U.S. patent application number 16/808117 was filed with the patent office on 2020-10-08 for laundry additive for providing antimicrobial effects to fabrics and interior surfaces of washing machines.
The applicant listed for this patent is Vinod S. Nair, Gregory van Buskirk. Invention is credited to Vinod S. Nair, Gregory van Buskirk.
Application Number | 20200318284 16/808117 |
Document ID | / |
Family ID | 1000004901446 |
Filed Date | 2020-10-08 |
![](/patent/app/20200318284/US20200318284A1-20201008-C00001.png)
United States Patent
Application |
20200318284 |
Kind Code |
A1 |
van Buskirk; Gregory ; et
al. |
October 8, 2020 |
Laundry Additive for Providing Antimicrobial Effects to Fabrics and
Interior Surfaces of Washing Machines
Abstract
A laundry additive composition is provided that includes at
least one zeta potential modifier, a fluoropolymer, a hydrophobic
agent with a melting point or glass transition temperature below
100.degree. C., and an antimicrobial active for imparting fabric
protection benefits to a fabric, such as improved stain and soil
resistance, oil repellency, water repellency, softness, wrinkle and
damage resistance, and better hand feel, as well as imparting
microbiocidal or microbiostatic properties to the fabric and/or
washing machine surfaces. Laundry additive compositions can be used
as a pretreatment prior to washing, through soaking a fabric or
garment. Alternately, they can be added to a washing treatment
liquor that comprises either the wash or rinse cycle of an
automatic washing machine, to first provide and then maintain and
refresh fabric protection benefits imparted to the fabric.
Following use of a first treatment composition, protective benefits
are maintained and refreshed by means of a second treatment
operation employing a second treatment composition. The second
treatment composition may have lower active levels of the
protective agents to provide for economical and periodic
maintenance of the imparted fabric protection benefits and/or
refresh the microbiocidal or microbiostatic properties imparted to
fabrics and/or washing machine surfaces.
Inventors: |
van Buskirk; Gregory;
(Danville, CA) ; Nair; Vinod S.; (San Jose,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
van Buskirk; Gregory
Nair; Vinod S. |
Danville
San Jose |
CA
CA |
US
US |
|
|
Family ID: |
1000004901446 |
Appl. No.: |
16/808117 |
Filed: |
March 3, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14716871 |
May 19, 2015 |
10577743 |
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16808117 |
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14549555 |
Nov 21, 2014 |
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14716871 |
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12983864 |
Jan 3, 2011 |
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14549555 |
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11614197 |
Dec 21, 2006 |
7893014 |
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12983864 |
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10338350 |
Jan 8, 2003 |
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11614197 |
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60371452 |
Apr 9, 2002 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D06M 2200/01 20130101;
A01N 25/34 20130101; A01N 59/16 20130101; D06M 15/71 20130101 |
International
Class: |
D06M 15/71 20060101
D06M015/71; A01N 59/16 20060101 A01N059/16; A01N 25/34 20060101
A01N025/34 |
Claims
1. A method for treating a fabric to provide at least one fabric
protective property to the fabric, comprising: (1) depositing a
composition onto the fabric in a treatment liquor, wherein the
composition comprises: a. from 5 to 30 weight % of a hydrophobic
agent that does not cause significant color change, nor impart
discoloration to a fabric, characterized as having a melting point
or glass transition temperature of less than 100.degree. C.; b. a
fluoropolymer; c. an effective amount of a zeta potential modifier;
and d. an antimicrobial active; wherein the treatment liquor has a
zeta potential that is positive and greater than zero millivolts;
and (2) curing the fabric at a drying temperature above ambient
temperature but less than 100.degree. C.; wherein: i. the fabric
protective property is selected from the group comprising:
increased water repellency, increased oil repellency, soil and
stain release, improved handfeel, improved softness, improved
resistance to damage, residual antimicrobial efficacy, and any
combination thereof; ii. the hydrophobic agent is not a
fluoropolymer; iii. the zeta potential modifier comprises a
cationic or cationically modified material; iv. the ratio of
hydrophobic agent to zeta potential modifier is at least from 1:1
to 300:1; and v. the antimicrobial active provides residual
antimicrobial efficacy beyond the time of the washing process.
2. The method for treating a fabric of claim 1, wherein at least
one fabric protective property is imparted to the fabric in
addition to residual antimicrobial efficacy.
3. The method for treating a fabric of claim 2, wherein the
depositing step and the curing step are repeated at least once.
4. A composition for treating a fabric to provide at least one
fabric protective property to the fabric, comprising: (1) from 5 to
30 weight % of a hydrophobic agent that does not cause significant
color change, nor impart discoloration to a fabric, characterized
as having a melting point or glass transition temperature of less
than 100.degree. C.; (2) a fluoropolymer; (3) an effective amount
of a zeta potential modifier; and (4) an antimicrobial active;
wherein: i. the fabric protective property is selected from the
group comprising: increased water repellency, increased oil,
repellency, soil and stain release, improved handfeel, improved
softness, improved resistance to damage, residual antimicrobial
efficacy, and any combination thereof; ii. the hydrophobic agent is
not a fluoropolymer; iii. the zeta potential modifier comprises a
cationic or cationically modified material; iv. the ratio of
hydrophobic agent to zeta potential modifier is at least from 1:1
to 300:1; and v. the antimicrobial active provides residual
antimicrobial efficacy beyond the time of the washing process.
5. (canceled)
6. (canceled)
7. (canceled)
8. (canceled)
9. The method for treating a fabric of claim 1, wherein the
antimicrobial active contains a metal/polymer complex.
