U.S. patent application number 10/112219 was filed with the patent office on 2003-03-27 for multifunctional textiles.
This patent application is currently assigned to University of California. Invention is credited to Sun, Gang.
Application Number | 20030056297 10/112219 |
Document ID | / |
Family ID | 23074162 |
Filed Date | 2003-03-27 |
United States Patent
Application |
20030056297 |
Kind Code |
A1 |
Sun, Gang |
March 27, 2003 |
Multifunctional textiles
Abstract
The present invention provides a multifunctional textile
composition, the textile composition comprises a textile having an
antimicrobial functionality; and a chemical agent attached thereto
to impart an additional functionality. Suitable additional
functionalities include, but are not limited to, waterproof
finishing, soil repellent finishing, fire resistance finishing,
wrinkle free finishing, anti-UV finishing, and antistatic
finishing. By imparting additional functionalities, the textile
composition is rendered more versatile.
Inventors: |
Sun, Gang; (Davis,
CA) |
Correspondence
Address: |
TOWNSEND AND TOWNSEND AND CREW, LLP
TWO EMBARCADERO CENTER
EIGHTH FLOOR
SAN FRANCISCO
CA
94111-3834
US
|
Assignee: |
University of California
Berkeley
CA
|
Family ID: |
23074162 |
Appl. No.: |
10/112219 |
Filed: |
March 29, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60280687 |
Mar 30, 2001 |
|
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|
Current U.S.
Class: |
8/115.51 |
Current CPC
Class: |
D06M 15/3562 20130101;
D06M 15/29 20130101; D06M 13/364 20130101; D06P 1/39 20130101; D06M
13/352 20130101; D06M 13/358 20130101; D06M 15/285 20130101; D06M
13/355 20130101; D06M 15/263 20130101 |
Class at
Publication: |
8/115.51 |
International
Class: |
D06M 010/00 |
Claims
What is claimed is:
1. A multifunctional textile composition, said textile composition
comprising: a textile having an antimicrobial functionality; and a
chemical agent attached thereto to impart an additional
functionality.
2. The multifunctional textile composition of claim 1, wherein said
additional functionality is a member selected from the group
consisting of a waterproof finishing, soil repellent finishing,
fire resistance finishing, wrinkle free finishing, anti-UV
finishing, and antistatic finishing.
3. The multifunctional textile composition of claim 2, wherein said
additional functionality is a waterproof finishing.
4. The multifunctional textile composition of claim 3, wherein said
waterproofing finishing is imparted with an agent selected from the
group consisting of a fluorocarbon agent and a silicone agent.
5. The multifunctional textile composition of claim 2, wherein said
additional functionality is a fire resistant finishing.
6. The multifunctional textile composition of claim 5, wherein said
fire resistance finishing is imparted with a agent selected from
the group consisting of a phosphorus agent, a nitrogen agent, a
bromine agent, an antimony agent and combinations thereof.
7. The multifunctional textile composition of claim 2, wherein said
additional functionality is a wrinkle free finishing.
8. The multifunctional textile composition of claim 2, wherein said
additional functionality is an anti-UV finishing.
9. The multifunctional textile composition of claim 8, wherein said
anti-UV finishing is imparted with agent selected from the group
consisting of an ultraviolet absorbent or a light stabilizer.
10. The multifunctional textile composition of claim 2, wherein
said additional functionality is an antistatic and softening
finishing.
11. The multifunctional textile composition of claim 1, wherein
said textile is a member selected from the group consisting of
cellulosic, cellulosic-polyester, polyester, nylon, polypropylene,
acrylics, cotton, wool, silk, polyamide, aramid, olefin, spandex,
vinyon, vinyl, graphite, and combinations and blends thereof.
12. The multifunctional textile composition of claim 1, wherein
said antimicrobial functionality is imparted with a member selected
from the group consisting of a heterocyclic N-halamine and an
antimicrobial polymer.
13. The multifunctional textile composition of claim 12, wherein
said antimicrobial functionality is imparted with a heterocyclic
N-halamine.
14. The multifunctional textile composition of claim 13, wherein
said heterocyclic N-halamine is a halogenated product of a member
selected from the group consisting of
monomethylol-5,5-dimethylhydantoin (MDMH),
1,3-dimethylol-5,5-dimethylhydantoin (DMDMH); monomethylolated and
dimethylolated derivatives of
2,2,5,5-tetramethyl-1,3-imidazolidin-4-one,
6,6-dimethyl-1,3,5-triazine-2, 4-dione,
4,4,5,5-tetramethyl-1,3-imidazoli- din-2-one, cyanuric acid and
5,5-dimethylhydantoin; and monomethoxylated and dimethoxylated
derivatives of monomethylolated and dimethylolated derivatives of
2,2,5,5 -tetramethyl- 1,3-imidazolidin-4-one, 6,6-dimethyl-
1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazoli-
din-2-one, cyanuric acid, 5,5-dimethylhydantoin.
15. The multifunctional textile composition of claim 12, wherein
said antimicrobial functionality is imparted with an antimicrobial
polymer.
16. The multifunctional textile composition of claim 15, wherein
said antimicrobial polymer comprises a mixture of monomeric units
having the formulae: 4wherein: A is a member selected from the
group consisting of NH, N--R.sup.8 and CR.sup.1R.sup.2, wherein
R.sup.8 is a halogen; R.sup.1 and R.sup.2, are each independently
selected from the group consisting of optionally substituted
(C.sub.1-C.sub.6)alkyl, optionally substituted
(C.sub.2-C.sub.6)alkenyl, optionally substituted
(C.sub.2-C.sub.6)alkynyl- , optionally substituted cycloalkyl,
optionally substituted (C.sub.1-C.sub.6)alkoxy, optionally
substituted aryl and optionally substituted heteroaryl; or, R.sup.1
and R.sup.2 and the carbon to which they are bound join to form an
optionally substituted carbocyclic or optionally substituted
heterocyclic ring; Q is a member selected from the group consisting
of C(O), NH, N--R.sup.9 and CR.sup.3R.sup.4, wherein R.sup.9 is a
halogen; R.sup.3 and R.sup.4, are each independently selected from
the group consisting of optionally substituted (C.sub.1
-C.sub.6)alkyl, optionally substituted (C.sub.2-C.sub.6)alkenyl,
optionally substituted (C.sub.2-C.sub.6)alkynyl, optionally
substituted cycloalkyl, optionally substituted
(C.sub.1-C.sub.6)alkoxy, optionally substituted aryl and optionally
substituted heteroaryl; or, R.sup.3 and R.sup.4 and the carbon to
which they are bound, join to form an optionally substituted
carbocyclic or optionally substituted heterocyclic ring. X is a
member selected from the group consisting of C(O)--NR.sup.10 and
CR.sup.6R.sup.7, wherein R.sup.10 is a member selected from the
group consisting of hydrogen, halogen, optionally substituted
(C.sub.2-C.sub.6)alkenyl and optionally substituted
(C.sub.1-C.sub.6)alkyl; R.sup.6 and R.sup.7, are each independently
selected from the group consisting of optionally substituted
(C.sub.1-C.sub.6)alkyl, optionally substituted
(C.sub.2-C.sub.6)alkenyl, optionally substituted
(C.sub.2-C.sub.6)alkynyl, optionally substituted cycloalkyl,
optionally substituted (C.sub.1-C.sub.6)alkoxy, optionally
substituted aryl and optionally substituted heteroaryl; or, R.sup.6
and R.sup.7 and the carbon to which they are bound join to form an
optionally substituted carbocyclic or optionally substituted
heterocyclic ring; Z is a member selected from the group consisting
of optionally substituted (C.sub.1-C.sub.3)alkylene, C(O), or a
single bond; R.sup.11 is a member selected from the group
consisting of hydrogen, halogen, hydroxyl, cyano,
(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl,
(C.sub.1-C.sub.6)alkoxy- , (C.sub.1-C.sub.6)alkylcarbonyl,
(C.sub.1-C.sub.6)alkylcarboxyl, aldehydo, amido, aryl and
heterocyclyl; R.sup.12 is a member selected from the group
consisting of hydrogen, halogen, hydroxyl, cyano,
(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl,
(C.sub.1-C.sub.6)alkoxy- , (C.sub.1 -C.sub.6)alkylcarbonyl,
(C.sub.1-C.sub.6)alkylcarboxyl, aldehydo, amido, aryl and
heterocyclyl; R.sup.13 is a member selected from the group
consisting of hydrogen, halogen, hydroxyl, cyano,
(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl,
(C.sub.1-C.sub.6)alkoxy- , (C.sub.1 -C.sub.6)alkylcarbonyl,
(C.sub.1-C.sub.6)alkylcarboxyl, aldehydo, amido, aryl and
heterocyclyl; R .sup.14 is a member selected from the group
consisting of hydrogen, halogen, hydroxyl, cyano,
(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl,
(C.sub.1-C.sub.6)alkoxy- , (C.sub.1-C.sub.6)alkylcarbonyl,
(C.sub.1-C.sub.6)alkylcarboxyl, aldehydo, amido, aryl and
heterocyclyl; n and y are each independently an integer from 1 to
250 inclusive.
17. The multifunctional textile composition of claim 16, wherein: n
is 1 and y is 1.
18. The multifunctional textile composition of claim 16, wherein: A
is NH and Z is CH.sub.2.
