U.S. patent application number 14/917073 was filed with the patent office on 2016-07-07 for spandex fibers for enhanced bonding.
This patent application is currently assigned to INVISTA NORTH AMERICA S.A.R.L.. The applicant listed for this patent is INVISTA TECHNOLOGIES S.A.R.L.. Invention is credited to Ronald D. BING-WO, Achille Mayelle BIVIGOU KOUMBA, Hong LIU, Steven W. SMITH.
Application Number | 20160194787 14/917073 |
Document ID | / |
Family ID | 52666355 |
Filed Date | 2016-07-07 |
United States Patent
Application |
20160194787 |
Kind Code |
A1 |
BIVIGOU KOUMBA; Achille Mayelle ;
et al. |
July 7, 2016 |
SPANDEX FIBERS FOR ENHANCED BONDING
Abstract
An elastic fiber is provided that includes polyurethane and/or
polyurethaneurea and an additive such as polystyrene, an acrylic
polymer, polyvinylpyrrolidone, copolymers thereof, derivatives
thereof, and combinations thereof. The elastic fiber is useful in
laminate structures, such as disposable hygiene articles as wells
as in knit, woven and nonwoven fabric constructions.
Inventors: |
BIVIGOU KOUMBA; Achille
Mayelle; (Charlottesville, VA) ; LIU; Hong;
(Waynesboro, VA) ; BING-WO; Ronald D.;
(Waynesboro, VA) ; SMITH; Steven W.; (Waynesboro,
VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
INVISTA TECHNOLOGIES S.A.R.L. |
St. Gallen |
|
CH |
|
|
Assignee: |
INVISTA NORTH AMERICA
S.A.R.L.
WILMINGTON
DE
|
Family ID: |
52666355 |
Appl. No.: |
14/917073 |
Filed: |
September 12, 2014 |
PCT Filed: |
September 12, 2014 |
PCT NO: |
PCT/US2014/055519 |
371 Date: |
March 7, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61877609 |
Sep 13, 2013 |
|
|
|
Current U.S.
Class: |
442/329 ; 156/60;
156/73.2; 428/221; 428/423.1 |
Current CPC
Class: |
A61F 13/15593 20130101;
D01F 8/16 20130101; D01F 6/94 20130101; D01F 1/10 20130101; D01F
6/72 20130101; A61F 13/4902 20130101; D01F 6/70 20130101 |
International
Class: |
D01F 6/70 20060101
D01F006/70 |
Claims
1. A laminate structure comprising: an elastic fiber comprising
polyurethane and about 0.01% to about 30% by weight of at least one
additive selected from the group consisting of a polystyrene, an
acrylic polymer, polyvinylpyrrolidone, copolymers thereof,
derivatives thereof, and combinations thereof; wherein said elastic
fiber is adhered to one or more layers of a substrate selected from
the group consisting of fabric, nonwoven, film, and combinations
thereof.
2. The laminate structure of claim 1, wherein said additive is
selected from polystyrene, polystyrene co-polymers, polystyrene
derivatives, and combinations thereof.
3. The laminate structure of claim 1, wherein said additive is
selected from polystyrene, styrene-acrylonitrile copolymer (SAN),
styrene-butadiene copolymer (SBS), styrene-butadiene block
copolymer, acrylonitrile-butadienestyrene copolymer (ABS), and
combinations thereof.
4. The laminate structure of claim 1, wherein said elastic fiber is
adhered by an adhesive, ultrasonic bonding, thermal bonding or
combinations thereof.
5. The laminate structure of claim 1, wherein said elastic fiber is
solution-spun.
6. The laminate structure of claim 1, wherein said elastic fiber is
a sheath-core bicomponent fiber and said additive is present only
in said sheath.
7. The laminate structure of claim 6, wherein said sheath includes
said additive in an amount of about 0.5% to about 70% by weight of
said sheath.
8. The laminate structure of claim 1, wherein said acrylic polymer
is selected from poly(butyl methacrylate), poly(ethyl
methacrylate), poly(methyl methacrylate), polyacrylonitrile,
poly(methyl methacrylate-co-butyl methacrylate), and combinations
thereof.
9. The laminate structure of claim 1, wherein said elastic fiber
further comprises a topical finish comprising mineral oil, silicon
oil, or combinations thereof in an amount of 0.1% to about 2% by
weight of the fiber.
10. The laminate structure of claim 9, wherein said topical finish
has a viscosity of about 5 centistokes to about 150
centistokes.
11. The laminate structure of claim 1, wherein said elastic fiber
further comprises an additional additive selected from magnesium
stearate, organic stearates, silicon oil, mineral oil, and
combinations thereof.
12. An elastic fiber comprising polyurethane and about 0.01% to
about 0.90% by weight of at least one additive selected from the
group consisting of a polystyrene, an acrylic polymer, copolymers
thereof, derivatives thereof, and combinations thereof.
13. An elastic fiber comprising polyurethane and at least one
additive selected from the group consisting of a polystyrene, an
acrylic polymer, copolymers thereof, derivatives thereof, and
combinations thereof, wherein the additive has a number average
molecular weight of 300 to less than 50,000.