10. The method for treating a fabric of claim 9, wherein a metal
ion comprising the metal/polymer complex is selected from the group
comprising silver, copper, zinc, oxides of any of the foregoing, as
well as combinations of any of the foregoing.
11. The method for treating a fabric of claim 9, wherein the
metal/polymer complex is anionic.
12. The method for treating a fabric of claim 1, wherein depositing
step (1) is delayed until some time t after any laundry detergent
is introduced into the treatment liquor.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Prov'l. Appl.
No. 62/000,444 filed 19 May 2014, which is hereby incorporated by
reference in its entirety. This application is a Divisional of
co-pending application for patent U.S. Ser. No. 14/716,871 filed 19
May 2015, which is a Continuation-in-Part of co-pending application
for patent U.S. Ser. No. 14/549,555 filed 20 Nov. 2014, which is a
Continuation-in-Part of U.S. Ser. No. 12/983,864 filed 3 Jan. 2011
(abandoned), which in turn is a Continuation-in-Part of U.S. Ser.
No. 11/614,197 filed 21 Dec. 2006, now U.S. Pat. No. 7,893,014,
issued 22 Feb. 2011. U.S. Ser. No. 11/614,197 is in turn a
Divisional of U.S. Ser. No. 10/338,350 filed 8 Jan. 2003
(abandoned), which claims the benefit of U.S. Prov'l. Appl. No.
60/371,452 filed 9 Apr. 2002 (expired). All of the foregoing are
incorporated fully by reference herein.
BACKGROUND OF THE DISCLOSURE
1. Field of the Disclosure
[0002] The instant disclosure relates to laundry additive
compositions for treating fabrics in order to provide fabric
protection benefits, including stain and soil resistance, oil
repellency, water repellency, softness, wrinkle and damage
resistance, and improved hand-feel, as well as antimicrobial
benefits such as microbiocidal or microbiostatic properties to a
fabric and/or a washing machine surface. The composition can be
used as a pretreatment prior to washing, through soaking or direct
spray application, or added to a treatment cycle, such as the wash
or rinse cycle of an automatic washing machine.
2. Discussion of the Related Art
[0003] Microbes or microorganisms are single- or multicellular
organisms, and are both diverse and ubiquitous. They include
bacteria, viruses, fungi, and algae, and live in every part of the
biosphere including air, water, and soil. Microorganisms are a
vital part to life, however a relatively small number are
pathogenic, capable of causing disease and death in plants and
animals. Some microbes, while not necessarily pathogenic, produce
by-products that are aesthetically displeasing, such as foul odors
and discoloration.
[0004] The development of non-fouling coatings has applications in
products ranging from medical devices, sensors and textiles. A
report by R. D. Scott II, "The Direct Medical Costs of
Healthcare-Associated Infections in U.S. Hospitals and the Benefits
of Prevention", Division of Healthcare Quality Promotion National
Center for Preparedness, Detection, and Control of Infectious
Diseases Coordinating Center for Infectious Diseases Centers for
Disease Control and Prevention (March 2009) estimated the direct
medical costs of hospital-acquired infections to be between $25 to
$31.5 billion. See www.cdc.gov/hai/pdfslhai/scott_costpaper.pdf).
Multiple research papers have been published with textiles being a
possible source of patient infections. Passive strategies for
overcoming bacterial infections include the physical and chemical
modifications of surfaces to prevent bacterial adhesion. Protocols
for infection prevention in most US hospitals necessitates the use
of disposable garments. This practice is becoming increasingly
unsustainable since the garments are not biodegradable and they
need to be disposed of in landfills.
[0005] Laundries associated with healthcare facilities need to
ensure that the cleaned linen is free of microbes and need to
maintain a protocol that ensures no cross-contamination of clean
and dirty clothes. All this care still does not prevent the growth
of bacterial colonies on clean linen once the linen returns to the
health care facility. It would be useful if the benefits of
disposable garments could be provided without the added burden of
high disposal costs. A number of attempts have been made to impart
antimicrobial effects to laundry. A sampling of references
follows.
[0006] U.S. Pat. Nos. 4,115,422 and 4,174,418 to Welch, et al.
describes treatment of fabric substrate with zirconium salts and
peroxide compounds to provide residual antimicrobial effects. The
inventors prescribe that the treatments can be applied via padding.
The patent does not indicate that this process can be carried out
in a home or institutional laundering process, and in fact one of
the inventors has shown that it would not be effective in such
processes.
[0007] U.S. Pat. No. 4,199,322 to Danna, et al. describes treatment
of fabric substrate with zinc salts and peroxide compounds to
provide residual antimicrobial effects. The inventors prescribe
that the treatments can be applied via padding. The patent does not
indicate that this process can be carried out in a home or
institutional laundering process. Discussion indicates that it
would not be effective in such processes.
[0008] Morris et. al., "Binding of Organic Antimicrobial Agents to
Cotton Fabric as Zirconium Complexes", Textile Research Journal,
51(2), pp. 90-96, February 1981, describes treatment of fabrics
with zirconium (IV) salts and subsequent padding on of
antimicrobial agents such as tetracycline, oxytetracycline, and
zinc pyridinethione. The residual effect is claimed to be effective
for up to twenty subsequent washings. The authors indicate that the
treatments can be applied via padding. The reference does not
indicate whether this process can be carried out in a home or
institutional laundering process, indeed they state that while
antimicrobial activity imparted by some of the one-bath treatments
was initially extremely high, it was less durable to laundering.
One of the authors shows that it would not be effective in home or
institutional laundering processes.