19. The multifunctional textile composition of claim 15, wherein
said antimicrobial polymer comprises at least one functional
monomeric unit having the formula: 5wherein: R.sup.15, R.sup.16 and
R.sup.17 are each independently, a member selected from the group
consisting of hydrogen, halogen, hydroxyl, cyano,
(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkeny- l,
(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylcarbonyl,
(C.sub.1-C.sub.6)alkylcarboxyl, aldehydo, amido, aryl and
heterocyclyl; R.sup.18 is a member selected from the group
consisting of --CO.sub.2.sup.-X.sup.1+, SO.sub.3.sup.--X.sup.1+,
--O.sup.-X.sup.1+, --PO.sub.4.sup.-2Z X.sup.1+ and
--PO.sub.3.sup.-2Z X.sup.1+; X.sup.1 is a member selected from the
group consisting of a quaternary ammonium salt, a basic dye, and a
mixture thereof; Z.sup.1 is a member selected from the group
consisting of hydrogen and an alkaline earth metal; and m is an
integer from 1 to 250 inclusive.
20. The antimicrobial polymer according to claim 19, wherein said
polymer is a long-chain synthetic acrylic polymer or fiber
comprising at least 35% by weight of acrylonitrile units.
21. The antimicrobial polymer according to claim 19, wherein said
polymer is a nylon.
22. A process for preparing a multifunctional textile, said process
comprising: (a) preparing a textile having an antimicrobial
functionality to generate an antimicrobial textile; and (b)
treating said antimicrobial textile with a chemical agent to impart
an additional functionality, thereby preparing said multifunctional
textile.
23. The process of claim 22, wherein said additional functionality
is a member selected from the group consisting of waterproofing,
soil repellent finishing, fire resistance finishing, wrinkle free
finishing, anti-UV finishing, and antistatic and softening
finishing.
24. The method of claim 23, wherein said additional functionality
is a waterproofing finishing.
25. The method of claim 24, wherein said waterproofing finishing is
imparted with a fluorocarbon agent or silicone agent.
26. The method of claim 23, wherein said additional functionality
is a fire resistant finishing.
27. The method of claim 26, wherein said fire resistance finishing
is imparted with a agent selected from the group consisting of a
phosphorus agent, a nitrogen agent, a bromine agent, an antimony
agent and combinations thereof.
28. The method of claim 23, wherein said additional functionality
is a wrinkle free finishing.
29. The method of claim 23, wherein said additional functionality
is an anti-UV finishing.
30. The method of claim 29, wherein said anti-UV finishing is
imparted with agent selected from the group consisting of an
ultraviolet absorbent or a light stabilizer.
31. The method of claim 23, wherein said additional functionality
is an antistatic and softening finishing.
32. The method of claim 22, wherein said textile is a member
selected from the group consisting of cellulosic,
cellulosic-polyester, polyester, nylon, polypropylene, acrylics,
cotton, wool, silk, polyamide, aramid, olefin, spandex, vinyon,
vinyl, graphite, and combinations and blends thereof.
33. The method of claim 22, wherein said antimicrobial
functionality is imparted with a member selected from the group
consisting of a heterocyclic N-halamine and an antimicrobial
polymer.
34. The method of claim 33, wherein said antimicrobial
functionality is imparted with a heterocyclic N-halamine.
35. The method of claim 33, wherein said antimicrobial
functionality is imparted with an antimicrobial polymer.
36. The method of claim 34, wherein said heterocyclic N-halamine is
a halogenated product of a member selected from the group
consisting of monomethylol-5,5-dimethylhydantoin (MDMH),
1,3-dimethylol-5,5-dimethylhyd- antoin (DMDMH); monomethylolated
and dimethylolated derivatives of
2,2,5,5-tetramethyl-1,3-imidazolidin-4-one,
6,6-dimethyl-1,3,5-triazine-2- ,4-dione,
4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and
5,5-dimethylhydantoin; and monomethoxylated and dimethoxylated
derivatives of monomethylolated and dimethylolated derivatives of
2,2,5,5-tetramethyl-1,3-imidazolidin-4-one,
6,6-dimethyl-1,3,5-triazine-2- ,4-dione, 4,4,5,5-tetramethyl-
1,3-imidazolidin-2-one, cyanuric acid, and
5,5-dimethylhydantoin.
37. A garment, said garment comprising: an antimicrobial
functionality; and a chemical agent attached thereto to impart an
additional functionality.
38. The garment of claim 37, wherein said additional functionality
is a member selected from the group consisting of a waterproof
finishing, soil repellent finishing, fire resistance finishing,
wrinkle free finishing, anti-UV finishing, and antistatic
finishing.
39. The garment of claim 37, wherein said garment is selected form
the group consisting of a surgeon's gown, a cap, a mask, a surgical
cover, a patient drape, carpeting, a bedding material, underwear, a
sock and a uniform.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 60/280,687, filed Mar. 30, 2001, the
teaching of which are incorporated herein by reference in their
entirety.
BACKGROUND OF THE INVENTION
[0002] Textiles are very important materials related to human life
and living that provide decorative and protective functions. Our
modem lifestyle has created increased demands on new textile
products, ranging from simply comfort feeling to multi-protective
functions against various hazardous or severe environments. Today's
textile products are not simply apparels, decorations, and
classical textiles, but should also be advanced shields to human
bodies that are capable of preventing attacks from pathogenic
microorganisms, toxic chemicals, flame, UV radiation, and
potentially any natural hazards. There are more demands in many
specialty textiles in the current textile market, for example,
durable and reusable hygienic clothing that can inactivate
pathogens and prevent skin infections, antiodor or antimicrobial
carpets that can improve indoor air quality, as well medical-use,
institutional-use textiles, and the like.
[0003] Antimicrobial textiles play an important role in preventing
cross transmission of infectious diseases in hospital and
healthcare facilities due to the proven evidence that the textiles
are major hosting media for the microorganisms (see, Sun, G. et
al., Durable and Regenerable Antimicrobial Finishing of Fabrics
with a New Hydantoin Derivative, Industrial Engineering Chemistry
Research, Vol. 41, 1016-1021. 2001; Worley, S. D. et al., (1996)
"Biocidal Polymers" Trends in Polymer Science. V4, p. 364-370; and
Rigby, A. J. et al., (1993), Textile Horizons, Dec., 42-46).
[0004] These antimicrobial materials can be divided into two
categories based on their abilities to combat microorganisms, i.e.,
biocidal and biostatic functions. Biocidal functions refer to the
complete inactivation of microorganisms on the materials or total
kill, while biostatic properties indicate the inhibition of growth
of microorganisms by the materials or partial kill. Based on these
definitions, bio-protective clothing should be made of biocidal
fabrics instead of the ones in the second category because of the
specific functions required for the protection. Biostatic fabrics
would be more appropriate for aesthetic and hygienic type
applications of textile products, as well as used in antiodor
textiles.
[0005] In recent years, there has been the development of
innovative technologies that prepare durable functional textiles,
including biocidal clothing. For example, cellulose related
materials have been generated by using covalent bonding (see, Sun,
G., et al., Textile Chemist and Colorist, 30(6):26 (1998); Sun, G.,
et al., Textile Chemist and Colorist, 31(5):31 (1999)); Sun, G., et
al., Textile Chemist and Colorist, 31(1):21-24 (1999)). However,
due to the lack of reactive groups in most synthetic fibers, there
exist limited practical options i.e. few intermolecular
interactions to achieve durable functions on polymers.
[0006] Among the currently investigated biocidal materials,
N-halamines have been shown to provide almost instant and total
kill of a wide range of microorganisms. (see, Worley, S. D. et al.,
Trends Polym. Sci ., 11:364 (1996)). There are many advantages
associated with using N-halamine structures. First, they are stable
in long-term use and storage over a wide temperature range. Second,
they are regenerable when activity is lost due to normal use
patterns. (see, Sun, G. et al., Polymer, 37:3753 (1996); Worley, S.
D. et al., The Polymeric Materials Encyclopedia, 1, A-B, p. 550
(1996); Sun, G. et al. Water Res. Bull., 1996, 32:793 (1996)). More
recently, N-halamine materials have been incorporated into
cellulose-containing fabrics. (see, Bickert, J. R. et al.,
International Conference on Safety &Protective fabric '98,
1998, p 1; Sun, G. et al., Textile Chem. Colorist, 6:26 (1998);
Sun, G. et al., Textile Chem. Colorist, 31:21 (1999)). Results
indicate that as little as 1% (wt) add-on of halamine structures
provide powerful biocidal efficacy (6-7 log reduction) against the
most common pathogens, at a contact time of two minutes.
[0007] U.S. Pat. No. 5,882,357, issued to Sun et al., on Mar. 16,
1999, discloses durable and regenerable microbiocidal textiles and
methods for preparing the same. The microbiocidal textiles are
prepared using a wet finishing process to covalently attach a
heterocyclic N-halamine to a cellulose-based material or other
polymeric material. The biocidal activity of the textiles can be
regenerated by washing with a halogenated solution.
[0008] Moreover, PCT Publication WO 00/15897 published Mar. 23,
2000, to Sun et al., discloses durable and refreshable
antimicrobial polymers such as textiles, that have excellent
colorfastness and washfastness. The textiles are suitable for
sportswear, antiodor carpets, films, plastics, toys and medical
uses. In that invention, dye molecules are used as connectors or
bridges between the textile and antimicrobial agents.
[0009] In addition, U.S. patent application Ser. No. 09/662,999,
entitled "Antimicrobial Polymers," to Sun et al., filed Sep. 15,
2000, describes antimicrobial polymers compositions having a
functional monomeric unit; and an antimicrobial agent attached to
the functional monomeric unit. The monomeric unit preferably
includes a functional group such as a carboxylate group, a
sulfonate group, an oxide group, an alkoxide, a phosphate or a
phosphonate group. The antimicrobial polymers are preferably
antimicrobial textiles, which can be used in a wide variety of
applications. Suitable applications include surgeon's gowns, caps,
masks, surgical covers, patient drapes, carpeting, bedding
material, underwear, socks, sportswear and healthcare uniforms.
[0010] U.S. Pat. No. 6,020,491, issued to Wonley et al., on Feb. 1,
2000, discloses cyclic amine monomers and polymers that are used to
form biocidal N-halamine polymers. The polymers are useful as
disinfectants for potable water, swimming pools, hot tubs,
industrial water systems, cooling towers, air-conditioning systems,
and the like.