14. The elastic fiber of claim 13, wherein the additive has a
number average molecular weight of 300 to 45,000.
15. A solution-spun bicomponent elastic fiber comprising a
sheath-core construction; wherein said core comprises polyurethane
and said sheath comprises at least one additive selected from the
group consisting of a polystyrene, an acrylic polymer,
polyvinylpyrrolidone, copolymers thereof, derivatives thereof, and
combinations thereof.
16. A fabric comprising: an elastic fiber comprising polyurethane
and about 0.01% to about 30% by weight of at least one additive
selected from the group consisting of a polystyrene, an acrylic
polymer, polyvinylpyrrolidone, copolymers thereof, derivatives
thereof, and combinations thereof.
17. The fabric of claim 16, wherein said fabric comprises a knit,
woven or nonwoven construction.
18. A method for preparing a laminate structure comprising:
providing an elastic fiber comprising polyurethane and about 0.01%
to about 30% by weight of at least additive selected from the group
consisting of a polystyrene, an acrylic polymer,
polyvinylpyrrolidone, copolymers thereof, derivatives thereof, and
combinations thereof; wherein said elastic fiber is adhered to one
or more layers of a substrate selected from the group consisting of
fabric, nonwoven, film, and combinations thereof.
19. The method of claim 18, wherein said elastic fiber is adhered
by ultrasonic bonding, an adhesive, thermal bonding, and
combinations thereof.
20. The method of claim 18, wherein said laminate article is
included in a disposable hygiene article.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to the formation of elastic
fibers (either bicomponent such as spandex sheath-core fibers) or a
single component (also referred to herein as monocomponent fiber)
suitable for bonding to a substrate such as one includes polyolefin
fiber. The spandex fibers are produced by dry spinning of polymer
blends into a monocomponent or sheath-core bicomponent fiber.
[0003] 2. Description of the Related Art
[0004] The global market for disposable diapers has an increased
demand for fibers with excellent resilience, high stretchability
and high bonding capacity to nonwovens. Because of their
outstanding properties, including high elongation and good elastic
recovery, spandex fibers continue to gain interest for their use as
elastic strands in disposable diapers. In incontinence products
such as baby and adult diapers spandex fibers are used in several
locations such as in leg bands and/or waistbands to provide an
excellent fit of the diapers.
[0005] To introduce stretchable regions in disposable diapers, a
hot melt adhesive is applied against a stretched elastomeric fiber
which is later laminated between two or more layers such as films
or nonwovens that may include polypropylene. While hot melt
adhesives are applied to create bond sites between elastomeric
strands and nonwoven substrates, significant lack of adhesion is
still observed between the different components of the diaper:
spandex strands, hot melt adhesive and nonwoven fabrics. It is
believed that hot melt adhesives are compatible with nonwoven
fabrics, while they are chemically incompatible with spandex
fibers.
[0006] To address this drawback, the most popular method available
for bonding spandex fibers to nonwoven fabrics is to overload
spandex strands with a hot melt adhesive. Since the cost of hot
melt adhesives is high, it is convenient to apply adhesive add-ons
lower than 18 gsm (grams of adhesive material per square meter of
substrate covered by the adhesive), more preferably equal to or
lower than 15 gsm, and most preferably equal to or lower than 12
gsm.
[0007] U.S. Pat. No. 7,255,820 discloses the use of polystyrene in
spandex, but only for the purpose of achieving improved heat set,
which is unrelated to the technical problem disclosed herein.
SUMMARY OF THE INVENTION
[0008] Blend spinning spandex with an economical alternative
polymer additive provides a route to reduce adhesive consumption
cost with no change in spandex fibers performance. Of the unique
benefits sheath-core fibers arrangement have over the conventional
one, is a potential cost savings associated with the use of less of
a more expensive polymeric additive to obtain the same desirable
characteristics or adding an expensive additive to only the sheath
polymer, taking advantage of the lower melting point of a polymer
spun in the sheath to promote bonding without a disruption in the
morphology of the core component, improving the efficiency of
elastic fibers made from a spinnable polymer core sheathed within a
polymer blend comprising polymers with poor and good
spinnability.
[0009] Some embodiments provide monocomponent and/or bicomponent
sheath-core spandex fibers with bonding enhancing additives which
enhance bonding between spandex fibers to substrates, such as
nonwovens. The sheath-core fibers include a higher-melting
polyurethaneurea core and a sheath including a low-melting
thermoplastic polymer as a bonding enhancing additive.
[0010] The reason for using low-melting polymer sheath is to
provide a higher bonding strength with adhesives and substrates
such as nonwovens or, in the alternative, to reduce the amount of
adhesive required for the same bonding strength.
[0011] In one embodiment the elastic material is attached to the
polyolefin nonwoven substrate when the melt adhesive is sprayed
onto the elastic strands at temperatures range 160.degree.
C.-200.degree. C., which is above the glass transition temperature
of the thermoplastic polymer sheath, the latter melts or softens
the bonding enhancing additive to form bond sites with hot melt
adhesives and nonwoven substrates upon cooling.