[0009] U.S. Pat. No. 4,851,139 to Lewis, et al. describes a stable,
isotropic fabric softening composition includes relatively high
levels of a 2-n-alkyl-4-isothiazoline-3-one to provide immediate
and residual mildewstatic activity on fabrics treated therewith.
Though designed to provide immediate residual antimicrobial
effects, inventors did not demonstrate whether the effect lasted
beyond the eventual drying of the fabric, nor whether the treatment
was effective in a subsequent washing which did not comprise the
antimicrobial agent.
[0010] U.S. Pat. No. 7,335,613 to Cottrell describes a treated
fiber substrate having a surface, wherein at least a portion of the
surface is treated with a finish comprising at least one
antimicrobial composition comprising a metal complexed with a
polymer, wherein the metal is selected from copper, silver, gold,
tin, zinc and combinations thereof. The inventors prescribe that
the treatments can be applied via padding or exhaustion. It is not
described whether this treatment can be applied in a home or
institutional laundering process.
[0011] U.S. Serial No. 2012/0076942 A1 to Liang, et al., describes
an antimicrobial composition for treating fabric, wherein said
antimicrobial composition is a liquid, and wherein said
antimicrobial composition comprises water and a metal/polymer
complex. The inventors state that the treatments can be applied via
padding or exhaustion. It is not described whether this treatment
can be applied in a home or institutional laundering process.
[0012] U.S. Pat. No. 6,482,424 B1 to Gabbay describes a method for
combating and preventing nosocomial infections, comprising
providing to health care facilities textile fabrics incorporating
fibers coated with an oxidant, cationic form of copper. The fabrics
are treated via immersion in concentrated baths. It is not
described whether this treatment can be applied in a home or
institutional laundering process.
[0013] U.S. Pat. No. 7,169,402 B2 to Gabbay describes an
antimicrobial and antiviral polymeric material, having microscopic
particles of ionic copper encapsulated therein and protruding from
surfaces thereof. The fabrics are treated via immersion in
concentrated baths. It is not described whether this treatment can
be applied in a home or institutional laundering process.
[0014] Gong, et al., "Quaternary Ammonium Silane-Functionalized
Methacrylate Resin Composition with Antimicrobial Activities and
Self-Repair Potential", Acta Biomater 8(9), pp. 3270-3282,
September 2012, describe an example of a polymeric quaternary
ammonium silane-functionalized methacrylate. It is not disclosed
whether this moiety is suitable for application to a fabric
surface, nor if so whether it would impart residual antimicrobial
activity."
[0015] Most textile treatment agents for stain release, water
repellency and oil repellency currently require industrial baths
with high concentrations of chemicals followed by curing at high
temperatures, that is, at temperatures substantially above
100.degree. C., often found in commercial drying ovens. For
example, U.S. Pat. No. 6,251,210 to Bullock, et al., discloses a
dual system consisting of an aqueous primary composition with 5-20
weight % fluorochemical textile agent directly applied to the
fabric, followed by drying, followed thereafter by an aqueous
secondary composition directly applied to the fabric, and again
followed by a secondary drying. The textile agent comprises, in
addition to the fluorochemical, a urethane latex, a compatible
acrylate latex and a cross-linking resin. The first treatment uses
a low-solids latex having a glass transition temperature from
10.degree. C. to 35.degree. C. The second treatment is a high
solids latex having the consistency of wood glue or wallpaper
paste, applied to one side of the fabric, and having a glass
transition temperature from -40.degree. C. to -10.degree. C. This
combined commercial treatment system is to produce a fabric that is
liquid repellent, stain resistant, and is easy to handle.
[0016] U.S. Pat. No. 5,047,065 to Vogel, et al., describes the
combination of a perfluoroaliphatic group-bearing water/oil
repellent agent dispersion, an emulsifiable polyethylene
dispersion, and a soft-hand extender based on a modified hydrogen
alkyl polysiloxane. The compositions are padded onto fabric at a
concentration of 70-150 g/L and then cured at 150.degree. C.
[0017] U.S. Pat. No. 5,019,281 to Singer, et al., describes the
combination of a water-soluble C.sub.9-C.sub.24 quaternary ammonium
salts of alkyl phosphonic acid, a separate C.sub.12-C.sub.24
quaternary ammonium compound, and a dispersed polyethylene wax. The
compositions are padded onto fabric at a concentration of 30 g/L
and then cured at 110.degree. C.
[0018] U.S. Pat. No. 5,153,046 to Murphy describes the combination
of fluorochemical textile antisoilant, lubricant, and combination
of cationic and nonionic surfactants. The compositions are intended
for commercial application to nylon yarns.
[0019] Water-proofing has traditionally been performed with
solvent-based wax and wax-like coating commonly using paraffin wax,
chlorinated paraffin waxes, and ethylene/vinyl acetate waxes such
as those materials cited in U.S. Pat. No. 4,027,062 to Englebrecht,
et al., and U.S. Pat. No. 4,833,006 to McKinney, et al. It is also
possible to make fabrics liquid resistant by using silicone
materials commonly known in the art.
[0020] Some technologies have been developed to provide a fabric
benefit on direct application or as an ironing aid. For example,
U.S. Pat. No. 5,532,023 to Vogel, et al. describes the post-wash
use of silicones and film-forming polymer for use on damp or dry
clothing to relax wrinkles. The composition is sprayed on the
fabric and then ironed or stretched by hand for wrinkle reduction
benefit. There is no indication that the composition can be applied
in the wash.
[0021] Products that are applied directly on the fabric, for
instance by spraying followed by curing with an iron or in a hot
dryer at high temperatures, such as above 100.degree. C., suffer
several disadvantages. Usually, a thick or uneven coat results,
which gives areas of incomplete oil and water repellency and a
fabric hand feel that lacks softness. These products can also
decrease the porosity of fabric, resulting in uncomfortable
conditions for the wearer during use. An additional drawback of
direct application products is that they cannot be used on fabrics
that are already stained or soiled because they lock in stains and
soils.