[0011] Despite the advances made in the art, there exists a need
for new antimicrobial textiles having additional functionality.
Textiles having multifunctional features are needed for myriad
applications. For example, medical-use clothing may require both
waterproofing and antimicrobial properties, while some sportswear
should provide both anti-UV and odor-free performance. The
development of multifunctional textiles based on antimicrobial
technologies is needed. The present invention provides these and
other needs.
SUMMARY OF THE INVENTION
[0012] Textiles having multifunctional features are needed for
medical applications, industrial safety clothing and sportswear
use. For example, medical-use clothing may require both
waterproofing and antimicrobial properties, while some sportswear
should provide both anti-UV and odor-free performance. As such, in
one embodiment, the present invention provides a multifunctional
textile composition, the textile composition comprising: a textile
having an antimicrobial functionality; and a chemical agent
attached thereto to impart an additional functionality. Suitable
additional functionalities include, but are not limited to,
waterproof finishing, soil repellent finishing, fire resistance
finishing, wrinkle free finishing, anti-UV finishing, and
antistatic finishing. By imparting additional functionalities, the
textile composition is rendered more versatile.
[0013] In another embodiment, the present invention provides a
process for preparing the multifunctional textiles of the present
invention. The process comprises (a) preparing a textile having an
antimicrobial functionality to generate an antimicrobial textile;
and (b) treating the antimicrobial textile with a chemical agent to
impart an additional functionality, thereby preparing the
multifunctional textile.
[0014] In still yet another embodiment, the present invention
provides a garment or article comprising: an antimicrobial
functionality; and a chemical agent attached thereto to impart an
additional functionality. The garment can be for example, a
surgeon's gown, a cap, a mask, a surgical cover, a patient drape,
and the like. The garment can be prepared for example, using the
textiles of the present invention.
[0015] Numerous benefits are achieved by way of the present
invention over conventional techniques. There are many potential
application areas for the new textile materials. For example, the
new textile material is not only a physical barrier to
microorganisms, in addition, it can provide a disinfectant property
as well. This regenerable and reusable biocidal material can
replace currently used disposable nonwoven fabrics in hospitals,
and serve as a safeguard to medical workers and patients. The
antimicroorganism properties of the textile materials of the
present invention, particularly the antiodor properties, can impart
beneficial properties to apparel products such as underwear, socks,
and sportswear. Moreover, the antimicrobial fabrics are
advantageous to hotels and institutions for such uses as towels,
bedding materials, carpets, and wall covers, as a safeguard in
preventing cross-contamination of infectious diseases. Depending
upon the embodiment, one or more of these benefits may be
achieved.
[0016] Various additional objects, features and advantages of the
present invention can be more fully appreciated with reference to
the detailed description and accompanying drawings that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a simplified diagram of a chemical modification
process according to an embodiment of the present invention;
[0018] FIG. 2 illustrates examples of heterocyclic N-halamines
precursors suitable for use in the present invention;
[0019] FIG. 3 is a simplified flow diagram that illustrates a
chemical modification process according to an embodiment of the
present invention;
[0020] FIG. 4 is a simplified diagram of a chemical modification
process according to an embodiment of the present invention;
[0021] FIG. 5 illustrates various disperse dyes suitable for use
according to an embodiment of the present invention;
[0022] FIG. 6 illustrates various acid dyes suitable for use
according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
I. MULTIFUNCTIONAL TEXTILES
[0023] The present invention provides durable multifunctional
textiles and fabrics. In one embodiment, the present invention
provides a multifunctional textile composition, the textile
composition comprising: a textile having an antimicrobial
functionality; and a chemical agent attached thereto to impart an
additional functionality. The terms "antimicrobial,"
"microbicidal," or "biocidal" as used herein, refer to the ability
to kill at least some types of microorganisms, or to inhibit the
growth or reproduction of at least some types of microorganisms.
The textiles prepared in accordance with the present invention have
microbicidal activity (antimicrobial) against a broad spectrum of
pathogenic microorganisms. The textiles have microbicidal activity
against representative gram-positive (such as Staphylococcus
aureus) or gram-negative bacteria (such as Escherichia coli) or
combinations thereof. In certain preferred aspects, the
microbicidal activity of such textiles is readily regenerable.
[0024] The term "multifunctional textile" as used herein, refers to
a microbiocidal textile as previously defined, comprising an
additional functionality. Suitable additional functionalities
include, but are not limited to, waterproof finishing, soil
repellent finishing, fire resistance finishing, wrinkle free
finishing, anti-UV finishing, and antistatic finishing. By
imparting additional functionalities, the textile composition is
rendered more versatile.
[0025] A. ANTIMICROBIAL FUNCTIONALITY
[0026] 1. Heterocyclic N-Halamines
[0027] The multifunctional textiles of the present invention
comprise, for example, antimicrobial properties. As discussed in
detail herein, the antimicrobial functionality can be imparted in a
variety of ways. In a preferred embodiment, the multifunctional
textile compositions of the present invention have antimicrobial
functionality imparted using heterocyclic N-halamine chemistry. For
example, U.S. Pat. No. 5,882,357, which issued to Sun et al. on
Mar. 16, 1999, and incorporated herein by reference, teaches an
antimicrobial textile composition comprising: a textile material
such as cellulose, cellulosic-polyester and polyester material; and
a heterocyclic N-halamine covalently attached to the textile
material. The antimicrobial textile material is both durable and
regenerable.
[0028] "Heterocyclic N-halamine," as used herein, refers to a 4- to
7-membered ring, wherein at least 3 members of the ring are carbon,
and from 1 to 3 members of the ring are nitrogen(s) heteroatom, and
from 0 to 1 member of the ring is an oxygen atom, wherein from 0 to
2 carbon members comprise a carbonyl group, and wherein at least 1
to 3 nitrogen atoms are substituted with a hydrogen or hydroxyalkyl
group, such as --CH.sub.2OH, or a alkoxyalkyl group, such as
--CH.sub.2OCH.sub.3. At least one ring nitrogen has bonded thereto
a halogen atom. In addition, the ring members can be further
substituted with alkyl groups, such as methyl, ethyl, and the like
or hydroxy groups. Heterocyclic N-halamines are generally disclosed
in U.S. Pat. No. 5,490,983 issued to Worley, et al. on Feb. 13,
1996, the teachings of which are incorporated herein by reference
for all purposes.
[0029] FIG. 1 shows schematically 100 an example of a heterocyclic
amine 110 being covalently bonded to cellulose 105 to produce a
cellulose-potential biocide moiety 120. After activation with a
halogen source 130, a cellulose-biocide is generated 150 (e.g.,
heterocyclic N-halamines). Precursors of the heterocyclic
N-halamines 120 suitable for use in the present invention are
exemplified in FIG. 2. Examples include, but are not limited to,
monomethylol-5,5-dimethylhydantoin (MDMH),
1,3-dimethylol-5,5-dimethylhydantoin (DMDMH); monomethylolated and
dimethylolated derivatives of
2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-
1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazoli-
din-2-one, cyanuric acid and 5,5-dimethylhydantoin; and
monomethoxylated and dimethoxylated derivatives of monomethylolated
and dimethylolated derivatives of
6,6-dimethyl-1,3,5-triazine-2,4-dione,
4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid,
5,5-dimethylhydantoin, 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one
and mixtures thereof.
[0030] With reference to FIG. 3, the antimicrobial functionality
can be imparted using process 300. This diagram is merely an
example, which should not limit the scope of the claims herein. One
of ordinary skill in the art would recognize many other variations,
modifications, and alternatives. As illustrated in FIG. 3, the
process comprising (a) immersing a cellulosic textile in an aqueous
treating solution, which comprises a catalyst, a wetting agent and
a heterocyclic amine 310; removing the excess treating solution
from the cellulosic textile 320; (c) drying the cellulosic textile
330; (d) curing the dried cellulosic textile 340; (e) washing the
cured cellulosic textile to remove excess reagents 350; (f) drying
the cellulosic textile to remove water 360; and (g) treating the
cellulosic textile with a halogenated aqueous solution to produce a
heterocyclic N-halamine, thereby preparing a microbiocidal
cellulosic textile 370. The foregoing process is claimed and taught
in U.S. Pat. No. 6,077,319, which issued to Sun et al. on Jun. 20,
2000 and is incorporated herein by reference in its entirety for
all purposes. In certain aspects, waterproofing, fire resistant
agents and the like, can be added in the finishing bath 310 so as
to achieve multifunctional textiles of the present invention.
[0031] Advantageously, the foregoing process is executed by the
utilization of redox reactions. Thus, the potential biocidal groups
110 can be activated by a common laundering process 130, which will
enable users to functionalize the materials at any convenient time.
In addition, laundering bleaches such a CLOROX.RTM. are household
chemicals that normally do not possess harmful effects to wearers
and handlers who wash and regenerate the functional fabrics.
[0032] In certain instances, a byproduct of producing antimicrobial
articles using heterocyclic N-halamine chemistry is the release of
free-formaldehyde. To reduce the amount of free-formaldehyde
release, in certain aspects, the above process optionally further
comprises: (a) immersing the article or textile in an aqueous
treating solution which comprises a heterocyclic amine and a
polyol; and (b) treating the article with a halogenated solution,
thereby rendering the article microbiocidal with a reduction in
free-formaldehyde release. Suitable polyols include, but are not
limited to, diethylene glycol or ethylene glycol. In certain
preferred embodiments, the heterocyclic amine is alkylated or
partially alkylated. Such processes are described and taught in
U.S. Pat. No. 6,241,783, issued to Sun on Jun. 5, 2001, and is
hereby incorporated by references in its entirety for all
purposes.