[0012] The thermoplastic binders include but not limited to
polystyrene, acrylic polymer, polyvinylpyrrolidone, copolymers
thereof, derivatives thereof and combinations thereof. The primary
reason for using polystyrene polymers is that they are inherently
capable of bonding to hot melt adhesive since these adhesives are
mostly made of polystyrene block copolymers. Finally, the low cost
of polystyrene polymers is another attractive reason to increases
cost saving in disposable diapers applications.
[0013] In one embodiment of a sheath-core elastic fiber, the core
fibers include 100% of polyurethane such as a higher-melting
segmented polyurethane/urea polymer and the sheath includes a
polymer blend including about 30% to 99.5% of at least one selected
polyurethane/urea polymer and about 0.5% to about 70% of at least
one additive such as an enhanced bonding additive. The elastic
monocomponent and bicomponent sheath-core fibers are capable of
providing enhanced bonding to substrates such as a polyolefin fiber
substrate (including nonwovens) when the former are heated above
the corresponding glass transition or melting temperature of the
enhanced bonding additive, optionally in the presence of a hot melt
adhesive. As an additional benefit, reduced tack of the fiber has
been observed which improves over-end take-off tension in dispenses
spandex.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Laminate structures are provided that include an elastic
fiber including polyurethane and about 0.01% to about 30% by weight
of at least one additive selected from the group consisting of a
polystyrene, an acrylic polymer, polyvinylpyrrolidone, copolymers
thereof, derivatives thereof, and combinations thereof; where the
elastic fiber is adhered to one or more layers of a substrate
selected from the group consisting of fabric, nonwoven, film, and
combinations thereof. The laminate structure may be adhered by any
known method, including but not limited to where the elastic fiber
is adhered by an adhesive, ultrasonic bonding, thermal bonding or
combinations thereof
[0015] The elastic fiber, which can be used in a fabrics or
laminate structures may include a topical finish including mineral
oil, silicon oil, or combinations thereof. This finish may be
present in any suitable amount such as an amount of 0.1% to about
2% by weight of the fiber including up to about 1% by weight of the
fiber. The topical finish has a viscosity of about 5 centistokes to
about 150 centistokes.
[0016] Other additives can be included in the fiber as desired.
Suitable fiber additives include magnesium stearate, organic
stearates, silicon oil, mineral oil, and combinations thereof.
[0017] The elastic fiber may include polyurethane and/or
polyurethaneurea and about 0.01% to about 0.90% (including about
0.3% to about 0.85% and about 0.60% to about 0.85%) by weight of at
least one additive selected from the group consisting of a
polystyrene, an acrylic polymer, copolymers thereof, derivatives
thereof, and combinations thereof. This fiber may be solution-spun.
The fiber may have a homogeneous cross-section (a monocomponent
fiber) or have a bicomponent elastic fiber comprising a sheath-core
construction; where the core includes polyurethane and said sheath
comprises at least one additive selected from the group consisting
of a polystyrene, an acrylic polymer, polyvinylpyrrolidone,
copolymers thereof, derivatives thereof, and combinations
thereof.
[0018] The elastic fiber may also be included in fabric, such as a
knit, a woven, or a nonwoven construction. The elastic fiber
includes polyurethane and about 0.01% to about 30% by weight of at
least one additive selected from the group consisting of a
polystyrene, an acrylic polymer, polyvinylpyrrolidone, copolymers
thereof, derivatives thereof, and combinations thereof.
[0019] A method for preparing a laminate structure is provided
including: [0020] providing an elastic fiber including polyurethane
and about 0.01% to about 30% (such as about 0.1% to about 3.0%) by
weight of at least additive selected from the group consisting of a
polystyrene, an acrylic polymer, polyvinylpyrrolidone , copolymers
thereof, derivatives thereof, and combinations thereof; [0021]
where the elastic fiber is adhered to one or more layers of a
substrate selected from the group consisting of fabric, nonwoven,
film, and combinations thereof.
[0022] The laminate structure may be adhered by ultrasonic bonding,
an adhesive, thermal bonding, and combinations thereof. This
laminate article may be included in a disposable hygiene
article.
[0023] Polyurethaneurea and Polyurethane Compositions
[0024] Polyurethaneurea compositions useful for preparing fiber or
long chain synthetic polymers that include at least 85% by weight
of a segmented polyurethane. Typically, these include a polymeric
glycol or polyol which is reacted with a diisocyanate to form an
NCO-terminated prepolymer (a "capped glycol"), which is then
dissolved in a suitable solvent, such as dimethylacetamide,
dimethylformamide, or N-methylpyrrolidone, and then reacted with a
difunctional chain extender. Polyurethanes are formed when the
chain extenders are diols (and may be prepared without solvent).
Polyurethaneureas, a sub-class of polyurethanes, are formed when
the chain extenders are diamines. In the preparation of a
polyurethaneurea polymer which can be spun into spandex, the
glycols are extended by sequential reaction of the hydroxy end
groups with diisocyanates and one or more diamines. In each case,
the glycols must undergo chain extension to provide a polymer with
the necessary properties, including viscosity. If desired,
dibutyltin dilaurate, stannous octoate, mineral acids, tertiary
amines such as triethylamine, N,N'-dimethylpiperazine, and the
like, and other known catalysts can be used to assist in the
capping step.
