially extended, and excess polyfunctional compounds
having molecular weights from 32 to 500 with primary or secondary
amino and/or hydroxyl groups. This dispersion composition reduces
the curing time to some degree, but still has deficiencies because
an additional distillation step to remove the acetone is
required.
[0013] U.S. Pat. No. 6,555,613 describes a solvent-free aqueous
dispersion of a reactive polyurethane having a number average
molecular weight (Mn) of from 800 to 14,000, a degree of branching
of from 0.0 to 3.0 mol/kg, and an isocyanate functionality from 2.0
to 6.0 per mole. The polyurethane is made from a polyester polyol,
a polyisocyanate and polyisocyanate adduct, with low molecular
weight polyol and anion-forming units after neutralizing
incorporated in the polymer chains, and with blocked isocyanate
groups capable of further reactions for crosslinking. The result of
such dispersion is a coating material that is hard, glossy and
elastic, but such coating material does not have the elastomeric
features and stretch/recovery properties required for an adhesive
to be used with stretch fabrics.
[0014] Polymer compositions such as polyurethaneurea films and
tapes comprising fully formed polyurethaneurea with blocked
isocyanate end groups are disclosed in U.S. Pat. No. 7,240,371.
These compositions are prepared from solvent-free systems of
prepolymers comprising at least one polyether or polyester polyoyl,
a mixture of MDI isomers and a diol.
[0015] U.S. Pat. No. 9,346,932 discloses aqueous polyurethane
dispersions provided in solvent-free systems of a prepolymer
comprising at least one polyether, polyester, or polycarbonate
polyol, a mixture of MDI isomers, and a diol and shaped three
dimensional articles formed therefrom.
[0016] Carmen, C. et al. disclose a method to add polymer
composition on the edge of garments to form the garment edge bands
and to add film on garments such as brassiere to form laminate
fabrics in patent EP 2280619B1 and published U.S. Patent
Application Publication No. 2009/0181599A1 discloses fabric
laminates or fabric bands having multiple layered structures,
including at least one fabric layer and at least one polymer layer
that have been attached or bonded together.
[0017] Other examples of polymer compositions are polyurethane
tapes such as those commercially available from Bemis, and
polyolefin resins that can be formed into films such as those
commercially available from ExxonMobil under the trade name
VISTAMAXX. These films may be bonded to fabric with application of
heat.
SUMMARY OF THE INVENTION
[0018] The inventors herein have found that application of an
aqueous polyurethane dispersion comprising a prepolymer comprising
a glycol, an isocyanate and a diol compound, and optionally
1-hexonal and further comprising water, a neutralizer, a
surfactant, a defoamer, an antioxidant and/or a thickener can be
applied at a selected intensity and/or at a selected location or
selected locations of a fabric article to improving localized
shaping and/or support functionalities, shape retention, stay
and/or comfort of the fabric article.
[0019] Accordingly, an aspect of the present invention relates to a
method for improving localized shaping and/or support
functionalities of apparel and other fabric articles. The method
comprises applying the aqueous polyurethane dispersion at a
selected intensity and/or one or more selected locations of apparel
or other fabric articles. The method further comprises curing of
the aqueous polyurethane dispersion to the apparel or other fabric
articles following application of the aqueous polyurethane
dispersion at the selected intensity and/or selected one or more
locations so that shaping and/or support is improved.
[0020] Another aspect of the present invention relates to a method
for improving stay of apparel and other fabric articles. The method
comprises applying the aqueous polyurethane dispersion at a
selected intensity and/or at one or more selected locations of
apparel or other fabric articles wherein stay of the apparel or
other fabric articles is desired. The method further comprises
curing of the apparel or other fabric articles following
application of the aqueous polyurethane dispersion at the selected
intensity and/or one or more locations so that stay of the apparel
or other fabric articles is improved.
[0021] Another aspect of the present invention relates to a method
for improving comfort of apparel and other fabric articles. The
method comprises applying the aqueous polyurethane dispersion at a
selected intensity and/or at one or more selected locations of
apparel or other fabric articles wherein improved comfort of the
apparel or other fabric articles is desired. The method further
comprises curing of the apparel or other fabric articles following
application of the aqueous polyurethane dispersion at the selected
intensity and/or one or more locations so that comfort of the
apparel or other fabric articles is improved.
[0022] Another aspect of the present invention relates to a method
for improving shape retention of apparel and other fabric articles.
The method comprises applying the aqueous polyurethane dispersion
at a selected intensity and/or at one or more selected locations of
apparel or other fabric articles wherein improved shape retention
of the apparel or other fabric articles is desired. The method
further comprises curing of the apparel or other fabric articles
following application of the aqueous polyurethane dispersion at the
selected intensity and/or one or more locations so that shape
retention of the apparel or other fabric articles is improved.