[0022] Fluoropolymers and hydrophobic agents have previously been
suggested for laundry use. U.S. Pat. No. 6,075,003 to Haq, et al.,
disclose the use of fluoropolymers with cationic fabric softeners.
U.S. Pat. No. 5,910,557 to Audenaert, et al., discloses the use of
fluorochemical polyurethane compounds to impart oil and water
repellency. These patents do not suggest the additional use of
hydrophobic agents with fluoropolymers in the wash for combined oil
and water repellency, while maintaining a soft hand. The use of
generally less expensive hydrophobic agents, such as wax, allows
products whose value is more acceptable to the consumer. Further,
Haq, et al., teach that exposure of fabric to their composition
should be followed by drying or ironing of the fabric at
temperatures at or above 150.degree. C., a temperature at which the
treatment becomes affixed in semi-permanent fashion.
[0023] U.S. Pat. No. 6,180,740 to Fitzgerald describes an aqueous
emulsion containing a fluoro copolymer composition that provides
oil- and water-repellency to textiles. The composition is
apparently stable under conditions of high alkalinity, high anionic
concentration, and/or high shear conditions. The stability of
emulsions having either positive or negative zeta potentials is
said to be achieved by controlling the relative amounts of cationic
and anionic surfactants. Emulsions with a positive zeta potential
are desirable for applications where the emulsion is used to apply
a coating to textile fabrics, which are typically anionic in
character. Fabric treatment requires drying at relative high
temperatures of between 110.degree. C. to 190.degree. C.
[0024] U.S. Pat. No. 4,724,095 to Gresser concerns a detergent
composition having an effective amount of at least one
hydrophobic/hydrophilic anti-redeposition copolymer that comprises
at least one of the recurring units ethylene oxide and alkylene
oxide. The copolymer reduces the zeta potential of the fibers of
the textile substrate to a value of 0.5 times, or less, that of the
bare fiber. Close examination of the patent reveals that the zeta
potential is determined solely for the bare and treated fabrics,
that is, not for the liquid composition, and that while the zeta
potential becomes less negative, it never attains a positive charge
value. An example in Gresser describes a soiling composition, which
includes a hydrophobic compound such as paraffin. The paraffin is
used to discolor a test fabric. It should be noted that Gresser's
goal is to completely remove the soil--and therefore the
paraffin--from the fabric.
[0025] U.S. Pat. No. 6,379,753 to Soane, et al., describes methods
for modifying textile materials to render them water repellant,
among other things, by covalently bonding multifunctional molecules
to the textile material. The multifunctional molecules are polymers
with plural functional groups or regions, such as binding groups,
hydrophobic groups, and hydrophilic groups and oleophobic
groups.
SUMMARY OF THE DISCLOSURE
[0026] Since the introduction of front-loading washing machines, in
particular the so-called "high efficiency" or HE washing machines,
many consumers have voiced displeasure at perceived unpleasant
odors originating from the HE machines after a number of use
cycles. Upon hearing of this phenomenon, the researchers involved
with the work described herein took note of this potentially
significant problem and were successfully able to elucidate the
origin and cause therefor.
[0027] During washing and rinsing processes, washing machine
surfaces are exposed to water and organic substances, including
detergents, solvents, soils, and etc., that can act as nutrients
for microbes. When the door of a HE washing machine is closed
between cycles when in use and when the machine sits idle and is
not being used, the interior of the washing machine remains moist
if not wet. The inability to completely dry out the washing
compartment provides ideal conditions for microbes to incubate and
thrive. This results in formation of a biofilm, in which cells are
embedded within a self-produced matrix of extracellular polymeric
substance--also referred to as slime--a mixture of extracellular
DNA, proteins, and polysaccharides. Once biofilms form on the
inside surfaces of washing machines, they often produce musty
odors, which are not only unpleasant but can in fact be transferred
to clothing that is subsequently washed in the machine. The
biofilms are highly resistant to removal except through mechanical
means or very aggressive chemical means.
[0028] The fact that this phenomenon was more prevalent with HE
machines and less so with non-HE washing machines is perhaps
understandable. For the most part, non-HE machines are top-loading
machines. Users of traditional home top-loading washing machines
often leave the lids of the machines up for a time after the
machines have been used so that they can dry out. This provides an
opportunity for the ambient air to circulate and dry out the
washing machine tub compartment. The change in door configuration
with HE machines, however, has meant that this usual practice is
less likely to occur. Most front-loading HE machines have a door
that when open, impedes the ability to pass by directly in front of
the machine. That is, in order to leave the door of a front-loading
HE machine open, the door becomes an impediment to foot-traffic for
most families in front of the HE machine. As most home washing
machines are typically located in an area that is prone to heavy
foot traffic, the doors of HE machines are more likely to be shut
between washing machine cycles than non-HE washing machines.
[0029] The lack of an opportunity to permit washing machine
surfaces to dry and therefore the inability to remove
microbe-associated biofilms has resulted in tens of millions of
dollars in lawsuits, and led to numerous products introduced to the
market to try to combat its formation. These products, however,
attempt to remove the biofilm and microbes through a single wash
through use of oxidants (such as sodium hypochlorite, sodium
percarbonate, or peracids) and surfactants. They do not provide any
residual action against subsequent introduction of microbes and new
biofilm formation.