[0025] Suitable polyol components include polyether glycols,
polycarbonate glycols, and polyester glycols of number average
molecular weight of about 600 to about 3,500. Mixtures of two or
more polyols or copolymers can be included.
[0026] Examples of polyether polyols that can be used include 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, such as 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 of Wichita, Kans.) with a functionality of 2, is one
example of a specific suitable polyol. Co-polymers can include
poly(tetramethylene-co-ethyleneether) glycol.
[0027] Examples of polyester polyols 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. Examples 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 an example of a specific
polyester polyol.
[0028] Examples of polycarbonate polyols 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 an example of a specific polycarbonate polyol.
[0029] The diisocyanate component can also include a single
diisocyanate or a mixture of different diisocyanate including an
isomer mixture of diphenylmethane diisocyanate (MDI) containing
4,4'-methylene bis(phenyl isocyanate) and 2,4'-methylene bis(phenyl
isocyanate). Any suitable aromatic or aliphatic diisocyanate can be
included. Examples of diisocyanates that can be used include, but
are not limited to,
1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene,
1-isocyanato-2-[(4-cyanatophenyl)methyl]benzene,
bis(4-isocyanatocyclohexyl)methane,
5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane,
1,3-diisocyanato-4-methyl-benzene, 2,2'-toluenediisocyanate,
2,4'-toluenediisocyanate, and mixtures thereof. Examples of
specific polyisocyanate components include Mondur.RTM. ML (Bayer),
Lupranate.RTM. MI (BASF), and Isonate.RTM. 50 O, P' (Dow Chemical),
and combinations thereof.
[0030] A chain extender may be either water or a diamine chain
extender for a polyurethaneurea. Combinations of different chain
extenders may be included depending on the desired properties of
the polyurethaneurea and the resulting fiber. Examples of suitable
diamine chain extenders include: hydrazine; 1,2-ethylenediamine;
1,4-butanediamine; 1,2-butanediamine; 1,3-butanediamine;
1,3-diamino-2,2-dimethylbutane; 1,6-hexamethylenediamine;
1,12-dodecanediamine; 1,2-propanediamine; 1,3-propanediamine;
2-methyl-1,5-pentanediamine;
1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane;
2,4-diamino-1-methylcyclohexane; N-methylamino-bis(3-propylamine);
1,2-cyclohexanediamine; 1,4-cyclohexanediamine;
4,4'-methylene-bis(cyclohexylamine); isophorone diamine;
2,2-dimethyl-1,3-propanediamine; meta-tetramethylxylenediamine;
1,3-diamino-4-methylcyclohexane; 1,3-cyclohexane-diamine;
1,1-methylene-bis(4,4'-diaminohexane);
3-aminomethyl-3,5,5-trimethylcyclohexane; 1,3-pentanediamine
(1,3-diaminopentane); m-xylylene diamine; and Jeffamine.RTM.
(Texaco).
[0031] When a polyurethane is desired, the chain extender is a
diol. Examples of such diols that may be used include, but are not
limited to, ethylene glycol, 1,3-propanediol, 1,2-propylene glycol,
3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-trimethylene diol,
2,2,4-trimethyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol,
1,4-bis(hydroxyethoxy)benzene, and 1,4-butanediol and mixtures
thereof.
[0032] A blocking agent which is a monofunctional alcohol or a
monofunctional dialkylamine may optionally be included to control
the molecular weight of the polymer. Blends of one or more
monofunctional alcohols with one or more dialkylamine may also be
included.
[0033] Examples of monofunctional alcohols useful with the present
invention include at least one member selected from the group
consisting of aliphatic and cycloaliphatic primary and secondary
alcohols with 1 to 18 carbons, phenol, substituted phenols,
ethoxylated alkyl phenols and ethoxylated fatty alcohols with
molecular weight less than about 750, including molecular weight
less than 500, hydroxyamines, hydroxymethyl and hydroxyethyl
substituted tertiary amines, hydroxymethyl and hydroxyethyl
substituted heterocyclic compounds, and combinations thereof,
including furfuryl alcohol, tetrahydrofurfuryl alcohol,
N-(2-hydroxyethyl)succinimide, 4-(2-hydroxyethyl)morpholine,
methanol, ethanol, butanol, neopentyl alcohol, hexanol,
cyclohexanol, cyclohexanemethanol, benzyl alcohol, octanol,
octadecanol, N,N-diethylhydroxylamine, 2-(diethylamino)ethanol,
2-dimethylaminoethanol, and 4-piperidineethanol, and combinations
thereof.
[0034] Examples of suitable mono-functional dialkylamine blocking
agents include: N,N-diethylamine, N-ethyl-N-propylamine,
N,N-diisopropylamine, N-tert-butyl-N-methylamine,
N-tert-butyl-N-benzylamine, N,N-dicyclohexylamine,
N-ethyl-N-isopropylamine, N-tert-butyl-N-isopropylamine,
N-isopropyl-N-cyclohexylamine, N-ethyl-N-cyclohexylamine,
N,N-diethanolamine, and 2,2,6,6-tetramethylpiperidine.