[0023] Yet another aspect of the present invention relates to
apparel and other fabric articles with an aqueous polyurethane
dispersion applied and cured at a selected intensity and/or one or
more selected locations which exhibit improved localized shaping
and/or support functionalities, shape retention, stay and/or
comfort.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Provided by this disclosure are methods for improving
localized shaping and/or support functionalities, shape retention,
stay and/or comfort of apparel and other fabric articles via
application of an aqueous polyurethane dispersion at selected
intensities and/or at one or more selected locations on the apparel
or other fabric article.
[0025] By "improved", "improving", or "improvement", as used
herein, it is meant any enhancement detectable visually, physically
or by quantification of localized shaping and/or support
functionalities, shape retention, stay and/or comfort of apparel
and other fabric articles with the applied aqueous polyurethane
dispersion as compared to apparel and other fabric articles without
the aqueous polyurethane dispersion.
[0026] By "intensity" as used herein, it meant that to include both
application weight and design of the application pattern of the
aqueous polymeric dispersion.
[0027] Aqueous polyurethane dispersions falling within the
disclosure are provided from particular urethane prepolymers, which
also are disclosed herein. The aqueous polyurethane dispersions and
prepolymers do not contain an organic solvent or cosolvent, alkyl
ethoxylates or organotin catalyst.
[0028] As used herein, the term "dispersion" refers to a system in
which the disperse phase consists of finely divided particles, and
the continuous phase can be a liquid, solid or gas.
[0029] As used herein, the term "aqueous polyurethane dispersion"
refers to a composition containing at least a polyurethane or
polyurethane urea polymer or prepolymer (such as the polyurethane
prepolymer described herein) that has been dispersed in an aqueous
medium, such as water, including de-ionized water.
[0030] A dried aqueous polyurethane dispersion, as used herein, is
an aqueous polyurethane dispersion that has been subjected to
curing or drying by any suitable method. The dried aqueous
polyurethane dispersion may be in the form of a shaped article,
e.g., a film.
[0031] As used herein, the term "solvent," unless otherwise
indicated, refers to a non-aqueous medium, wherein the non-aqueous
medium includes organic solvents, including volatile organic
solvents (such as acetone) and somewhat less volatile organic
solvents (such as MEK, or NMP).
[0032] As used herein, the term "essentially solvent-free" or
"essentially solvent-free system" refers to a composition or
dispersion wherein the bulk of the composition or dispersed
components has not been dissolved or dispersed in a solvent.
[0033] Prepolymers for use in the aqueous polyurethane dispersions
used in the present invention comprise a glycol, an aliphatic
diisocyanate and a diol.
[0034] Glycol components suitable as a starting material for
preparing prepolymers used in the present invention include
polycarbonates, and polyesters, polycarbonate glycols, polyether
glycols, and polyester glycols.
[0035] Examples of polyether glycols that can be used include, but
are not limited to, those glycols with two or more hydroxy groups,
from ring-opening polymerization and/or copolymerization of
ethylene oxide, propylene oxide, trimethylene oxide,
tetrahydrofuran, and 3-methyltetrahydrofuran, or from condensation
polymerization of a polyhydric alcohol, preferably a diol or diol
mixtures, with less than 12 carbon atoms in each molecule, such as
ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol
1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol,
1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol
and 1,12-dodecanediol. A linear, bifunctional polyether polyol is
preferred, and a poly(tetramethylene ether) glycol of molecular
weight of about 1,700 to about 2,100, such as Terathane.RTM. 1800
(Invista) with a functionality of 2, is particularly preferred for
use in the prepolymers used in the present invention.
[0036] Examples of polyester glycols that can be used include those
ester glycols with two or more hydroxy groups, produced by
condensation polymerization of aliphatic polycarboxylic acids and
polyols, or their mixtures, of low molecular weights with no more
than 12 carbon atoms in each molecule. Examples of suitable
polycarboxylic acids are malonic acid, succinic acid, glutaric
acid, adipic acid, pimelic acid, suberic acid, azelaic acid,
sebacic acid, undecanedicarboxylic acid and dodecanedicarboxylic
acid. Example of suitable polyols for preparing the polyester
polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol,
1,5-pentanediol 1,6-hexanediol, neopentyl glycol,
3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol,
1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear,
bifunctional polyester polyol with a melting temperature of about
5.degree. C. to about 50.degree. C. is preferred.
[0037] Examples of polycarbonate glycols that can be used include
those carbonate glycols with two or more hydroxy groups, produced
by condensation polymerization of phosgene, chloroformic acid
ester, dialkyl carbonate or diallyl carbonate and aliphatic
polyols, or their mixtures, of low molecular weights with no more
than 12 carbon atoms in each molecule. Examples of suitable polyols
for preparing the polycarbonate polyols are diethylene glycol,
1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and
1,12-dodecanediol. A linear, bifunctional polycarbonate polyol with
a melting temperature of about 5.degree. C. to about 50.degree. C.
is preferred.