[0033] 2. Polymer:Bridge:Biocide Motif
[0034] In other embodiments, the antimicrobial properties can be
imparted using a dye or colorant as a bridge between the textile
and an antimicrobial agent. The chemistry is illustrated in FIG. 4.
This schematic diagram 400 is merely an example, which should not
limit the scope of the claims herein. One of ordinary skill in the
art would recognize many other variations, modifications, and
alternatives.
[0035] FIG. 4 shows an antimicrobial polymer composition 440
comprising: a polymer material having a colorant 420 and an
antimicrobial agent or biocide 430 attached to the colorant 420.
The colorant 420 acts as a bridge and can be a dye or a pigment. In
one embodiment, the polymer 410 is a textile, such as a fabric. In
certain preferred aspects, colorants, such as dyes, are used as
connectors, bridges or links 420, to firmly attach the microbicidal
agents to the polymer. In other aspects, the dyes contain
auxochromes, such as sulfonic, hydroxyl and amino groups that can
be used to facilitate color shades and solubility requirements. The
antimicrobial agents 430 are amphipathic molecules. Preferably, the
antimicrobial agents are quaternary ammonium salts. Such
antimicrobial textile can be generated using a process comprising:
a) dyeing a polymer with a colorant to form a polymer having the
colorant attached thereto; and b) attaching a antimicrobial agent
to the colorant, thereby making the polymer antimicrobial. The
colorant can be a dye or a pigment.
[0036] In certain aspects, the biocide 430 is a quaternary ammonium
salt. Suitable quaternary ammonium salts include, but are not
limited to, dodecyltrimethyl ammonium bromide (DTAB),
N-(3-chloro-2-hydroxypropyl)-N,- N-dimethyldodecylammonium
chloride, 1,3-Bis-(N,N-dimethyldodecylammonium
chloride)-2-propanol, dodecyltrimethyl ammonium chloride (DTAC),
N-(1-(2,3-dioleoyloxy)propyl)-N,N,N-trimethylammonium chloride
(DOTAP), N-(1-(2,3-dioleyloxy)propyl)-N,N,N-trimethylammonium
chloride (DOTMA), dimethyldioctadecyl ammonium bromide (DDAB),
N,N-dioleyl-N,N-dimethylammo- nium chloride (DODAC) and
1,2-dioleoyloxy-3-(N,N,N--trimethylamino)propane chloride (DOTAP).
Preferably, the quaternary ammonium salts are dodecyltrimethyl
ammonium bromide (DTAB), N-(3-chloro-2-hydroxypropyl)-N,-
N-dimethyldodecylammonium chloride,
1,3-Bis-(N,N-dimethyldodecylammonium chloride)-2-propanol, cetyl
pyridinium chloride (CPC), and benzyldimethylhexadedylammonium
chloride (BDHAC).
[0037] Antimicrobial textiles formed using the
polymer:brige:biocide motif are set forth and taught in U.S. patent
application Ser. No. 09/151,891, filed Sep. 11, 1998, published as
WO 00/15897 on Mar. 23, 2000, and is hereby incorporated by
reference for all purposes.
[0038] The refreshing process 480 is the regular laundering
practice, which removes cell bodies 450 that are killed by the
biocides but are left on the surface. In certain aspects,
waterproofing, fire resistant agents and the like, can be added in
the finishing bath so as to achieve multifunctional textiles of the
present invention.
[0039] 3 . Antimicrobial Heterocyclic Polymers
[0040] In certain other embodiments, the antimicrobial
functionality can be imparted using heterocyclic vinylic amines,
which can be readily polymerized with most acrylic,
substituted-acrylic and vinyl monomers. The polymers thus generated
exhibit biocidal efficacy after exposure to a halogen source, such
as chlorine bleach. The antimicrobial polymer comprises a mixture
of monomeric units having the formulae: 1
[0041] wherein:
[0042] A is a member selected from the group consisting of NH,
N--R.sup.8 and CR.sup.1R.sup.2, wherein R.sup.8 is a halogen;
[0043] R.sup.1 and R 2, are each independently selected from the
group consisting of optionally substituted (C.sub.1-C.sub.6)alkyl,
optionally substituted (C.sub.2-C.sub.6)alkenyl, optionally
substituted (C.sub.2-C.sub.6)alkynyl, optionally substituted
cycloalkyl, optionally substituted (C.sub.1-C.sub.6)alkoxy,
optionally substituted aryl and optionally substituted
heteroaryl;
[0044] or, R.sup.1 and R.sup.2 and the carbon to which they are
bound join to form an optionally substituted carbocyclic or
optionally substituted heterocyclic ring;
[0045] Q is a member selected from the group consisting of C(O),
NH, N--R.sup.9 and CR.sup.3R.sup.4, wherein R.sup.9 is a
halogen;
[0046] R.sup.3 and R.sup.4, are each independently selected from
the group consisting of optionally substituted
(C.sub.1-C.sub.6)alkyl, optionally substituted
(C.sub.2-C.sub.6)alkenyl, optionally substituted
(C.sub.2-C.sub.6)alkynyl, optionally substituted cycloalkyl,
optionally substituted (C.sub.1-C.sub.6)alkoxy, optionally
substituted aryl and optionally substituted heteroaryl;
[0047] or, R.sup.3 and R.sup.4 and the carbon to which they are
bound, join to form an optionally substituted carbocyclic or
optionally substituted heterocyclic ring.
[0048] X is a member selected from the group consisting of
C(O)--NR.sup.10 and CR.sup.6R.sup.7, wherein R.sup.10 is a member
selected from the group consisting of hydrogen, halogen, optionally
substituted (C.sub.2-C.sub.6)alkenyl and optionally substituted
(C.sup.1-C.sub.6)alkyl;
[0049] R.sup.6 and R.sup.7, are each independently selected from
the group consisting of optionally substituted
(C.sub.1-C.sub.6)alkyl, optionally substituted
(C.sub.2-C.sub.6)alkenyl, optionally substituted
(C.sub.2-C.sub.6)alkynyl, optionally substituted cycloalkyl,
optionally substituted (C.sub.1-C.sub.6)alkoxy, optionally
substituted aryl and optionally substituted heteroaryl;
[0050] or, R.sup.6 and R.sup.7 and the carbon to which they are
bound join to form an optionally substituted carbocyclic or
optionally substituted heterocyclic ring;
[0051] Z is a member selected from the group consisting of
optionally substituted (C.sub.1-C.sub.3)alkylene, C(O), or a single
bond;
[0052] R.sup.11 is a member selected from the group consisting of
hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.6)alkyl,
(C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)alkoxy,
(C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)alkylcarboxyl,
aldehydo, amido, aryl and heterocyclyl;
[0053] R.sup.12 is a member selected from the group consisting of
hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.6)alkyl,
(C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)alkoxy,
(C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)alkylcarboxyl,
aldehydo, amido, aryl and heterocyclyl;
[0054] R.sup.13 is a member selected from the group consisting of
hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.6)alkyl,
(C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)alkoxy,
(C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)alkylcarboxyl,
aldehydo, amido, aryl and heterocyclyl;
[0055] R.sup.14 is a member selected from the group consisting of
hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.6)alkyl,
(C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)alkoxy,
(C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)alkylcarboxyl,
aldehydo, amido, aryl and heterocyclyl; and
[0056] n and y are each independently an integer from 1 to 250
inclusive. In certain preferred aspects, n is 1 and y is 1. In
equally preferred aspects, A is NH and Z is CH.sub.2. The biocidal
heterocyclic vinylic amines are taught in U.S. patent application
Ser. No. 09/535,348, filed Mar. 24, 2000, published as WO 01/72715
on Oct. 4, 2001, and is hereby incorporated by reference in its
entirety for all purposes.
[0057] Vinyl monomers suitable for use in the present invention
include, but are not limited to, an acrylic monomer, a
monofunctional vinyl monomer, a polyfunctional vinyl monomer and
mixtures thereof. The polymerization reaction proceeds with a
compound set forth below: 2
[0058] where in A, Q X, N and Z were defined above previously, and
at least one other existing vinyl monomer, optionally in the
presence of a free radical initiator. The reaction can take place
in bulk, an aqueous solution, a suspension, an organic solvent, or
emulsion.
[0059] Once formed, the polymers can be made biocidal by reacting
the corresponding unhalogenated polymers, with a halogen source.
Suitable halogenating agents include, but are not limited to,
calcium hypochlorite, sodium hypochlorite (e.g., CLOROX.RTM.),
N-chlorosuccinimide, N-bromosuccinimide, sodium
dichloroisocyanurate, trichloroisocyanuric acid, tertiary butyl
hypochlorite, N-chloroacetamide, N-chloramines, N-bromamines, and
the like. In certain aspects, waterproofing, fire resistant agents
and the like, can be added in the finishing bath so as to achieve
multifunctional textiles of the present invention.
[0060] The halogenation of the unhalogenated polymers can be
accomplished in aqueous media or in mixtures of water with common
inert organic solvents such as methylene chloride, chloroform, and
carbon tetrachloride, or in inert organic solvents themselves, at
room temperature. Those of skill in the art will know of other
solvents or solvent mixtures suitable for use in the present
invention. In certain instances, the unhalogenated polymers can be
a previously-utilized cyclic N-halamine polymer that needs to be
regenerated due to inactivation of the N-halamine moieties. As used
herein, "halogenating" or "halogenated" polymers refers to
partially as well as fully halogenated. Preferred halogens are
chlorine and bromine.
[0061] 4. Antimicrobial Polymers
[0062] In another embodiment, the antimicrobial functionality of
the multifunctional textile composition of the present invention
can be imparted using other antimicrobial polymers. For example,
reactive or functional groups in polymers (e.g. acrylics and
nylons) such as anionic groups, can be employed as a point of
attachment for antimicrobial agents. Dye molecules having a
complementary functional group, such as a cationic group, can
penetrate into and reside in the polymers to form strong
interactions, such as ionic interactions, with their counterparts
(e.g., anionic group). The present invention provides a
multifunctional textile having an antimicrobial polymer composition
comprising: a) a polymer having a functional monomeric unit; and b)
an antimicrobial agent attached to the functional monomeric unit.