[0035] Bonding Enhancing Additives
[0036] The bonding enhancing additives may be any suitable
hydrocarbon resin such as those selected from polystyrene, acrylic
polymer, polyvinylpyrrolidone, copolymers thereof, derivatives
thereof, and combinations thereof. Derivatives can include esters,
acids, amides, and the like. The bonding enhancing additives may be
of any suitable molecular weight such as number average molecular
weight of 300 to 500,000. A higher number average molecular weight
may be 50,000-500,000 or 150,000 to 300,000. A lower number average
molecular weight may be less than 50,000. Suitable ranges for the
lower number average molecular weight hydrocarbon resin may be
about 300 to 45,000 or 1000 to 40,000.
[0037] The styrene additive may include polystyrene, polystyrene
copolymers, polystyrene derivatives, and combinations thereof.
Examples of suitable styrene-based polymers include, but are not
limited to, polystyrene, p-alkylpolystyrene, such as
p-methylpolystyrene, p-arylpolystyrene and the like. Further, the
example of the polystyrene copolymer includes styrene-acrylonitrile
copolymer (SAN), styrene-butadiene copolymer (SBS),
styrene-butadiene block copolymer, acrylonitrile-butadienestyrene
copolymer (ABS), styrene co-polymer with (1-methylethenyl)benzene,
and combinations thereof.
[0038] The acrylic polymer may include any of a variety of
monomers. As monomers, those including an acryl moiety, for example
acrylic acid and methacrylic acid, as well as their derivatives or
mixtures thereof, are suitable. Esters, amides, acrylic acid
nitrile and their mixtures are considered preferably as
derivatives. Examples include poly(butyl methacrylate), poly(ethyl
methacrylate), poly(methyl methacrylate), polyacrylonitrile,
poly(methyl methacrylate-co-butyl methacrylate), and combinations
thereof.
[0039] Examples of C.sub.1-12 hydrocarbon group-containing
(meth)acrylic acid ester monomer as component include (meth)acrylic
acid alkyl esters, (meth)acrylic acid alkenyl esters, (meth)acrylic
acid cycloalkyl esters, (meth)acrylic acid cycloalkenyl esters,
(meth)acrylic acid aryl esters, (meth)acrylic acid alkylaryl
esters, (meth)acrylic acid aralkyl esters, (meth)acrylic acid
alkylaralkyl esters, (meth)acrylic acid aralkylaryl esters, and the
like. Among these, (meth)acrylic acid alkyl esters and
(meth)acrylic acid cycloalkyl esters are suitable.
[0040] Examples of useful acrylic polymers include poly(butyl
methacrylate), poly(ethyl methacrylate), poly(methyl methacrylate),
polyacrylonitrile, poly(methyl methacrylate-co-butyl methacrylate),
and combinations thereof.
[0041] Additives
[0042] Classes of additives that may be optionally included in
polyurethaneurea compositions are listed below. An exemplary and
non-limiting list is included. However, additional additives are
well-known in the art. Examples include: anti-oxidants, UV
stabilizers, colorants, pigments, cross-linking agents, phase
change materials (paraffin wax), antimicrobials, minerals (i.e.,
copper), microencapsulated additives (i.e., aloe vera, vitamin E
gel, aloe vera, sea kelp, nicotine, caffeine, scents or aromas),
nanoparticles (i.e., silica or carbon), calcium carbonate, flame
retardants, antitack additives, chlorine degradation resistant
additives, vitamins, medicines, fragrances, electrically conductive
additives, dyeability and/or dye-assist agents (such as quaternary
ammonium salts). Other additives which may be added to the
polyurethaneurea compositions include adhesion promoters,
anti-static agents, anti-creep agents, optical brighteners,
coalescing agents, electroconductive additives, luminescent
additives, lubricants, organic and inorganic fillers,
preservatives, texturizing agents, thermochromic additives, insect
repellants, and wetting agents, stabilizers (hindered phenols, zinc
oxide, hindered amine), slip agents(silicone oil) and combinations
thereof.
[0043] The additive may provide one or more beneficial properties
including: dyeability, hydrophobicity (i.e.,
polytetrafluoroethylene (PTFE)), hydrophilicity (i.e., cellulose),
friction control, chlorine resistance, degradation resistance
(i.e., antioxidants), adhesiveness and/or fusibility (i.e.,
adhesives and adhesion promoters), flame retardance, antimicrobial
behavior (silver, copper, ammonium salt), barrier, electrical
conductivity (carbon black), tensile properties, color,
luminescence, recyclability, biodegradability, fragrance, tack
control (i.e., metal stearates), tactile properties, set-ability,
thermal regulation (i.e., phase change materials), nutriceutical,
delustrant such as titanium dioxide, stabilizers such as
hydrotalcite, a mixture of huntite and hydromagnesite, UV
screeners, and combinations thereof.