[0038] In one nonlimiting embodiment, the prepolymer contains at
least 65%, or at least 71%, or at least 72% of the glycol, based
upon total weight of the prepolymer.
[0039] The isocyanate component suitable as another starting
materials for making prepolymers useful in the present invention is
a dicyclohexylmethane diisocyanate such as Vestanate.RTM. H12MD1
(Evonik).
[0040] In one nonlimiting embodiment, the prepolymer contains at
least 10%, or at least 22%, or at least 24% of the isocyanate,
based upon total weight of the prepolymer.
[0041] Diols suitable as further starting materials for preparing
prepolymers disclosed herein, include at least one diol with two
hydroxy groups capable of reacting with the isocyanate and at least
one carboxylic acid group capable of forming salt upon
neutralization and incapable of reacting with the isocyanate.
Examples of diols having a carboxylic acid group include, but are
not limited to, 2,2-dimethylopropionic acid (DMPA) such as Bis-MPA
(GEO), 2,2-dimethylobutanoic acid, 2,2-dimethylovaleric acid, and
DMPA initiated caprolactones such as CAPA.TM. HC 1060 (Solvay).
DMPA is preferred.
[0042] In one nonlimiting embodiment, the prepolymer may contain at
least 1%, or at least 2.2%, or at least 2.4% of the diol, based
upon total weight of the prepolymer.
[0043] In one nonlimiting embodiment, the prepolymer further
comprises a monofunctional alcohol including methanols, ethanols,
propanols, butanols and 1-hexanol. In this nonlimiting embodiment,
the prepolymer contains less than 1% or less than 0.5% of the
1-hexaonol, based upon total weight of the prepolymer.
[0044] The prepolymer can be prepared by mixing the glycol,
isocyanate and diol together in one step and by reacting at
temperatures of about 50.degree. C. to about 100.degree. C. for
adequate time until all hydroxy groups are essentially consumed and
a desired % NCO of the isocyanate group is achieved. Alternatively,
this prepolymer can be made by charging molten glycol into a
reactor at about 55.degree. C. followed by addition of a DMPA solid
powder with agitation and circulation until the diol solid
particles are dispersed and dissolved in the glycol. Molten
isocyanate is then charged into the reactor with continuous
agitation and the capping reaction is allowed to take place at
about 90.degree. C. for about 240 minutes, still with continuous
agitation. The formed viscous prepolymer is then sampled to
determine the extent of the reaction by measuring the weight
percentage of the isocyanate groups (% NCO) of the prepolymer
through a titration method. The theoretical value of the % NCO
after the reaction is completed is 2.97 assuming the glycol MW is
at 1800. If the determined % NCO value is higher than the
theoretical value, the reaction should be allowed to continue until
the theoretical value is reached or the % NCO number becomes
constant. Once it is determined that the reaction is complete, the
prepolymer temperature is maintained between 85.degree. C. and
90.degree. C. Significantly, the prepolymers are essentially
solvent free and contain no alkyl ethoxylates or organotin
catalysts. Preferred is that the reaction to prepare the prepolymer
be carried out in a moisture-free, nitrogen-blanketed atmosphere to
avoid side reactions.
[0045] The prepolymer of the present invention is then used to
produce an aqueous polyurethane dispersion comprising the
prepolymer and water as well as a neutralizer, a surfactant, a
defoamer, an antioxidant and/or a thickener.
[0046] In one nonlimiting embodiment, the prepolymer is added in an
amount such that the final aqueous polyurethane dispersion contains
at least 30% glycol, at least 10% isocyanate, and at least about 1%
dial, based upon total weight of the aqueous polyurethane
dispersion.
[0047] In one nonlimiting embodiment, the aqueous polyurethane
dispersion further contains at least 50% water, at least 1%
surfactant and/or thickener and/or less than 1% neutralizer,
antioxidant, or defoamer.
[0048] Neutralizers used in these dispersions must be capable of
converting the acid groups to salt groups. Examples include, but
are not limited to, tertiary amines (such as triethylamine,
N,N-diethylmethylamine, N-methylmorpholine,
N,N-diisopropylethylamine, and triethanolamine) and alkali metal
hydroxides (such as lithium, sodium and potassium hydroxides).
Primary and/or secondary amines may be also used as the
neutralizers for the acid groups. The degrees of neutralization are
generally between about 60% to about 140%, for example, in the
range of about 80% to about 120% of the acid groups.
[0049] Examples of surfactants include, but are not limited to,
anionic, cationic, or nonionic dispersants or surfactants, such as
alkyldiphenyloxide disulfonate, sodium dodecyl sulfate, sodium
dodecylbenzenesulfonate, ethoxylated nonyphenols, and lauryl
pyridinium bromide.