The functional monomeric unit serves as a point of attachment for
interaction with the antimicrobial agent. In certain instances, the
antimicrobial composition employs ionic interactions between
polymers such as acrylic polymers, and polyamides, and
antimicrobial agents such as quaternary ammonium salts. In certain
aspects, the finishing conditions, polymer morphology, and
structure of the antimicrobial agents play important roles in
achieving durable performance of the compositions. Preferably, the
composition comprises a synthetic organic polymer such as an
acrylic polymer, or polyamides (nylons and Aramid), or cationic
dyeable polyester. The polymer can be a fiber woven into a
textile.
[0063] In a preferred embodiment, the antimicrobial polymer
comprises at least one functional monomeric unit having the
formula: 3
[0064] wherein:
[0065] R.sup.15, R.sup.16 and R .sup.17are each independently, a
member selected from the group consisting of hydrogen, halogen,
hydroxyl, cyano, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl,
(C.sup.l-C.sub.6)alkoxy- ,
(C.sub.1-C.sub.6)alkylcarbonyl),C.sup.1-C.sup.6 )alkylcarboxyl,
aldehydo, amido, aryl and heterocyclyl;
[0066] R.sup.18 is a member selected from the group consisting of
--CO.sub.2.sup.-X.sup.1+, SO.sub.3.sup.-X.sup.1+,
--O.sup.-X.sup.1+, --PO.sub.4.sup.-2Z X.sup.1+ and
--PO.sub.3.sup.-2Z X.sup.1+;
[0067] X.sup.1 is a member selected from the group consisting of a
quaternary ammonium salt, a basic dye, metal ions such as Ag.sup.+,
Au.sup.+, Cu.sup.++ and the like, and a mixtures thereof;
[0068] Z.sup.1 is a member selected from the group consisting of
hydrogen and an alkaline earth metal; and m is an integer from 1 to
250 inclusive. In certain preferred embodiments, such antimicrobial
polymers comprise a long-chain synthetic acrylic polymer or fiber
comprising at least 35% by weight of acrylonitrile units or fibers
containing other reactive groups such as nylons.
[0069] A wide variety of polymers can be used in the present
invention. Suitable polymers include, but are not limited to,
fibers from plants, polymers from animals, natural organic
polymers, synthetic organic polymers and inorganic substances. In a
preferred aspect, synthetic organic polymers such as acrylic
polymers and polyamides are used. In certain aspects, the acrylic
polymers suitable for use in the present invention have a number
average molecular weight of about 40,000 to about 60,000 or about
1000 to about 1500 repeat units. The weight average molecular
weight is about 90,000 to about 140,000, with the polydispersity
index between about 1.5 to about 3.0.
[0070] Moreover, in certain embodiments, the polymer is a plurality
of polymers. Suitable plurality of polymers include, but are not
limited to, fibers, films, textiles and plastics. In preferred
aspects, the antimicrobial fibers are acrylic fibers or polyamides
fibers. As used herein, the term "acrylic fiber" means any manmade
fiber derived from acrylic resins comprising a minimum of 85%
acrylonitrile, contained therein. Acrylic fiber is a manufactured
fiber in which the fiber forming substance is any long-chain
synthetic polymer comprising at least 85% by weight of
acrylonitrile units (--CH.sub.2--CH[CN]--).sub.x. As used herein
the term "modacrylic fiber" means a fiber having less than 85% by
weight of acrylonitrile units, but at least 35% by weight of
acrylonitrile units.
[0071] In a preferred embodiment, the acrylic fibers used in the
present invention are made from acrylonitrile and at least one
other functional monomer. The functional monomers have a functional
group, preferably an ionic functional group. Suitable functional
groups include, but are not limited to, a carboxylate
(--CO.sub.2.sup.-) group, a sulfonate (SO.sub.3.sup.-) group, a
hydroxide (--OH) group, an alkoxide (--RCH.sub.2O.sup.-) group, a
phosphate (--PO.sub.4.sup.-2) group and a phosphonate
(--PO.sub.3.sup.-2) group. In a preferred aspect, the functional
monomer comprises a negatively charged functional monomer such as a
sulfonate (SO.sub.3.sup.-) group. Functional monomers comprising a
sulfonate group include, but are not limited to, sodium
styrenesulfonate, sodium methyallyl sulfonate and sodium
sulfophenyl methyallyl ether.
[0072] Suitable acrylic fibers are produced by various
manufactures. Suitable acrylic fibers for use in the present
invention include, but are not limited to, MicroSupreme.RTM.,
Creslof.TM., Creslan.RTM. Plus, BioFresh.TM., WeatherBloc.TM.
(commercially available from Sterling Fibers, Inc.); Dralon.TM.
(commercially available from Bayer Inc.) Acrilan.RTM.,
Bounce-Back.RTM., Duraspun.RTM., Pil-Trol.RTM., Sayelle.RTM.,
Sno-Brite.TM., The Smart Yarns.RTM., Wear-Dated.RTM. and
Wintuk.RTM. (commercially available from Solutia Inc.). Other
acrylic fibers include Orlon.RTM., Acrilin.RTM. acrylic,
Dolan.RTM., Dralon.RTM., Vinyon N.RTM., Dynel.RTM., Verel.RTM., SEF
modacrylic.RTM.. Polyamide fibers include, but are not limited to,
all nylon fibers such as nylon 6, nylon 66, Nomex, Kermel, and
Kevlar. Those of skill in the art will know of other manufactures
and trade names of acrylic fibers suitable for use in the present
invention.
[0073] In certain aspects, waterproofing, fire resistant agents and
the like, can be added in the finishing bath so as to achieve
multifunctional textiles of the present invention.
[0074] B. ADDITIONAL FUNCTIONALITIES
[0075] In addition to antimicrobial features, the present invention
provides textiles having additional functionalities. Suitable
additional functionalities include, but are not limited to,
waterproof finishing, soil repellent finishing, fire resistance
finishing, wrinkle free finishing, anti-UV finishing, and
antistatic finishing. By imparting additional functionalities, the
textile composition is rendered more versatile.
[0076] 1. Durable Waterproofing and Soil Repellent Finishing
[0077] In certain aspects, the textiles of the present invention
have functionalities of waterproofing and soil repellency.
Waterproofing can be imparted by treating the fabrics in a
finishing bath containing a chemical agent such as fluorocarbons,
silicones, or other waterproofing agents. Preferably, hydrophilic
fabrics or materials are used. These hydrophilic fabrics include,
but are not limited to, cotton, cotton containing fabrics, wool,
wool containing fabrics, silk and silk containing fabrics.
[0078] Soil-repellent finishing can be used to prevent the fabrics
and materials from soiling easily. Preferred soil-repellant
chemical agents are fluorocarbon chemicals. Suitable waterproofing
and soil-repellent chemical agents include, but are not limited to,
3M Protective Chemical.RTM. (commercially available from 3M),
SEQUAPEL.RTM. (commercially available from Omnova Solutions Inc.),
FREE PEL.RTM. (commercially available from BF Goodrich Performance
Materials), BARPEL.RTM. (commercially available from Apollo
Chemical Corp.), GLO-PEL.RTM. and GLO-GUARD.RTM. (commercially
available from Glo-Tex International Inc.).
[0079] 2. Fire-Resistant Finishing
[0080] In certain aspects, the textiles of the present invention
have a fire resistant functionally. Fire-resistant treatments are
used advantageously for home furnishing and some apparel textiles.
The function can be achieved by treating the materials with flame
retardant chemicals such as phosphorus, nitrogen, bromine, and
antimony containing compounds, and combinations thereof. Examples
include, but not limited to, GUARDEX PFR.RTM. (commercially
available from Glo-Tex International Inc.), BARFIRE.RTM.
(commercially available from Apollo Chemical Corp.), PYROVATEX
CP.RTM. (commercially available from Ciba Specialty Chemicals) and
PYROSAN.RTM. (commercially available from BF Goodrich Performance
Materials).
[0081] 3. Wrinkle Free Finishing
[0082] In another aspect, the textiles of the present invention
have wrinkle free functionality. A wrinkle free functionality is an
important feature for pure cotton and cotton blend fabrics, and
fabrics containing other natural fibers such as wool and silk.
Examples include, but are not limited to, FREEREZ.RTM.
(commercially available from BF Goodrich Performance Materials) and
PERMAFRESH.RTM. (commercially available from Omnova Solutions
Inc.).
[0083] 4. Anti-UV Finishing
[0084] In certain other aspect, the textiles of the present
invention have anti-UV functionality. Anti-UV functions are
advantageously used for protection of both wearers and textile
materials. Both employ similar chemicals, i.e. ultraviolet
absorbents or light stabilizers. Typical examples include, but are
not limited to, CBAFAST.RTM. (commercially available from Ciba
Specialty Chemicals), SUNLIFE.RTM. (commercially available from
NICCA USA Inc.), and ORCO SUNGUARD.RTM. (commercially available
from Organic Dyestuffs Corp).
[0085] 5. Antistatic Finishing
[0086] In certain other aspects, the textiles of the present
invention have antistatic functionality. Antistatic treatment
advantageously removes static charges built up on surfaces of
textiles. The mechanism is to create a conductive layer on the
surface, so charges cannot accumulated upon friction between
surfaces of textile materials. Antistatic function is required for
some institutional clothing and textiles, such as garments worn by
petroleum workers, firefighters, and micro-electronic workers.
Examples of antistatic agents include, but are not limited to,
BARSTAT.RTM. (commercially available from Apollo Chemical Corp.),
ZEROSTAT.RTM. (commercially available from Ciba Specialty
Chemicals), and DOW CORNING FLUID.RTM. (commercially available from
Dow Coming Corp).