[0030] The present disclosure therefore provides compositions and
methods for imparting stain repellency and/or stain-release
properties to a fabric or garment, while simultaneously introducing
antimicrobial properties to the fabric or garment as well as to
washing machine surfaces.
[0031] U.S. Pat. No. 7,893,014 B2 to van Buskirk, et al., and
continuations thereof teach the use of laundry compositions to
provide stain and soil repellency and release. While the use of
antimicrobial agents to preserve the composition may have been
mentioned in passing, the '014 patent is silent on the use of
actives to provide residual antimicrobial efficacy. Moreover, the
'014 patent includes mention of such antimicrobial agents as either
cationic or nonionic. Indeed, this work neither anticipates nor
teaches the challenges one faces when trying to incorporate such
additives into the stain and soil repellent compositions described
herein. This is similar to antimicrobial adjuvants described in
U.S. Pat. No. 4,851,139 to Lewis, see above. In both the '014
patent to van Buskirk and the '139 patent to Lewis, it might be
expected that the overall cationic nature of the respective product
matrices would be incompatible with antimicrobial agents that are
anionic in nature, such as metal/polymer agents described above.
Such incompatibility would take the form of either diminishing the
stain repellent and/or fabric softening benefits of the product, or
negating the antimicrobial effect of the anionic antimicrobial
agent. Clearly, a mechanism whereby the user can derive benefit
from both the base product form as well as residual antimicrobial
properties--especially of an anionic nature--would be highly
desirable.
[0032] To date, the investigators of the work described herein have
found no reference in which an antimicrobial treatment has been
applied in a home or institutional laundering process, that
provides the end user with garments that maintain these properties
through multiple wearings and washings. Further, references that
disclose the use of such treatments for providing antimicrobial
properties to washing machine surfaces subsequent to washing have
not been found. It is believed that the instant disclosure is the
first to teach the benefit of reducing the ability of microbes to
adhere to fabric and washing machine surfaces through a combination
of anti-soiling actives--both hydrophobic and oleophobic--as well
as introducing at least one substance that can provide a residual
antimicrobial effect.
[0033] The discussion below firstly describes non-limiting examples
of fabric treatment compositions for providing protective
properties to a fabric or garment. As can be appreciated, there is
a need for a product that combines the controlled and even coating
of commercial fabric treatment operations with the convenience and
ease of home use. Additionally, the coating should be curable at
temperatures that are readily attainable in a residential clothes
dryer. This is because curing at high temperatures can make
coatings excessively durable, owing to excessive buildup over
numerous treatment cycles. This, in turn, typically results in an
unfavorable hand-feel. Furthermore, reduced temperature curing
results in improved hand-feel, and also allows for an easily
reversible and/or removable coating, if desired. Such non-permanent
or transient coatings reduce total coating buildup over multiple
applications or treatments, and also reduce the possibility of
leaving a visible residue or undesirable changes in appearance on
fabrics, such as yellowing or discoloration of white or
lighted-colored fabrics. The product should also not lock in
pre-existing stains or soils and thereby ruin fabrics. According to
the U.S. Consumer Products Safety Commission, household dryers
typically attain average temperatures of at least 175.degree. C.,
and under normal usage reach much higher temperatures. In fact,
typical average household dryer temperatures are in the range of
250.degree. C.-350.degree. C., see: Final Report on Electric
Clothes Dryers and Lint Ignition Characteristics, U.S. Consumer
Products Safety Commission, May 2003, p. 105;
http://www.cpsc.gov/library/foia/foia03/os/dryer.pdf.
[0034] Prior art that mentions one dryer temperature, for example
U.S. Pat. No. 4,920,000 to Green, makes no mention of the
potentially deleterious consequences of using excessive drying
temperatures. Green discloses treating a blended fabric of cotton,
nylon and heat-resistant fibers with a surrogate cleaning solution,
i.e., aqueous sodium hydroxide, then rinsing the fabric and drying
it in a conventional home dryer to a maximum dryness at 71.degree.
C. Green does not state that 71.degree. C. is the maximum
temperature to which a fabric should be subjected, nor that
71.degree. C. is the maximum temperature achieved in a conventional
home dryer, but rather states that 71.degree. C. was the maximum
temperature that was used.
[0035] The present disclosure concerns the discovery that (1)
compositions containing at least one zeta potential modifier, a
hydrophobic agent, a fluoropolymer, and an antimicrobial agent,
when applied to fabrics and cured by drying and/or heating, will
impart numerous fabric protection benefits to a fabric or garment,
and (2) if properly formulated and delivered during a laundering
process, will impart antimicrobial properties to fabric and washing
machine surfaces while maintaining stain removal properties of the
base laundry detergent as well as stain repelling properties due to
the novel composition.
Definitions
[0036] In the present specification and claims, reference will be
made to phrases and terms of art which are expressly defined for
use herein as follows:
[0037] Active ingredient or active material refers to substances
that contribute to the cleaning of stains and soils and/or
disinfecting of fabrics or surfaces. A chemical mixture as procured
from suppliers may be diluted with a solvent such as water, which
serves no purpose in cleaning and/or disinfection; in such case,
the active ingredient refers only to the portion of the chemical
mixture that serves a purpose to clean and/or disinfect. This term
does not generally include aesthetic ingredients such as fragrance
materials, colorants, viscosity modifiers, preservatives, or the
like.
[0038] An antimicrobial active is an agent that kills
microorganisms such as bacteria, viruses, fungi including mold and
mildew, yeast and the like, or suppresses their multiplication or
growth.