[0050] Examples of suitable defoamers include, but are not limited
to, mineral oils and/or silicone oils such as BYK 012 and Additive
65 (a silicone additive from Dow Corning), and Surfynol.TM. DF 110L
(a high molecular weight acetylenic glycol non-ionic surfactant
from Air Products & Chemicals).
[0051] Examples of suitable thickeners include, but are not limited
to, polyurethanes such as Tafigel PUR 61 by Munzing,
hydrophobically-modified ethoxylate urethanes (HEUR),
hydrophobically-modified alkali swellable emulsions (RASE), and
hydrophobically-modified hydroxy-ethyl cellulose (HMHEC).
[0052] Examples of antioxidants include, but are not limited to,
hindered phenols such as Irganox 245 (BASF) or Cyanox 1790 (Cytec).
Additionally, diamines including ethylene diamine and similar
materials can be used as a diamine chain extender in place of
water.
[0053] In one nonlimiting embodiment, the dispersion is prepared by
the addition of the prepolymer using a rotor/stator high speed
disperser. The prepolymer as made above is transferred directly
into the disperser head and dispersed under high shear forces into
deionized water preferably containing at least a surfactant, a
neutralizer, an anti-oxidant and/or a foam control agent. Slightly
more prepolymer than required by the dispersion recipe is needed to
compensate for loss in the transfer line and in the reactor. Once
the addition of the prepolymer is complete, a thickener can be
added.
[0054] Aqueous polyurethane dispersions for use in the present
invention should be expected to have a solids content of from about
10% to about 50% by weight, for example from about 30% to about 45%
by weight. The viscosity of aqueous polyurethane dispersions for
use in the present invention may be varied in a broad range from
about 10 centipoises to about 100,000 centipoises depending on the
processing and application requirements. For example, in one
nonlimiting embodiment, the viscosity is in the range of about 500
centipoises to about 30,000 centipoises. The viscosity may be
varied by using an appropriate amount of thickening agent, such as
from about 0 to about 5.0 wt %, based on the total weight of the
aqueous polyurethane dispersion.
[0055] The aqueous polyurethane dispersion can be applied to
selected locations of apparel or other fabric articles and/or at
selected intensities by methods such as, but not limited to,
padding, coating, printing, bonding, laminating, spraying and other
application/treatment methods, and then cured (or dried) with a
residence time of about 1 to about 5 minutes.
[0056] The aqueous polyurethane dispersion may be diluted to a
desired solid content prior to application to the apparel or other
fabric article.
[0057] These aqueous polyurethane dispersions when applied at
selective intensities and/or selected locations of apparel and
other fabric articles have now been found to be useful improving
localized shaping and/or support functionalities, shape retention,
stay and/or comfort of the apparel and other fabric articles.
[0058] Examples of apparel that can be improved using the
dispersions and methods in accordance with the present invention,
include but are not limited to: disposable undergarments,
brassieres, panties, lingerie, swimwear, shapers, camisoles,
hosiery, leggings, sleepwear, aprons, wetsuits, ties, scrubs, space
suits, uniforms, hats, garters, sweatbands, belts, activewear,
outerwear, rainwear, cold-weather jackets, pants, shillings,
dresses, blouses, men's and women's tops, sweaters, corsets, vests,
knickers, socks, knee highs, dresses, blouses, tuxedos, bisht,
abaya, hijab, jilbab, thoub, Burka, cape, costumes, diving suit,
kilt, kimono, jerseys, gowns, protective clothing, sari, sarong,
skirts, spats, stola, suits, straitjacket, toga, tights, towel,
uniform, veils, wetsuit, medical compression garments, bandages,
suit interlinings, waistbands, and all components therein.
[0059] Examples of other fabric articles that can be improved using
the dispersions and methods in accordance with the present
invention include, but are not limited to, seating and seats,
cushions, pads, footwear, footwear inserts, bedding, packaging
protecting materials and automobile interiors.
[0060] In one nonlimiting embodiment, the inventors herein have now
found that selective location of an aqueous polymeric dispersion
on, for example, a garment improves fit and shaping in unexpected
ways. More specifically, it has been found that applying the
aqueous polymeric dispersion in one location on a garment can
influence, trigger and/or guide the fit and shaping in other
locations of the garment. Further such garments are more
comfortable. Use of the aqueous polymeric dispersion in this manner
provides for symmetric correction of dissimilar breast size/shape
by selective application of the dispersion to locations of a bra or
other supportive undergarment. In particular, printing of the
dispersion on lower cup of a bra resulting in less visually
discernible and less measurable, as determined by a 3-dimensional
body scanner, difference between the two breasts/cups is a model
with dissimilar size/shape of breasts. Further, for a bralette for
a keyhole top or sheath dress such as available from Tommy
Hilfiger, printing of the dispersion on the bra cup resulted in
smoothing the keyhole and elimination of flipping of the keyhole on
the back, a common issue with this design. In addition, printing of
the dispersion on a bra at the bottom and side of the breast area
provides push-in and push-up shaping on the breast. Printing of the
dispersion on the tummy section of a legging resulted in the back
waist adhering better. Accordingly, this use of the aqueous
polymeric dispersions provides an invisible treatment which retains
the elegant and simplistic design of the garment while avoiding the
appearance of functional elements, provides designers and garment
makers a means to create new and differentiated garments with
improved functionality and enables viable mass customization of
garments.