II. TEXTILES
[0087] The textiles suitable for the present invention include, but
are not limited to, naturally occurring fibers from plants, such as
cellulose, cotton, linen, hemp, jute and ramie. They include
polymers from animals, based upon proteins and include, but are not
limited to, wool, mohair, vicuna and silk. Textiles also include
manufactured fibers based upon natural organic polymers such as,
rayon, lyocell, acetate, triacetate and azlon. Textiles suitable
for use in the present invention include synthetic organic polymers
which include, but are not limited to, acrylic, aramid, nylon,
olefin, polyester, spandex, vinyon, vinyl and graphite. Textiles
also include inorganic substances such as glass, metallic and
ceramic.
[0088] Considering both antibacterial and mechanical properties of
the finished textiles prepared using the methods and compositions
set forth herein, those of skill will readily appreciate that such
finished textiles can advantageously be used in the preparation of
the following articles/garments: surgeon's gowns, caps, masks,
surgical cover, patient drapes, carpeting, bedding materials,
underwear, socks, uniforms, and the like. Those of skill in the art
will readily appreciate that the finished textiles of the present
invention can also advantageously be used for a variety of other
purposes, such as in hotel-use towels, bedding materials, hygienic
products, in various clothing to protect against pesticides and
other toxic chemicals, and the like.
[0089] Numerous applications for the multifunctional textiles of
the present invention exist. For instance, the multifunctional
textiles can provide biocidal protective clothing to personnel in
the medical area as well as in the related healthcare and hygiene
area. The regenerable and reusable biocidal materials can replace
currently used disposable, nonwoven fabrics as medical textiles,
thereby significantly reducing hospital maintenance costs and
disposal fees. The multifunctional textiles of the present
invention can be advantageously used for women's wear, underwear,
socks, sportswear and other hygienic purposes. In addition, the
multifunctional properties can be imparted to carpeting materials
to create odor-free and germ-free carpets. Moreover, all germ-free
environments, such as required in biotechnology and pharmaceutical
industry, would benefit from the use of the microbicidal textiles
of the present invention to prevent any contamination from air,
liquid, and solid media.
[0090] The multifunctional textiles are effective against all
microorganisms. Such microorganisms include, for example, bacteria,
protozoa, fungi, viruses and algae. Moreover, the multifunctional
textiles described herein can be employed in a variety of
disinfecting applications, such as water purification. They will be
of importance in controlling microbiological contamination or
growth of undesirable organisms in the medical and food
industries.
III. METHODS
[0091] One or more beneficial functionalities can be imparted to
the textiles of the present invention. For example, the durable and
regenerable antimicrobial function can be incorporated to textile
materials possessing UV-protection with one or more of the above
regular wet finishing processes.
[0092] In certain aspects, fabrics can be treated in one finishing
bath containing the biocidal agent (such as DMDMH) and other
functional agents (such as anti-UV chemicals or flame retardants).
In other aspects, fabrics are first treated with the antimicrobial
agents and then treated with other functional agents. In still
further aspects, fabrics are treated with other functional agents
and then with the antimicrobial agents. All such treatment
sequences and combinations are contemplated in the present
invention.
[0093] In a preferred method, the chemical finishing of fabrics by
biocidal or potential biocidal agents and other functional
compounds are carried out concurrently in a wet finishing process.
The effects of concentrations of finishing agents, catalysts,
carrier of biocides, and other chemicals are optimized in terms of
the best biocidal and mechanical properties as well as the best
economical concerns.
[0094] In a preferred method, an aqueous treating solution
comprises a heterocyclic amine or a polymer comprising a
heterocyclic amine as described above, a wetting agent and a
catalyst. In certain aspects, waterproofing, fire resistant agents
and the like, can be added in the finishing bath so as to achieve
multifunctional textiles of the present invention. As used herein,
"wetting agent" refers to a substance that increases the rate at
which a liquid spreads across a surface, i.e., it renders a surface
nonrepellent to a liquid. Examples of suitable wetting agents
include, but are not limited to, Triton X-100.RTM. (Sigma Chemical
Co., St. Louis, Mo.), SEQUAWET.RTM. (Sequal Chemical Inc., Chester,
S.C.), and AMWET.RTM. (American Emulsions Co., Dalton, Ga.). Other
wetting agents suitable for use in the present invention will be
known to and used by those of skill in the art. As used herein,
"catalyst" refers to a substance which augments the rate of a
chemical reaction without itself being consumed. Suitable catalysts
for use in the present invention include, but are not limited to,
the following: magnesium salts, zinc salts and ammonium salts. In a
presently preferred embodiments, the catalyst employed is one of
the following: MgCl.sub.2, Mg(NO.sub.3).sub.2, Zn(NO.sub.3).sub.2
and NH.sub.4NO.sub.3.
[0095] Those of skill in the art will readily appreciate that the
concentration of the various components of the aqueous treating
solution can be widely varied depending upon the particular
components employed and the results desired. Typically, the
heterocyclic amine is present at a concentration of at least about
0.2%. More typically, the heterocyclic amine is present at a
concentration ranging from about 0.2% to about 20%, more preferably
at a concentration ranging from about 0.5% to about 10% and, more
preferably at a concentration ranging from about 1% to about 5%. It
will be readily apparent to those of skill in the art that higher
heterocyclic amine concentrations (e.g., 50%) can be employed, but
such higher concentrations are not required to impart microbiocidal
activity. Again, suitable microbiocidal activity can be imparted
using a heterocyclic amine concentration as low as about 0.2%. The
wetting agent is typically present at a concentration ranging from
about 0.1% to about 3% and, more preferably, at a concentration
ranging from about 0.2% to about 1%. The concentration of the
catalyst employed will depend on the concentration of the
heterocyclic amine employed. Typically, the ratio of heterocyclic
amine to catalyst present will range from about 10:1 to about 5:1.
The pH of the aqueous treating solution will typically range from a
pH of about 2 to about 6 and, more preferably, from a pH of about
2.5 to about 4.5.
[0096] Those of skill in the art will readily appreciate that other
additives can be incorporated into the aqueous treating solution to
impart favorable characteristics to the cellulosic,
cellulosic/polyester or polyester textile. Such additives can
include softeners and waterproofing agents which are known to and
used by those of skill in the art.
[0097] In carrying out step 310 in FIG. 3, the textile used may be
roving, yarn or fabric regardless of whether spun, knit, or woven,
or may be nonwoven sheets or webs. Moreover, the textile may be
made of cellulosic fibers, polyester fibers or blends of these. In
addition, other polymer materials having reactive functional groups
(e.g., --OH groups) can be used. Such polymer materials include,
but are not limited to, polyvinyl alcohol (PVA), starches and
proteins. In wetting the textile in the finishing or treating bath,
ordinary textile equipment and methods suitable for batchwise or
continuous passage of roving, yarns or fabrics through an aqueous
solution may be used, at any speed permitting thorough and uniform
wetting of the textile material.
[0098] In step 320, the excess aqueous treating solution is removed
by ordinary mechanical methods such as by passing the textile
between squeeze rolls, by centrifugation, by draining or by
padding. In a preferred embodiment, the excess aqueous treating
solution is removed by padding.
[0099] In step 330, the cellulosic, cellulosic/polyester or
polyester textile is dried at a temperature ranging from about
50.degree. C. to about 90.degree. C. and, more preferably, at a
temperature ranging from about 75.degree. C. to about 85.degree. C.
for a period of time ranging from about 3 to about 8 minutes and,
more preferably, for about 5 minutes.
[0100] In step 340, the dried cellulosic, cellulosic/polyester or
polyester textile is cured at a temperature ranging from about
100.degree. C. to about 200.degree. C. and, more preferably, at a
temperature ranging from about 140.degree. C. to about 160.degree.
C. for a period of time ranging from about 3 to about 8 minutes
and, more preferably, for about 5 minutes. The heating can be
carried out in an oven, preferably one having a forced draft of air
directed at the surface of the textile and exhausting through a
vent to remove fumes.
[0101] In step 350, the dried cellulosic, cellulosic/polyester or
polyester textile is washed. Washing of the treated textile, step
(d), may be done with either hot or cold water. The covalent bonds
formed are stable, insoluble, and durable to the mechanical
agitation, spraying and rubbing that occurs in washing machines or
in large scale continuous or batchwise textile washing
equipment.
[0102] Final drying, step 360, can be carried out by any ordinary
means such as oven drying, line drying or tumble drying in a
mechanical clothes dryer. A drying temperature of about 80.degree.
to about 120.degree. C. for about 1 to about 5 minutes is
particularly preferred.
[0103] Antimicrobial, waterproofing, or fire-resistant
functionalities, together with mechanical properties of the fabrics
are evaluated by following related AATCC or ASTM test methods.
After every five times of washing, the textile materials are
regenerated with diluted bleach solutions and tested against
microorganisms according to American Association of Textile
Chemists and Colorists (AATCC) test methods. The breaking strengths
of the regenerated fabrics are examined. A standard commercial
dryer is used to evaluate the stability of modified cellulose under
different drying conditions after bleaching. Drying temperature is
varied from room temperature to high temperature tumble dry. After
each drying circle, biocidal properties and tensile strengths of
the dried textile materials will be tested again.
[0104] As described earlier, in the polymer:brige:biocide motif,
colorants, such as dye molecules, are used as connectors or bridges
between the textile and the antimicrobial agent. The dye molecules
suitable for different synthetic polymers have excellent
washfastness and durability. The dyes which can be used include,
but are not limited to, an acid dye, a disperse dye, a direct dye
and a reactive dye. With reference to FIG. 5, various disperse dyes
are suitable for use in the present invention. These disperse dyes
include, but are not limited to, Disperse Blue 1, Disperse Yellow 7
and Disperse Yellow 9. Those skilled in the art will be aware of
various other disperse dyes suitable for use in the present
invention.