[0044] Process of Making Fibers
[0045] The fiber of some embodiments is produced by solution
spinning (either wet-spinning or dry spinning) of the
polyurethane-urea polymer from a solution with conventional
urethane polymer solvents (e.g., DMAc). The polyurethaneurea
polymer solutions may include any of the compositions or additives
described above. The polymer is prepared by reacting an organic
diisocyanate with appropriate glycol, at a mole ratio of
diisocyanate to glycol in the range of 1.6 to 2.3, preferably 1.8
to 2.0, to produce a "capped glycol". The capped glycol is then
reacted with a mixture of diamine chain extenders. In the resultant
polymer, the soft segments are the polyether/urethane parts of the
polymer chain. These soft segments exhibit melting temperatures of
lower than 60.degree. C. The hard segments are the
polyurethane/urea parts of the polymer chains; these have melting
temperatures of higher than 200.degree. C. The hard segments amount
to 5.5 to 9%, preferably 6 to 7.5%, of the total weight of the
polymer.
[0046] In one embodiment of preparing fibers, the polymer solutions
containing 30-40% polymer solids are metered through desired
arrangement of distribution plates and orifices to form filaments.
Distribution plates are arranged to combine polymer streams in a
one of concentric sheath-core, eccentric sheath-core, and
side-by-side arrangement followed by extrusion thru a common
capillary. Extruded filaments are dried by introduction of hot,
inert gas at 300.degree. C.-400.degree. C. and a gas:polymer mass
ratio of at least 10:1 and drawn at a speed of at least 400 meters
per minute (preferably at least 600 m/min) and then wound up at a
speed of at least 500 meters per minute (preferably at least 750
m/min). All examples given below were made with 80.degree. C.
extrusion temperature in to a hot inert gas atmosphere at a take-up
speed of 762 m/min. Standard process conditions are well-known in
the art.
[0047] The additive which enhances bonding, such as polystyrene, an
acrylic polymer, or polyvinylpyrrolidone may be added to the
polymer solution for the core, the sheath only, or for a
monocomponent (not bicomponent) fiber. For example, in a
sheath-core bicomponent fiber, the additive may be present only in
the sheath. When the additive is only in the sheath, it may be
present in an amount of about 0.5% to about 70% by weight of the
sheath.
[0048] Yarns formed from elastic fibers made in accordance with the
present invention generally have a tenacity at break of at least
0.6 cN/dtex, a break elongation of at least 400%, an unload modulus
at 300% elongation of at least 27 mg/dtex.
[0049] Strength and elastic properties of the spandex were measured
in accordance with the general method of ASTM D 2731-72. For the
examples reported in Tables below, spandex filaments having a 5 cm
gauge length were cycled between 0% and 300% elongation at a
constant elongation rate of 50 cm per minute. Modulus was
determined as the force at 100% (M100) and 200% (M200) elongation
on the first cycle and is reported in grams. Unload modulus (U200)
was determined at 200% elongation on the fifth cycle and is
reported in the Tables in grams. Percent elongation at break and
force at break was measured on the sixth extension cycle.
[0050] Percent set was determined as the elongation remaining
between the fifth and sixth cycles as indicated by the point at
which the fifth unload curve returned to substantially zero stress.
Percent set was measured 30 seconds after the samples had been
subjected to five 0-300% elongation/relaxation cycles. The percent
set was then calculated as % Set=100(Lf-Lo)/Lo, where Lo and Lf are
the filament (yarn) length, when held straight without tension,
before (Lo) and after (Lf) the five elongation/relaxation
cycles.
[0051] The features and advantages of the present invention are
more fully shown by the following examples which are provided for
purposes of illustration, and are not to be construed as limiting
the invention in any way.
EXAMPLES
[0052] Representative embodiments of the present invention will be
described with reference to the following examples that illustrate
the principle and practice of the present invention. In these
examples, Polyurethane/urea prepared according to a conventional
method is a linear polymer (commercially available from Invista, S.
a. r. L., of Wichita, Kans. and Wilmington, Del.);
[0053] St stands for polystyrene;
[0054] St1 stands for lower number average molecular weight
polystyrene;
[0055] BM stands for poly(butyl methacrylate);
[0056] IBM stands for poly(isobutyl methacrylate);
[0057] MMA stands for poly(methyl methacrylate);
[0058] AN stands for polyacrylonitrile;
[0059] SMMA stands for copolymer poly(styrene-co-methyl
methacrylate);
[0060] SAN stands for copolymer poly(styrene-co-acrylonitrile);
[0061] PVP stands for polyvinylpyrrolidone
[0062] MB2766: thermoplastic acrylic resin
[0063] ZeroCreep.TM. stands for hot melt elastic attachment
adhesive.
[0064] The compounds listed above are commercially available from
the Sigma Aldrich) except for MB2766 and ZeroCreep.TM. which were
provided by Dianal America, Inc and the hot melt adhesive by
Bostik.
Example 1
[0065] Core Solution
[0066] Segmented polyurethane was completely dissolved in a
dimethylacetamide solvent, to obtain a spinning core solution. As
such, a mixing ratio by weight of polyurethane to DMAC was 35:65
(w/w).
[0067] Sheath solution
[0068] Polystyrene was completely dissolved in a dimethylacetamide
solvent, to obtain a polystyrene stock solution, which was then
mixed with a segmented polyurethane solution (see core solution).