[0061] In another nonlimiting embodiment, the inventors herein have
now found that location selective application of the aqueous
polymeric dispersion, coupled with selected application weight and
design of the application pattern, creates localized shaping and
support functionality for garments. Further, such garments have
improved comfort. Various selected patterns for application of the
dispersion include, but are not limited to, dots, shapes such as
triangles, circles, and rectangles, zigzags and/or lines depending
upon what shaping and support functionality is desired. Such
application of the aqueous polymeric dispersion as a dispersion
provides for flexibility in designing graduated elastic modulus in
garments and enables seamless garment technology with improved
functional benefits while eliminating steps of cutting and sewing,
layering, seaming and/or use of elastic bands. Accordingly, use of
the aqueous polymeric dispersion in this manner gives flexibility
to designers, reduces steps and saves time and saves money in
production. In addition, apparel produced in accordance with this
method may be thinner and lighter. Apparel produced in accordance
with this method exhibits a smoother appearance, especially at any
modulus interface. Further, printing of the aqueous polymeric
dispersion at, for example, the thigh/calf/leg on leggings is
expected to increase garment power for training and activities.
[0062] In another nonlimiting embodiment, the inventors herein have
now found that selective application of the aqueous polymeric
dispersion in strategic areas of the garment can result in garments
staying in place during movement, exercise, and wear. For example,
printing of the dispersion in the tummy area of, for example,
leggings or yoga pants can result in support and shaping of tummy,
better fit at the back waist, and improved stay-in-place of the
garment during activity, all at the same time. Similarly, it has
been found that selectively printing the dispersion at different
places such as the band, the legging leg, the bra cup and wing, the
seamless top/sport tank cup and straps results in improved stay-in
place while still providing for the required stretch and/or
recovery. Application at selected locations of the bra strap can
eliminate the need for uncomfortable plastic strap adjusters while
improving both function and comfort. This use thus provides for
invisible, seamless, simplified, more flexible garment design while
decreasing manufacture time. Further, selective application of the
dispersion to edges, bands and hems of a garment reduces rolling of
such bands, hems, and garment edges without making the garment more
complex, thicker, heavier, expensive, and uncomfortable.
[0063] Further, the inventors herein have found that the ability of
the aqueous polymeric dispersion to improve shape retention, stay,
and comfort when applied at selected locations and/or intensity in
accordance with the methods of the present invention has many
useful applications beyond apparel. For example, application of the
aqueous polymeric dispersion at selected locations and/or intensity
improves comfort of seats, cushions, and pads. Unexpectedly, it was
found that when modifying foam by padding the dispersion and then
subjecting the foam to a static weight/pressure, increased
resistance to compressive collapse, reduced rate of collapse,
reduced extent of collapse, increased rate of recovery once the
weight was removed, and increased extent of recovery were all
observed. Such better compression resistance improves the lifetime
of such cushions and pads. In addition, application of the aqueous
polymeric dispersion on such fabric articles can reduce effects of
vibration/shock and reduce packaging volume by creating thinner and
better protective material.
[0064] Methods of the present invention can also be used to improve
shape retention of, for example, footwear, inserts, and
seating.
[0065] In addition, the methods of the present invention can be
used to assist with items such as, but not limited to, footwear
inserts, automobile fabrics, and bedding materials staying
inplace.
[0066] As shown herein, application of the aqueous polymeric
dispersion in accordance with the methods of the present invention
allows for highly selective and precisely controlled amounts of
enhancement in elastic modulus of apparel and other fabric articles
and provides advantages to incumbent techniques such as PU
dispersions, PU foam, fiberfill, spring cushions, cut/sewn fabric
panels generally more broad and indiscriminate.
[0067] All patents, patent applications, test procedures, priority
documents, articles, publications, manuals, and other documents
cited herein are fully incorporated by reference to the extent such
disclosure is not inconsistent with this invention and for all
jurisdictions in which such incorporation is permitted.
Test Methods and Examples
[0068] The following Test Methods and Examples demonstrate the
present invention and its capability for use. The invention is
capable of other and different embodiments, and its several details
are capable of modifications in various apparent respects, without
departing from the scope and spirit of the present invention.
Accordingly, the Test Methods and Examples are to be regarded as
illustrative in nature and non-limiting.