[0105] In a preferred embodiment, an acid dye is used. Suitable
acid dyes include, but are not limited to, Acid Black dye, an Acid
Blue dye, an Acid Orange dye, an Acid Red dye, an Acid Violet dye,
and an Acid Yellow dye. FIG. 6 lists various acid dyes suitable for
use in the present invention.
[0106] In one embodiment, acid dyes are preferably used with Nylon
66, Nylon 6, wool, and silk. In another embodiment, disperse dyes
are used with Nylon 66, Nylon 6, Nomex, acetate, triacetate,
acrylics, polyester, polypropylene, and blended fabrics. Disperse
dyes are also suitable for use in plastic products, such as colored
films, toys, computer keyboards and other polymeric products
wherein a antimicrobial material is needed.
[0107] In certain embodiments, the colorants, such as dye
molecules, also contain auxochromes, including, but not limited to,
sulfonic groups, hydroxyl groups, quaternary groups and amino
functional groups. These auxochromes facilitate the color and
solubility requirements of the colorant. In addition, these
reactive groups serve to anchor the microbicidal agent. The
auxochromes of the dyes serve to chemically modify the polymers
such as fibers. These dye molecules then serve as bridges by
bringing functional groups onto the polymers, such as fibers, and
then linking the biocidal agents. For example, a sulfonate group
can form an ionic bond with a cationic species like a quaternary
salt, or vice versa. In another example, an amino group and a
hydroxyl group are reactive with alkyl halides, epoxide, and acetyl
groups. Hence, the dye molecules act as bridges to bring functional
groups onto polymers and thereby serving as a point of attachment
for the biocidal agents.
[0108] In one embodiment, the linkage between the colorant and the
antimicrobial agent is an ionic bond formation between a sulfonate
anion on an acid dye and an amphipathic molecule, such as a
quaternary ammonium salt of a antimicrobial agent. In another
embodiment, the linkage is a covalent bond between an amino or
hydroxyl group on a disperse dye and an epoxy or alkyl halide
structures of a antimicrobial agent. In both cases, quaternary
ammonium salts are employed as the antimicrobial agent.
[0109] Anionic dyes can interact with positive quaternary ammonium
salts due to coulumbic forces, such an interaction can be reflected
from the add-on rates of the salts on dyed and undyed fabrics, as
well as the weight loss of the sample after repeated washing.
Moreover, polyamide structures can form hydrogen bonds or van der
Waals interactions with the quaternary ammonium salts, which can
result in an add-on of the salts on undyed fabrics. Disperse dyes
can covalently link to reactive quaternary ammonium salts,
including, but not limited to, N-(3-chloro-2-hydroxypropy-
l)-N,N-dimethyldodecylammonium chloride.
[0110] In this process various colorants can be used. These
include, but are not limited to pigments and dye molecules. The
colorants are used as connectors between the textile and the
antimicrobial agents. The dye molecules suitable for different
synthetic polymers have excellent washfastness and durability. The
dyes which can be used include, but are not limited to, an acid
dye, a disperse dye, a direct dye and a reactive dye. In a
preferred embodiment, an acid dye is used. Suitable acid dyes
include, but are not limited to, Acid Black dye, an Acid Blue dye,
an Acid Orange dye, an Acid Red dye, an Acid Violet dye, and an
Acid Yellow dye.
[0111] In certain embodiments, the colorants, such as dye molecules
also contain auxochromes, such as sulfonic, hydroxyl and amino
functional groups. These auxochromes facilitate the color and
solubility requirements of the colorant.
[0112] Those of skill in the art will readily appreciate that the
concentration of the various components of the aqueous treating
solution can be widely varied depending upon the particular
components employed and the results desired. Typically, the
colorant is present at a concentration for an "on weight fabric"
(o.w.f.) of about 0.1% to about 15%. More typically, the colorant
is present at a concentration ranging from about 0.2% to about 5%,
more preferably at a concentration ranging from about 0.5% to about
2%.
[0113] The polymer, such as a textile material, is dyed in the
colorant solution at about 80.degree. C. to about 100.degree. C.
for about 1 hour to about 3 hours. More typically, about 90.degree.
C. to about 95.degree. C. for about 80 min. to about 90 min. The
liquor ratio, which is the ratio of fabric to dye solution (w/w),
ranges from about 1:100 to about 1:25, and more preferably about
1:75 to about 1:45, most preferably about 1:50. The pH of the dye
bath is adjusted to about pH=1 to about pH=6, more preferably,
pH=2.0 to about pH=5 with a weak acid, including, but not limited
to, acetic acid. The dyed polymers, such as fabrics, are then
washed with an AATCC standard detergent after dyeing and cured. The
curing temperature is set to about 90.degree. C. to about
150.degree. C., more preferably 100.degree. C. to about at
125.degree. C., most preferably 115.degree. C. to about 125.degree.
C. The cure time is about 5 min to about 30 mins, more preferably
10 min to about 20 minutes.
[0114] The antibacterial finishing bath is then prepared by
dissolving an antimicrobial agent, such as a quaternary ammonium
salt, in distilled water. In certain aspects, waterproofing, fire
resistant agents and the like, can be added in the finishing bath
so as to achieve multifunctional textiles of the present invention.
The pH value is adjusted to about pH=1 to about pH=6, more
preferably, pH=2.0 to about pH=5 with a weak acid, such as acetic
acid. The dyed textile is dipped in the antibacterial agent
solution, padded to a wet pick up of about 50% to about 120%, more
preferably about 60% to about 100% and then cured at an elevated
temperature for an extended period. The antimicrobial agent is
typically present at a concentration ranging from about 0.1% to
about 30% and, more preferably, at a concentration ranging from
about 0.2% to about 10%.
[0115] In another embodiment, the textiles, such as fabrics, are
dyed by an acid dye and then treated in a quaternary ammonium salt
solution wherein the treatment is performed in a pressurized dyer
or by padding and then curing at a high temperature. Another
embodiment involves mixing the acid dye with a quaternary ammonium
salt in a bath and directly dyeing or treating the fabric
simultaneously.
[0116] When using the disperse dye, the treatment can be done by
dyeing fabrics first with a disperse dye, then dipping the dyed
fabrics in a quaternary ammonium salt solution and padding the
fabrics to a wet pick-up rate of 60-120%. The fabrics are cured at
about 150-170.degree. C. for 5-15 minutes and then washed. Disperse
dyes or pigments can be mixed with reactive quaternary ammonium
salts under basic conditions (pH>10) in an aqueous solution. The
mixture is stirred and warmed for about 30 minutes, and then
diluted to 1% o.w. f. Fabrics can be either dipped into the
solution, padded at a wet pick-up rate of 60-120%, and cure at
150-170.degree. C. for about 5-30 minutes, or immersed in the
solution in a pressure dyer, and treated at 120.degree. C., 20 atm
pressure for 30 minutes. The fabrics are then washed and dried and
ready for testing.
[0117] The invention will be described in greater detail by way of
specific examples. The following examples are offered for
illustrative purposes, and are not intended to limit the invention
in any manner.
IV. EXAMPLES
EXAMPLE I
[0118] This example illustrates the finishing of fabrics with
antibiocidal and waterproofing functionalities.
[0119] A finishing bath containing 24 grams of
monomethylol-5,5-dimethyl-h- ydantoin, 4.8 grams magnesium
chloride, and 0.6 gram of Triton X-100 (a wetting agent) in 600
milliliters of deionized water was prepared. Waterproofing agents
can be added in the finishing baths so as to achieve
multifunctional properties on the products. The pH of the finishing
bath was adjusted to 3.4 with one milliliter of 0.1 N HCl solution.
Then, 140.9 grams of pure cotton fabric (#400 Testfabrics, Inc.,
Middlesex, N.J.) and 141.4 grams of cotton/polyester (35/65) blend
fabric (#7409, Testfabrics, Inc., Middlesex, N.J.) were dipped in
the bath for more than five minutes and padded through a padder
with a more than 80% pick-up rate. The fabrics were dipped and
padded again, and dried at 80.degree. C. for 5 minutes. The fabrics
were then cured at 160.degree. C. for 5 minutes. Finally, the
finished fabrics were machine washed with 90 grams of American
Association of Textile Chemists and Colorists (AATCC) Standard
Reference Detergent 124 at a low water level and a temperature of
about 60.degree. C. for 30 minutes. The fabrics were dried and
weighed, yielding 42.8 grams (1.35% add-on) of the cotton fabric
and 142.4 grams (0.71% add-on) of the cotton/polyester blend
fabric. The cotton product exhibited prominent infrared adsorption
bands in a KBr pellet at 1718 and 1770 cm.sup.-1.
[0120] Thereafter, the finished fabrics were washed with a diluted
Clorox solution containing about 0.01% active chlorine.
Antibacterial properties of the fabrics were tested against
representative gram-positive (such as Staphylococcu aureus (ATCC
5368)) and gram-negative bacteria (such as Escherichia coli (ATCC
2666)).
EXAMPLE II
[0121] This example illustrates the finishing of fabrics with
1,3-dimethylol-5,5-dimethylhydantoin (antimicrobial) and fire
resistance.
[0122] A finishing bath containing 48 grams of
1,3-dimethylol-5,5-dimethyl- hydantoin (DMDMH), 9.6 grams magnesium
chloride and 0.8 gram of Triton X-100 (a wetting agent) in 800
milliliters of deionized water was prepared. Fire resistant agents
can be added in the finishing baths so as to achieve
multifunctional properties on the products. The pH of the finishing
bath was adjusted to 3.1 with 20 milliliters of 0.01 N HCl
solution. Then, 144.7 grams of pure cotton fabric (#400
Testfabrics, Inc., Middlesex, N.J.) and 143.2 grams of
cotton/polyester (35/65) blend fabric (#7409, Testfabrics, Inc.,
Middlesex, N.J.) were dipped in the bath for more than five minutes
and padded through a padder with more than an 80% pick up rate. The
fabrics were dipped and padded again, and dried at 80.degree. C.
for 5 minutes. The fabrics were then cured at 160.degree. C. for 5
minutes. Finally, the finished fabrics were machine washed with 90
grams of AATCC Standard Reference Detergent 124 at a low water
level low and a temperature of about 60.degree. C. for 30 minutes.