[0039] Fabric protective benefits or fabric protection benefits is
understood to refer to at least one of: stain resistance, oil
repellency, water repellency, soil and stain release, improved
handfeel, improved softness, improved resistance to damage,
residual antimicrobial efficacy, wrinkle and damage resistance,
improved hand-feel, residual antimicrobial properties, as well as
combinations of any of the foregoing. Fabric protection benefits
are also understood to include reduction of fiber wear, i.e.,
retention of fiber tensile strength, maintain fabric appearance by
reducing fiber pilling, reduction of color loss, inhibition of the
deposition of fugitive dyes onto a fabric during a washing cycle or
overall laundering process. These benefits, individually and
collectively, increase the useful longevity of a garment or fabric
that is treated with the novel laundry additive compositions
disclosed and described herein.
[0040] Microbiocidal activity is the property of killing
microorganisms such as bacteria, viruses, fungi including mold and
mildew, yeast and the like.
[0041] Microbiostatic activity is the property of suppressing
multiplication or growth of microorganisms such as bacteria,
viruses, fungi including mold and mildew, yeast and the like.
Microbiostatis is the state of such microorganisms being suppressed
in their multiplication or growth.
[0042] Residual antimicrobial efficacy is understood to be the
action of killing microorganisms such as bacteria, viruses, fungi
including mold and mildew, yeast and the like, or suppresses their
multiplication or growth beyond the time of the washing process.
The suppression may be for minutes, hours or days after completion
of the washing process.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0043] In one aspect, the instant disclosure is directed to a
method for treating fabrics in a washing machine. More
particularly, the method concerns providing at least one fabric
protective property to a fabric, which includes the steps of:
[0044] (1) depositing a composition onto the fabric in a treatment
liquor, wherein the composition comprises: [0045] a. a hydrophobic
agent that does not cause significant color change, nor impart
discoloration to a fabric, characterized as having a melting point
or glass transition temperature of less than 100.degree. C.; [0046]
b. a fluoropolymer; [0047] c. an effective amount of a zeta
potential modifier; and [0048] d. an antimicrobial active; [0049]
wherein the treatment liquor has a zeta potential that is positive
and greater than zero millivolts; and
[0050] (2) curing the fabric at a drying temperature above ambient
temperature but less than 100.degree. C.;
wherein: [0051] i. the fabric protective property is selected from
the group comprising: increased water repellency, increased oil
repellency, soil and stain release, improved hand-feel, improved
softness, improved resistance to damage, residual antimicrobial
efficacy, and any combination thereof; [0052] ii. the hydrophobic
agent is not a fluoropolymer; [0053] iii. the zeta potential
modifier comprises a cationic or cationically modified material;
[0054] iv. the ratio of hydrophobic agent to zeta potential
modifier is from 1:1 to 300:1; and [0055] v. the antimicrobial
active provides residual antimicrobial efficacy beyond the time of
the washing process.
[0056] In an alternate aspect, the instant disclosure is directed
to a method for treating fabrics in order to provide at least one
fabric protective property to the fabric in addition to residual
antimicrobial efficacy according to the prior aspect mentioned
above, further wherein at least one of the depositing step, the
curing step and any combination of the depositing step and the
curing step is repeated.
[0057] In a third aspect, the instant disclosure is directed to a
method for treating fabrics in order to provide at least one fabric
protective property to the fabric in addition to residual
antimicrobial efficacy according to the first aspect mentioned
above, further wherein the depositing step and the curing step are
repeated at least once.
[0058] In yet another aspect, the instant disclosure is directed to
a composition for treating fabrics in a washing machine. The
composition, in turn, can provide at least one fabric protective
property to a fabric, where the composition contains: [0059] a. a
hydrophobic agent that does not cause significant color change, nor
impart discoloration to a fabric, characterized as having a melting
point or glass transition temperature of less than 100.degree. C.;
[0060] b. a fluoropolymer; [0061] c. an effective amount of a zeta
potential modifier; and [0062] d. an antimicrobial active; [0063]
wherein: [0064] i. the fabric protective property is selected from
the group comprising: increased water repellency, increased oil,
repellency, soil and stain release, improved handfeel, improved
softness, improved resistance to damage, residual antimicrobial
efficacy, and any combination thereof; [0065] ii. the hydrophobic
agent is not a fluoropolymer; [0066] iii. the zeta potential
modifier comprises a cationic or cationically modified material;
[0067] iv. the ratio of hydrophobic agent to zeta potential
modifier is from 1:1 to 300:1; and [0068] v. the antimicrobial
active provides residual antimicrobial efficacy beyond the time of
the washing process.
[0069] In still another aspect, the instant disclosure is directed
to a method for treating a washing machine surface to provide
antimicrobial efficacy to the surface, comprising:
[0070] (1) contacting a composition onto the surface of the washing
machine during a wash cycle, the composition comprising: [0071] a.
a hydrophobic agent that does not cause significant color change,
nor impart discoloration to a fabric, characterized as having a
melting point or glass transition temperature of less than
100.degree. C.; [0072] b. a fluoropolymer; [0073] c. an effective
amount of a zeta potential modifier; and [0074] d. an antimicrobial
active; [0075] wherein the zeta potential of a wash liquor during
the wash cycle is positive and greater than zero millivolts;
and
[0076] (2) air drying, that is, allowing the composition to air dry
on the washing machine surface;
wherein: [0077] i. the hydrophobic agent is not a fluoropolymer;
[0078] ii. the zeta potential modifier comprises a cationic or
cationically modified material; [0079] iii. the ratio of
hydrophobic agent to zeta potential modifier is from 1:1 to 300:1;
and [0080] iv. the antimicrobial active provides residual
antimicrobial efficacy beyond the time of the washing process.