Test Methods for Garments
[0069] Wear force Test:
[0070] Force sensors were used to capture and record the force on
the body during wearing. The sensors were place between the garment
and fit model and detected the force at various locations such as
waist, back, shoulder, front, breast, under the bust, side of bust,
ankle, knee, buttock and tummy. The garments with and without
aqueous polyurethane dispersion treatment were compared. During the
measurement, the model stood still or acted in repeating movements
to mimic wearing motions that consumer would do in the garments.
The change of force during the motion was used to analysis the
comfort, support, shaping and stay.
3D Body Scanning:
[0071] A 3D body scanner was used to capture the silhouette of a
live model with or without a garment. The change in silhouette
showed the shaping effect of the aqueous polyurethane dispersion
treated garment on several body regions.
Fit Model Review:
[0072] Professional fit model with experiences in garment fitting
gave reviews of the garments after wearing. The comments include
the garment fit, comfort, support, look, stay, shape retention and
other expects regarding wearing experience.
Test Methods for Fabrics
Tensile Test:
[0073] A moving apparatus was used to fix fabrics at two ends and
stretch the fabric to certain elongation. The force, modulus, and
hysteresis during stretching and recovering was used to analyze the
fabric elastic and recovery power which is critical to the garment
shaping, supporting and comfort.
Wash Durability:
[0074] The aqueous polyurethane dispersion treated fabrics were
exposed to multiple (up to 50 washes) washing and drying cycles to
mimic the garment life-cycles. The washed and dried fabrics went
through other tests as mentioned. The change before and after
washing and drying was used to analyze the durability of the fabric
shape and functions.
Fabric Hand Test:
[0075] Testing people were asked to touch and feel the fabrics
blindly to examine the softness, smoothness and cooling expects of
the fabric.
Testing Methods Used on Forms and Fiberfill Materials:
Compression and Recovery Test:
[0076] Thickness changes in material are measured during change of
compression level by loading and unloading of a series of static
weights. The material was laid between flat plate holders. The
weight was loaded onto the top plate and maintained in place for a
few minutes before adding more weight. After adding weight to the
highest requirement, the weight was unloaded gradually at the same
levels as loading. The thickness was measured to determine the
compression resistance and percentage of recovery.
EXAMPLES
[0077] The following Examples describe nonlimiting embodiments of
compositions used in the present invention. The invention is
capable of other and different embodiments, and its several details
are capable of modifications in various apparent respects, without
departing from the scope and spirit of the present invention.
Accordingly, the Examples are to be regarded as illustrative in
nature and non-limiting.
[0078] In these examples, the following raw materials were
used:
TABLE-US-00001 TABLE 1 Ingredient Chemical Name CAS # Tradename
Vendor Glycol PTMEG 25190-06-1 Terathane .RTM. INVISTA 1800
Isocyanate Dicyclohexylmethane 5124-30-1 Vestanate Evonik
diisocyanate H12MDI DMPA Dimethylolpropionic 4767-03-7 D-MPA GEO
Acid Neutralizer Triethylamine 121-44-8 TEA BASF Surfactant
Alkyldiphenyloxide 119345-04-9 Dowfax 2A1 Dow Disulfonate Defoamer
mineral oil, silicone oil 3173-53-3 BYK 012 BYK Additives &
Instruments Antioxidant hindered phenols 36443-68-2 Irganox 245
BASF Thickener polyurethane Mixture Tafigel PUR 61 Munzing
Example 1: Prepolymer Preparation without 1-Hexanol
[0079] A polyurethane prepolymer was made using a
polytetramethylene ether glycol, an aliphatic diisocyanate such as
PICM (4,4'-methylene bis (cyclohexyl isocyanate), a hydrogenated
version of 4,4'-MDI) and a diol containing a sterically hindered
carboxylic acid group. More specifically, the following ingredients
and unit quantities were used to make the prepolymer:
TABLE-US-00002 TABLE 2 Ingredient CAS Number Unit Quantity
Terathane* 1800 251090-06-1 72.7806 1-Hexanol 111-27-3 0.0000
Vestanat* H12MDI 5124-30-1 24.7380 DMPA 4767-03-7 2.4814 Prepolymer
total 100.0000
[0080] The reaction to prepare the prepolymer was carried out in a
moisture-free, nitrogen-blanketed atmosphere to avoid side
reactions.
[0081] In this example, a 30 gallon reactor, jacketed with hot
water and equipped with an agitator, was used. This reactor was
heated to a temperature of about 55.degree. C. A pre-determined
weight of molten Terathane.RTM. 1800 glycol was charged into the
reactor. Then, DMPA solid powder was added to the reactor with
agitation and circulation, under nitrogen blanket, until the DMPA
solid particles were dispersed and dissolved in glycol.