The fabrics were dried and weighed, yielding 147.9 grams (2.22%
add-on) of the cotton fabric and 145.5 grams (1.62% add-on) of the
cotton/polyester blend fabric. The cotton product exhibited
prominent infrared adsorption bands in a KBr pellet at 1718 and
1770 cm.sup.-1.
[0123] Thereafter, the finished fabrics were washed with a diluted
Clorox solution containing about 0.01% active chlorine.
Antibacterial properties of the fabrics were tested against
representative gram-positive (such as Staphylococcu aureus (ATCC
5368)) and gram-negative bacteria (such as Escherichia coli (ATCC
2666)).
EXAMPLE III
[0124] This example illustrates the effectiveness of the technology
in the biological warfare agent.
[0125] The antibacterial textiles produced by using this technology
can effectively inactivate Bacillus subtilis (an anthrax
surrogate). Advantageously, by a contact time of 24 to 48 hours,
the fabrics can result in a 97-100% kill to this microorganism. The
results are as follows:
1 Treated non-woven textiles 1. 50/50 polyester/rayon 100% kill in
48 hours 2. Treated 100% rayon 97% kill in 24 hours 3. Treated
30/70 rayon/polypropylene 99.9% kill in 24 hours Treated woven
textiles 1. 100% cotton canvas 99.9% kill in 48 hours
EXAMPLE IV
[0126] This example illustrates the effectiveness of antibacterial
and water repellent treatment.
[0127] Bleached and desized cotton print cloth #400 and
cotton/polyester (35/65) #7409, supplied by Testfabrics Inc., were
used. Water and oil repellent Sequapel Wor were provided by Sequa
Chemicals, Inc. The fabrics were finished by using general wet
processes, and pad-dry-cure. A finishing bath containing 6% of
1,3-dimethylol-5,5-dimethylhydantoin (DMDMH), 2% Sequapel Wor
agent, 1.5% of magnesium chloride and 0.02% of Triton X-100 (a
wetting agent) in 800 milliliters of deionized water was prepared.
The pH of the finishing bath was adjusted to 3.5-4 by adding citric
acid. Then, pure cotton fabric (#400 Testfabrics, Inc., Middlesex,
N.J.) and cotton/polyester (35/65) blend fabric (#7409,
Testfabrics, Inc., Middlesex, N.J.) were dipped in the bath for
more than five minutes and padded through a padder with more than
an 80% pick up rate. The fabrics were dipped and padded again, and
dried at 80.degree. C. for 5 minutes. The fabrics were then cured
at 160.degree. C. for 5 minutes. Finally, the finished fabrics were
machine washed with 90 grams of AATCC Standard Reference Detergent
124 at a low water level and a temperature of about 60.degree. C.
for 30 minutes. The fabrics were dried and weighed, with 3.52%
add-on on the pure cotton and 2.17% add-on on the polyester/cotton
blend.
2TABLE 2 Water Droplet Angles on Treated Fabrics Treatment Washes
Fabric.sup.1 1 min 10 min 20 min 30 min 40 min 60 min 90 min 2% WR
+ 6% DMDMH 0 400 65 70 73 80 90 99 125 0 7409 65 70 73 77 84 90 120
2% WR + 6% DMDMH 5 400 63 79 87 87 98 112 140 5 7409 63 68 71 75 81
89 108 2% WR + 6% DMDMH 20 400 150 180 180 180 180 180 180 20 7409
92 92 103 106 111 131 175 2% WR + 6% DMDMH 50 400 165 180 180 180
180 180 180 50 7409 108 140 151 162 180 180 180 .sup.1400 Pure
Cotton; 7409 Cotton/Polyester Blend
[0128]
3TABLE 3 Antibacterial Results of Treated Fabrics Through 50 washes
Biocidal results of fabrics treated with Durability 2% WR & 6%
DMDMH Treatment Fabric E. Coli S. Au W0 bleach 400 6 log 6 log 7409
6 log 6 log W5 bleach 400 6 log 6 log 7409 6 log 6 log W10 bleach
400 6 log 6 log 7409 6 log 6 log W15 bleach 400 6 log 6 log 7409 6
log 6 log W20 bleach 400 6 log 6 log 7409 6 log 6 log W25 bleach
400 6 log 6 log 7409 6 log 6 log W30 bleach 400 6 log 6 log 7409 6
log 6 log W35 bleach 400 6 log 6 log 7409 6 log 6 log W40 bleach
400 6 log 6 log 7409 6 log 6 log W45 bleach 400 6 log 6 log 7409 6
log 6 log W50 bleach 400 6 log 6 log 7409 6 log 6 log
[0129] Advantageously, after 50 machine washings, the treated
fabrics were still maximally biocidally efficacious.
EXAMPLE V
[0130] This example illustrates the preparation of antibacterial
high performance fabrics Nomex, Kevlar, and Kermel (aromatic
imide-amide) fabrics treated by using the following method.
[0131] The finishing bath includes 3% 3-allyl-5,5-dimethylhydantoin
(ADMH), 2% poly(ethylene glycol)-diacrylate (PEG-DIA), 1.5% of a
commercial softener, and 0.5% of the initiator (such as benzoyl
peroxide (BPO) or 2,2'-Azobisisobutyronitrile(AIBN)). The fabrics
were dipped-padded twice at a 100% wet pick-up, dried at 50.degree.
C. for 5 min, cured at 140.degree. C. for 5 min, washed, dried at
60.degree. C. for 24 h, and stored in a condition room (25.degree.
C., 65% RH) for 48 h to reach constant weight. Percentage graft was
calculated from the relation:
Graft%=(W.sub.2-W.sub.1)/W.sub.1.times.100 (1)
[0132] wherein W.sub.1 and W.sub.2 are the weights of the original
and the grafted fabrics, respectively.
[0133] Halogenation
[0134] To transform the hydantoin structure in the grafted samples
to N-halamines, the grafted fabric was immersed in a diluted bleach
containing 3000 ppm active chlorine (bath ratio is 50:1) at room
temperature for 30 min, washed thoroughly with a large excess of
distilled water, and air dried. The active chlorine content of the
fabric was determined by a modified titration method. About 0.3
gram of the treated fabric was cut into small pieces, treated with
30 mL of 0.001 N sodium thiosulfate solution containing 0.05 wt %
of a non-ionic wetting agent (Triton X-100) at room temperature
under constant stirring over night. The excess sodium thiosulfate
was titrated with a 0.001 N iodine solution. Un-chlorinated grafted
fabrics were also titrated by using the same methods as controls.
Available active chlorine of the bleached grafted fabric was then
calculated from equation 2.
M.sub.c1=10.sup.-6.times.(V.sub.2-V.sub.1)/W (2)
[0135] Where V.sub.1 and V.sub.2 represent the volumes (mL) of
iodine solution used in the titration of the sodium thiosulfate
solutions treating the samples and the controls, respectively; and
W was the weight (g) of the bleached grafted fabric.
4TABLE 4 Percentage Reduction of E. coli and S. aureus After
Different Contact Time (Bacteria concentration:
10.sup.6.about.10.sup.7 CFU/mL) Mcl .times. 10.sup.5 E. coli S.
aureus Fabric Graft % (mol/g) 10 min 30 min 60 min 120 min 10 min
30 min 60 min 120 min Nomex 4.6 1.22 UD* 99.9 99.9999 99.9999 99
99.9999 99.9999 99.9999 Kemel 2.3 0.34 UD 90 99.9 99.9 UD 99.9
99.99 99.999 PBI/Kevlar 2.8 0.41 UD UD 99.9 99.9 UD 99.9999 99.9999
99.9999 *no reduction was detected.
[0136]
5TABLE 5 Percentage Reduction of the bacteria after Washing at a
Contact Time of 60 min (Bacteria concentration:
10.sup.6.about.10.sup.7 CFU/mL). All the samples were tested with
machine washing following AATCC Test Method 124. AATCC standard
reference detergent 124 was used in all the machine-washing tests).
Nomex Kermel PBI/Kevlar Wash M.sub.Cl .times. 10.sup.5 M.sub.Cl
.times. 10.sup.5 M.sub.Cl .times. 10.sup.5 times (mol/g) E. coli S.
aureus (mol/g) E. coli S. aureus (mol/g) E. coli S. aureus 0 1.22
99.9999 99.9999 0.33 99.9 99.999 0.41 99.9 99.9999 5 1.20 99.9999
99.9999 0.28 99.9 99.99 0.41 99.9 99.99 15 0.63 99.9999 99.999 0.23
99.9 99 0.37 99.9 99 30 0.27 99.9 99.99 UD* 90 90 0.20 90 99 50 UD*
90 90 UD* UD* UD* UD* UD* UD* 50** 1.14 99.9999 99.9999 0.29 99.9
99.999 0.43 99.9 99.9999 *no reduction was detected, and **these
samples were re-bleached after 50 times of washing.
[0137] It is to be understood that the above description is
intended to be illustrative and not restrictive. Many embodiments
will be apparent to those of skill in the art upon reading the
above description. The scope of the invention should, therefore, be
determined not with reference to the above description, but should
instead be determined with reference to the appended claims, along
with the full scope of equivalents to which such claims are
entitled. The disclosures of all articles and references, including
patent applications and publications, are incorporated herein by
reference for all purposes.
* * * * *