[0081] In an alternate aspect, the instant disclosure is directed
to a method for treating washing machine surfaces in order to
provide antimicrobial efficacy to the surface, further wherein at
least one of contacting step (1), air drying step (2) and any
combination of contacting step (1) and air drying step (2) is
repeated.
[0082] In a third aspect, the instant disclosure is directed to a
method for treating washing machine surfaces in order to provide
antimicrobial efficacy to the washing machine surfaces, wherein
contacting step (1) and air drying step (2) are repeated at least
once.
[0083] In yet another aspect, the instant disclosure is directed to
a composition for treating washing machine surfaces. More
particularly, the instant disclosure concerns compositions for
treating washing machine surfaces that are added to a treatment
liquor during a wash cycle in order to provide antimicrobial
efficacy to at least one surface of the washing machine, the
composition comprising: [0084] a. a hydrophobic agent that does not
cause significant color change, nor impart discoloration to a
fabric, characterized as having a melting point or glass transition
temperature of less than 100.degree. C.; [0085] b. a fluoropolymer;
[0086] c. an effective amount of a zeta potential modifier; and
[0087] d. an antimicrobial active; wherein: [0088] i. the zeta
potential of a wash liquor during the wash cycle is positive and
greater than zero millivolts; and [0089] ii. the hydrophobic agent
is not a fluoropolymer; [0090] iii. the zeta potential modifier
comprises a cationic or cationically modified material; [0091] iv.
the ratio of hydrophobic agent to zeta potential modifier is at
least 0.6:1 but less than 11:1; and [0092] v. the antimicrobial
active provides residual antimicrobial efficacy beyond the time of
the washing process.
[0093] According to still yet another aspect, the instant
disclosure is directed to a compositions and methods for treating
fabrics and washing machine surfaces in order to impart residual
antimicrobial activity that contain metal/polymer complexes. These
metal/polymer complexes, which are described in greater detail
below, contain metal ions. The metal ions, in turn, are selected
from the group comprising silver, copper, zinc, oxides of any of
the foregoing, as well as combinations of any of the foregoing. The
polymer portion of the metal/polymer complex is anionic in nature.
Further discussion of the characteristics and examples of these
metal/polymer complexes are provided below under the heading
Antimicrobials.
[0094] In a still further aspect, the present disclosure is
directed towards improved cleaning efficacy and improving fabric
performance imparted to fabrics. As will be discussed in greater
detail below, it has surprisingly been found that by delaying the
addition of laundry additives, such as fabric treatment
compositions, until after laundry detergents have had some time to
interact with fabrics, improved overall fabric properties and
qualities may be realized.
Fluoropolymer
[0095] According to the instant disclosure instant disclosure, the
fluoropolymers as prepared may contain some amount of surfactants,
especially mixtures of cationic and nonionic surfactants, but
usually the amounts are small. A generally suitable range for
fluoropolymers in a first laundry treatment composition presented
herein is 0.5 to 60%, more preferred is 1 to 40%, and further
preferred is 5 to 30%. The amount of fluoropolymer that may be
acceptable for use in a second laundry additive composition can be
somewhat less. Thus, a second laundry additive composition may
contain from 0.1-30 weight % fluoropolymer.
[0096] The fluoropolymers employed in the instant disclosure can be
water insoluble oily soil repellents and may have one or more
fluoroaliphatic radicals, and/or one or more perfluoroalkyl
radicals and/or partially or fully fluorinated radical
substituents. They can be nonionic in that they do not contain an
ionized functional group such as a quaternary ammonium group. They
can be cationic in that they contain an ionized or ionizable
functional group, such as a quaternary ammonium group in the first
instance, or a tertiary amine, which is protonatable to provide for
a positive charge center. They can be zwitterionic in that they
have both cationic and anionic groups present, suitably with the
number of cationic and anionic groups present being essentially
equivalent in number to provide an overall net nonionic property to
the fluoropolymer, and also suitably with the number of cationic
and anionic groups present being essentially non-equivalent in
number to provide an overall net positive or cationic charge to the
fluoropolymer. Useful classes of the fluoropolymers are the
fluorocarbonylimino biurets, the fluoroesters, the fluoroester
carbamates, and the fluoropolymers. The class of
fluorocarbonyliminobiurets is represented by U.S. Pat. No.
4,958,039 to Pechhold, which is incorporated herein by reference.
The class of fluorocarbonylimino biurets is particularly useful
because of the outstanding anti soilant protection it provides. The
class of fluoroesters is represented by U.S. Pat. No. 3,923,715 to
Dettre, et al., and U.S. Pat. No. 4,029,585 to Dettre, et al.,
which are incorporated herein by reference. These patents disclose
perfluoroalkyl esters of carboxylic acids of 3 to 30 carbon atoms.
An example is the citric acid ester of perfluoroalkyl aliphatic
alcohols such as a mixture of 2-perfluoroalkyl ethanols containing
8 to 16 carbon atoms. The class of fluoroester carbamates is also
disclosed in aforementioned U.S. Pat. No. 4,029,585. The class of
fluoropolymers is represented by U.S. Pat. No. 3,645,989 to Tandy
and U.S. Pat. No. 3,645,990 to Raynolds, which are incorporated
herein by reference. The patents describe, respectively,
fluorinated polymers from acrylic and methacrylic derived
fluoro-substituted monomers and methyl acrylate or ethylacrylate,
optionally with small amounts of other monomers.