[0082] Molten PICM was then charged into the reactor with
continuous agitation and the capping reaction was allowed to take
place at 90.degree. C. for 240 minutes, still with continuous
agitation. The formed viscous prepolymer was then sampled to
determine the extent of the reaction by measuring the weight
percentage of the isocyanate groups (% NCO) of the prepolymer
through a titration method. The theoretical value of the % NCO
after the reaction is completed is 2.97 assuming the glycol MW is
at 1800. If the determined % NCO value is higher than the
theoretical value, the reaction should be allowed to continue until
the theoretical value is reached or the % NCO number becomes
constant. Once it was determined that the reaction is complete, the
prepolymer temperature was maintained between 85 and 90.degree.
C.
Example 2: Preparation of Aqueous Polymer Dispersion with
Prepolymer of Example 1
[0083] The dispersion was prepared by the addition of the
prepolymer of Example 1 using a rotor/stator high speed disperser.
The prepolymer as made in Example 1 was transferred directly into
the disperser head and dispersed under high shear forces into
deionized water, containing a surfactant, a neutralizer, an
anti-oxidant and a foam control agent. Slightly more prepolymer
than required by the dispersion recipe was needed to compensate for
loss in the transfer line and in the reactor.
[0084] The ingredients for making the dispersion and the
composition of the dispersion are shown below in Table 3.
TABLE-US-00003 TABLE 3 Ingredient CAS Number Unit Quantity
Terathane* 1800 251090-06-1 30.1391 Vestanat* H12MDI 5124-30-1
10.2442 DMPA 4767-03-7 1.0276 1-Hexanol 111-27-3 0.0000 DI Water
7732-18-5 54.8093 Dowfax 2A1 119345-04-9 1.2652 Triethylamine
121-44-8 0.7830 Irganox 245 36443-68-2 0.6051 Tafigel PUR 61
Mixture 1.0000 BYK 012 Mixture 0.1265 Other 0.0000 Total
100.0000
[0085] In making a typical batch of 100 kg of the aqueous polymer
dispersion, Dowfax 2A1 surfactant (1.2652 kg), an anti-oxidizer
Irganox 245 (0.6051 kg), and foam control agent BYK-012 (0.1265 kg)
were mixed and dissolved in the deionized water (54.8093 kg). The
triethylamine neutralizer (0.783 kg) was added to the above water
mixture 5 minutes prior to the addition of the prepolymer. The
prepolymer (41.4109 kg) maintained at a temperature between 85 and
90.degree. C. was added into the water mixture with high speed
dispersing. The addition rate (typically at about 1.5 kg/min or
about 30 minutes) of the prepolymer should be controlled to allow
the formation of uniform dispersion, and the temperature of the
dispersion should be kept between 40 and 45.degree. C. Once the
addition of prepolymer was complete, mixing was continued for 60
minutes. Then, a thickener Tafigel PUR 61 (1.00 kg) was added and
allowed to mix for another 60 minutes. The as-made dispersion was
continuously agitated at low speed for 8 hours (or overnight) in
the container to eliminate foams and to ensure the reaction had
reached completion. The finished dispersion typically contains
about 42% solids, with viscosity about 4000 centipoises and pH in
the range of 7.0 to 8.5. Tenacity at break (T) is the maximum or
breaking force of a filament expressed as force per unit
cross-sectional area. The tenacity can be measured on an Instron
model 1130 available from Instron of Canton, Mass, and is reported
as grams per denier (grams per dtex). Filament tenacity at break
(and elongation at break) can be measured according to ASTM D
885.
[0086] The dispersion was then filtered through 100 micron bag
filters to remove big particles before packed for shipment. It is
recommended to use 55 gallon metal drums with polyethylene liner
inside to contain the dispersion for shipment.
[0087] Final product specifications were determined as shown in
Table 4.
TABLE-US-00004 TABLE 4 Parameters Aim .+-. Limits Method Prepolymer
% NCO* 3.00 0.10 Titration Dispersion Solids, % 44.0 2.0 Microwave
Dispersion Viscosity, 4000 1000 RV Spindle #3/10 rpm cps** @
25.degree. C. Dispersion pH 7.7 0.7 Dispersion Filterability
Passing through filter bags no more than 100 microns *Sampled 20-30
minutes before the prepolymer is dispersed. **Sampled and measured
24 hours after the dispersion is thickened.
Example 3: Preparation of Prepolymer with 1-Hexanol
[0088] The polyurethane prepolymer was made using a
polytetramethylene ether glycol, 1-Hexanol, an aliphatic
diisocyanate such as PICM (4,4'-methylene bis (cyclohexyl
isocyanate), a hydrogenated version of 4,4'-MDI) and a diol
containing a sterically hindered carboxylic acid group. Table 5
lists the ingredients and unit quantities used to make the
prepolymer.