As such, a mixing ratio by weight of polystyrene to polyurethane is
listed in Table 1. To assure uniformity, each copolymer sample was
thoroughly mixed for 6h before characterization or spinning was
started.
[0069] Thereafter, the core-sheath solutions were spun into a
single thread of 40 and 360 denier yarns with 4 filaments twisted
together at a wound-up speed of 930 meters per minute. Prior to
entering the spinning core-sheath cell, which was flushed with
nitrogen gas of 375.degree. C. at a flow rate of 5.5 kg per hour,
the polymer solution temperature was controlled at 50.degree. C.
The dried yarn was then winding-up into a tube. The as-spun yarn
properties of this test item were measured and listed in Table
1.
Example 2
[0070] The same procedures and conditions were used as described in
Example 1 except that polystyrene was replaced either by
poly(methyl methacrylate) or poly(acrylonitrile) and a mixing ratio
by weight (w/w) shown in Table 1. The as-spun yarn properties of
this test item were measured and listed in Table 1.
Example 3
[0071] Polystyrene was dissolved in a dimethylacetamide solvent, to
obtain a polystyrene solution (30%) and the formed polymer solution
was spun into a yarns. The as-spun yarn properties of this test
item were measured and listed in Table 3a.
Example 4
[0072] Both polystyrene and polyvinylpyrrolidone were separately
dissolved in a dimethylacetamide solvent, to obtain a polystyrene
solution (30%) and a polyvinylpyrrolidone solution (20%).
Thereafter, a polymer blend solutions made from a polystyrene
solution (30%) and polyvinylpyrrolidone solution (20%) were spun
into a yarns. The as-spun yarn properties of this test item were
measured and listed in Table 3.
Example 5
[0073] Lower average number molecular weight polystyrene was
dissolved in a dimethylacetamide solvent, to obtain a polystyrene
solution (60%) and the formed polymer solution was spun into a
yarns. The as-spun yarn properties of this test item were measured
and listed in Table 3b
TABLE-US-00001 TABLE 1 Comparison of sheath-core spandex as-spun
yarn properties with control spandex yarn. Sample Number P1 P2 P3
P4 P5 P6 P7 P8 P9 P10 P11 P12 Sheath PUU PUU/St PUU/St PUU/St
PUU/St/ PUU/ PUU/ PUU PUU/St PUU/ PUU/ PUU/ Polymer Type PU SMMA
SAN BM IBM MB2766/St Weight 0 5 5 5 5 5 5 0 5 5 5 5 percentage of
Sheath in fiber (%) Sheath 0 98.25/1.75 90/10 70/30 40/30/30 90/10
90/10 0 80/20 80/20 80/20 80/10/10 Composition (%) Core Polymer PUU
PUU PUU PUU PUU PUU PUU PUU PUU PUU PUU PUU Type Thermoplastic 0
0.09 0.5 1.5 3 0.5 0.5 0 1 1 1 1 polymer in fiber (%) Denier 369
379 338 363 364 368 374 370 368 372 369 369.4 ELO 500 519 524 520
510 537 537 531 540 530 506 529 SET 26.5 26.8 27 29.3 28.8 28 29
26.7 27.6 28.2 28.5 28.1 PUU: Control spandex yarn
(polyurethaneurea); PU: Polyurethaneurea; St: Polystyrene; SMMA:
Poly(styrene-co-methyl methacrylate); SAN:
Poly(styrene-co-acrylonitrile); BM: Poly(butyl methacrylate); IBM:
Poly(isobutyl methacrylate); MB2766: Acrylic resins.
[0074] Table 1 illustrates the properties of the sheath-core
bicomponent spandex fibers suitable to the present invention. While
P1 is the control, the regular spandex, samples P2-10 are
sheath-core spandex fibers made according to the present invention.
It can be seen from the above examples that dry spinning of a
solution mixture of a segmented polyurethane with polymeric
additive including but not limited to polystyrene,
poly(styrene-co-methyl methacrylate);
poly(styrene-co-acrylonitrile), poly(butyl methacrylate) and
derivatives has no significant negative impact to the yarn
properties. The slight deviations seen in the elongation and set
data of these fibers were expected and they are attributable to the
addition of polymeric additives into the individual spandex
yarns.
[0075] Overall, the sheath-core bicomponent spandex fibers P2-10
were found to have excellent properties such as high elongation and
similar set to the regular spandex, P1.
[0076] Bonding Results
[0077] After bonding the bicomponent spandex fibers to nonwovens,
the samples were tested for bond retention (100-% Creep Retention)
according to the method described earlier. In a diaper application,
bond performance for spandex fibers is said to be good typically
when the bond retention is either more than 60%, preferably more
than 70%, more preferably more than 75%, most preferably more than
80% in a specific test described hereinafter when it is done within
2 days after hot melt adhesive has been applied on substrates.
These tests are indicative of what level of adhesion and bond
retention can be achieved by a hot melt adhesive. Because of the
high cost of hot melt adhesives, the adhesives are used in an
add-on amount lower than 18 gsm (grams of adhesive material per
square meter of substrate covered by the adhesive material), more
preferably equal to or lower than 15 gsm, and most preferably equal
to or lower than 12 gsm, U.S. Pat. No. 20090264580.