TABLE-US-00005 TABLE 5 Ingredient CAS Number Unit Quantity
Terathane* 1800 251090-06-1 72.4492 1-Hexanol 111-27-3 0.4087
Vestanat* H12MDI 5124-30-1 24.6607 DMPA 4767-03-7 2.4814 Prepolymer
total 100.0000
[0089] The reaction to prepare the prepolymer was carried out in a
moisture-free, nitrogen-blanketed atmosphere to avoid side
reactions.
[0090] In this example, a 30 gallon reactor, jacketed with hot
water and equipped with an agitator, was used. This reactor was
heated to a temperature of about 55.degree. C. A pre-determined
weight of molten Terathane.RTM. 1800 glycol was charged into the
reactor. The 1-Hexanol was added second. Then, DMPA solid powder
was added to the reactor with agitation and circulation, under
nitrogen blanket, until the DMPA solid particles were dispersed and
dissolved in glycol.
[0091] Molten PICM was then charged into the reactor with
continuous agitation and the capping reaction was allowed to take
place at 90.degree. C. for 240 minutes, still with continuous
agitation. The formed viscous prepolymer was then sampled to
determine the extent of the reaction by measuring the weight
percentage of the isocyanate groups (% NCO) of the prepolymer
through a titration method. The theoretical value of the % NCO
after the reaction is completed is 2.80 assuming the glycol MW is
at 1800. If the determined % NCO value is higher than the
theoretical value, the reaction should be allowed to continue until
the theoretical value is reached or the % NCO number becomes
constant. Once it was determined that the reaction is complete,
maintain the prepolymer temperature between 85 and 90.degree.
C.
Example 4: Preparation of Aqueous Polymer Dispersion with
Prepolymer of Example 3
[0092] The dispersion was prepared by the addition of prepolymer of
Example 3 using a rotor/stator high speed disperser. The prepolymer
as made in Example 3 was transferred directly into the disperser
head and dispersed under high shear forces into deionized water,
containing a surfactant, a neutralizer, an anti-oxidant and a foam
control agent. Slightly more prepolymer than required by the
dispersion recipe is needed to compensate for loss in the transfer
line and in the reactor.
[0093] Table 6 lists the ingredients used in making the dispersion
and the composition of the dispersion.
TABLE-US-00006 TABLE 6 Ingredient CAS Number Unit Quantity
Terathane* 1800 251090-06-1 30.0000 Vestanat* H12MDI 5124-30-1
10.2116 DMPA 4767-03-7 1.0275 1-Hexanol 111-27-3 0.1692 DI Water
7732-18-5 54.8083 Dowfax 2A1 119345-04-9 1.2652 Triethylarnine
121-44-8 0.7866 Irganox 245 36443-68-2 0.6051 Tafigel PUR 61
Mixture 1.0000 BYK 012 Mixture 0.1265 Other 0.0000 Total
100.0000
[0094] In making a typical batch of this 100 kg dispersion Dowfax
2A1 surfactant (1.2652 kg), an anti-oxidizer Irganox 245 (0.6051
kg), and foam control agent BYK-012 (0.1265 kg) were mixed and
dissolved in the deionized water (54.8083 kg). The triethylamine
neutralizer (0.7866 kg) was added to the above water mixture 5
minutes prior to the addition of the prepolymer. The prepolymer
(41.4083 kg) maintained at a temperature between 85 and 90.degree.
C. was added into the water mixture with high speed dispersing. The
addition rate (typically at about 1.5 kg/min or about 30 minutes)
of the prepolymer should be controlled to allow the formation of
uniform dispersion, and the temperature of the dispersion should be
kept between 40 and 45.degree. C. Once the addition of prepolymer
was complete, mixing was continued for 60 minutes. Then, a
thickener Tafigel PUR 61 (1.00 kg) was added and allowed to mix for
another 60 minutes. The as-made dispersion was continuously
agitated at low speed for 8 hours (or overnight) in the container
to eliminate foams and to ensure the reaction had reached
completion. The finished dispersion typically contains about 42%
solids, with viscosity about 4000 centipoises and pH in the range
of 7.0 to 8.5.
[0095] The dispersion is then filtered through 100 micron bag
filters to remove big particles before packed for shipment. It is
recommended to use 55 gallon metal drums with vented caps, and with
a polyethylene liner inside to contain the dispersion for
shipment.
[0096] Final product specifications were determined as shown in
Table 7.
TABLE-US-00007 TABLE 7 Parameters Aim .+-. Limits Method Prepolymer
% NCO* 2.80 0.10 Titration Dispersion Solids, % 44.0 2.0 Microwave
Dispersion Viscosity, 4000 1000 RV Spindle #3/10 rpm cps** @
25.degree. C. Dispersion pH 7.7 0.7 Dispersion Filterability
Passing through filter bags no more than 100 microns *Sampled 20-30
minutes before the prepolymer is dispersed **Sampled and measured
24 hours after the dispersion is thickened.
* * * * *