[0078] In the present invention, the bond performance of
sheath-core spandex fibers is illustrated by the specific examples
shown in Table 2a-b.
TABLE-US-00002 TABLE 2a-b Comparison in bonding retention of
sheath-core spandex as-spun yarn properties with control spandex
yarn using 7, 11, and 15.5 gsm of ZeroCreep .TM. add-ons. Adhesive
Adhesive Adhesive add-on add-on add-on (gsm) % Bond (gsm) % Bond
(gsm) % Bond 7 gsm retention 11 gsm retention 15.5 gsm retention a)
P1 50.0 P1 65.0 P1 82.0 P2 59.0 P2 77.0 P2 85.0 P3 67.0 P3 74.0 P3
84.0 P4 66.0 P4 78.0 P4 85.0 P5 65.0 P5 76.0 P5 85.0 P6 57.0 P6
79.0 P6 83.0 P7 63.0 P7 77.0 P7 84.0 b) P8 67.0 P8 75.0 P8 86.0 P9
74.0 P9 82.0 P9 88.0 P10 72.0 P10 80.0 P10 86.0 P11 74.0 P11 79.0
P11 88.0 P12 75.0 P12 82.0 P12 88.0
[0079] From Table 2a-b, it is clear that the inventive bicomponent
fibers exhibited greater bond retention to nonwoven fabrics than
the control spandex fiber.
[0080] When the ZeroCreep.TM. add-on is 7 gsm, the bicomponent
spandex fibers P2-7 and P9-12 display good bond performance than
the control spandex fibers P1 or P8 (Table 2a-b). It should be
noted that fibers with polystyrene and poly(butyl methacrylate)
additives display higher bond retention.
[0081] At ZeroCreep.TM. add-on equivalents to 11 gsm, all six
bicomponent fibers claimed by the present invention have superior
bondability to nonwovens than the control spandex fiber. As seen
previously, the bond retention increased more when polystyrene and
poly(butyl methacrylate) are used in fibers sheath.
[0082] When the ZeroCreep.TM. add-on is 15.5 gsm, all inventive
fibers (P2-7 and P9-12) including the control ones (P1 and P8)
exhibited much higher bond retention. Still, the inventive
bicomponent fibers display a better creep retention compared to the
control fiber.
TABLE-US-00003 TABLE 3a Comparison of monocomponent spandex as-spun
yarn properties with control spandex yarn. Sample Number P13 P14
P15 Polymer PUU1 PUU1/St PUU1/St/PVP Type Thermoplastic 0 0.875
98.25/0.875/0.875 polymer in fiber (%) Denier 745.5 739.5 NA ELO
492.75 520.25 500.0 TEN 423.8 522.45 409.8 TP2 81.06 83.72 97.71
TM2 16.55 15.96 15.07 SET 25.55 27.95 28.5 PUU1: Control spandex
yarn (polyurethaneurea); St: Polystyrene; PVP:
polyvinylpyrrolidone.
TABLE-US-00004 TABLE 3b Comparison of monocomponent spandex as-spun
yarn properties with control spandex yarn. Sample Number P16 P17
P18 Polymer PUU2/St1 PUU2/St1 PUU2 Type Thermoplastic 2.5 4.2 0
polymer in fiber (%) Target Denier 720 720 720 ELO 465 477 503 TEN
380 410 388 TP2 84.2 84.8 85.3 TM2 15.7 15.4 15.3 SET 27.3 28.1
26.5 PUU2: Control spandex yarn (polyurethaneurea); St1: low
average number molecular weight polystyrene
TABLE-US-00005 TABLE 4 Comparison in bonding retention of
monocomponent spandex as-spun yarn properties with control spandex
yarn using 7, 11, and 15.5 gsm of ZeroCreep .TM. add-ons. Adhesive
Adhesive Adhesive add-on add-on add-on (gsm) % Bond (gsm) % Bond
(gsm) % Bond 7 gsm retention 11 gsm retention 15.5 gsm retention
P13 53.0 P13 80.0 P13 87.0 P14 63.0 P14 79.0 P14 87.0 P15 58.0 P15
78.0 P15 84.0
TABLE-US-00006 TABLE 5 Comparison in bonding retention of
monocomponent spandex as-spun yarn properties with control spandex
yarn using 15 and 20 mg/m/strand of Technomelt .RTM. DM 800B mady
be Henkel. Adhesive Adhesive add-on % Bond add-on % Bond 15
mg/m/strand retention 20 mg/m/strand retention P16 82.3 P16 89.2
P17 83.5 P17 88.7 P18 77.6 P18 87.7
[0083] Tables 4 and 5 show the inventive fibers exhibit better bond
retention than the control.
[0084] While there have been described what are presently believed
to be the preferred embodiments of the invention, those skilled in
the art will realize that changes and modifications may be made
thereto without departing from the spirit of the invention, and it
is intended to include all such changes and modifications as fall
within the true scope of the invention.
* * * * *