[0097] A useful fluoropolymer is the terpolymer formed by
polymerization of an aliphatic or aromatic alpha olefin or an alkyl
vinyl ether, a non-hydrolyzable perfluoroalkyl substituted monomer
and maleic anhydride as described in U.S. Pat. No. 6,245,116 to
Pechhold, et al., which is incorporated herein by reference. Useful
fluoropolymers are ZONYL 8412 and ZONYL RN available from
Ciba-Geigy; SCOTCHGARD FC 255, SCOTCHGARD FC 214-230, FLUORAD
series, such as FLUORAD FC 129, available from the 3M Corporation,
Minnesota Mining and Manufacturing Company, St. Paul, Minn.; and
TEFLON RN, TEFLON 8070, and TEFLON 8787, available from
Dupont.RTM.. Additional useful fluoropolymers include ZONYL 7950,
ZONYL 5180, ZONYL 6885, ZONYL 7910, ZONYL 6700, ZONYL 8300, ZONYL
6991, ZONYL 310 and ZONYL NWG, all from Dupont.RTM.. Useful
fluoropolymers also include fluoropolymers available from Asahi
Glass, Atochem (Atofina), Daikin, Clariant, Goldschmidt, Hoechst
Celanese, Mitsubishi, Peach State Laboratories, Shaw Industries and
Trichromatic Carpet. Examples include the FOMBLIN FE-20 series of
aqueous based perfluoro polyether microemulsions available from
Ausimont USA, Thorofare, N.J.; fluoropolymer emulsion 3310, 3311
and Unidyne.RTM. TG-532, available from Daikin Industries Ltd.,
Japan; fluoropolymer emulsions NlNA 5006, NlNA LB Liquid, NUVA LC
Liquid, available from Clariant Corporation, Charlotte, N.C.;
fluoropolymer REPEARL F-45, available from Mitsubishi International
Corporation, NY; and MYAFIX WS and MYAFIX EX.WS, available from
Peach State Labs, Rome, Ga. Other examples include NUVA FT
fluorochemical acrylate polymer, available from Clariant
Corporation; SHAWGUARD 353 fluoroalkyl acrylate copolymer,
available from Shaw Industries, Inc.; and BARTEX TII, BARTEX MAC,
both fluoroalkylacrylate polymers, available from Trichromatic
Carpets, Inc., Quebec, Canada.
[0098] Highly preferred materials of this class of fluoropolymers
are those that do not cause any significant color change, nor
impart any discoloration, such as graying or yellowing, to the
fabrics to which they are applied, either during treatment followed
by drying and/or curing, or after the drying and/or curing step
followed by normal exposure to the elements, such as air, moisture
or sunlight exposure.
Hydrophobic Agent
[0099] In general, a preferred range for hydrophobic agents is 0.5
to 60 weight %, more preferably 1 to 40 weight % and most
preferably 5 to 30 weight % of the laundry additive
composition.
[0100] The hydrophobic agent compounds of the invention include
those which are at least partly insoluble in water at a temperature
of 20.degree. C., and which have a melting point or glass
transition temperature below 100.degree. C. and preferably between
about 45.degree. C. to about 100.degree. C. Suitable hydrophobic
agents include hydrophobic polymers, copolymers, and copolymers
containing hydrophobic monomers. Suitable hydrophobic agents
include hydrophobic waxes, including, but not limited to paraffin
waxes. The paraffin waxes suitable for use in accordance with the
invention are generally complex mixtures without a clear-cut
melting point. For characterization purposes, their melting range
is normally determined by differential thermoanalysis or DTA, as
described in "The Analyst" 87 (1962), p. 420, and/or by their
solidification point. The glass transition temperature is
understood to be the temperature at which wax changes from a liquid
into a solid state through slow cooling. According to the
invention, paraffins can be completely liquid at room temperature,
i.e., those with a solidification point below 25.degree. C., and
paraffins that are solid at room temperature may both be used. The
paraffin wax is preferably solid at room temperature and can be
present in completely liquid form at 100.degree. C. Suitable
paraffin waxes for use in accordance with the invention maybe
obtained, for example, under the name of LUNAFLEX available from
Fuller and under the name of DEAWAX from DEA Mineralol AG.
[0101] Other suitable hydrophobic agents are produced from
ethylenically unsaturated monomers. Examples of such monomers are
styrene, acrylic acid or methacrylic acid esters of aliphatic
C.sub.1 to C.sub.18 alcohols, acrylonitrile, vinyl acetate, acrylic
acid and methacrylic acid. Poly(meth)acrylates of two or more of
these monomers, which may optionally contain other monomers in
small quantities, are particularly preferred. Most particularly
preferred are polymers that contain 1 to 30 parts by weight of
monomers containing carboxylic acid groups; 30 to 70 parts by
weight of monomers which form homopolymers having glass
temperatures below 20.degree. C., preferably esters of acrylic acid
with C.sub.1 to C.sub.18 alcohols and/or methacrylic acid with
C.sub.1 to C.sub.18 alcohols; and 30 to 70 parts by weight of
monomers which form homopolymers having glass transition
temperatures above room temperature, preferably methacrylic acid
esters of C1 to C3 alcohols or styrene. Examples of such polymers
include the following commercial products that are available as
dispersions: SYNTRAN 1501, available from Interpolymer, PRIMAL 644,
available from Rohm & Haas, NEOCRYL A 1049, available from ICI.
Other preferred polymers include low molecular weight (i.e., less
than 500,000 daltons) polyethylene, low-density polyethylene,
polypropylene, polyolefin, polyurethane, ethylvinyl acetate,
polyvinyl chloride, and co-polymers.
[0102] Another class of suitable hydrophobic agents are
emulsifiable waxes. Emulsifiable waxes, capable of forming wax
emulsions, include, for example, oxidized polyethylene, ethylene
acrylic acid copolymers, and montanic acid and ester waxes
available as LUWAX. Also suitable are polyolefin waxes, maleic
grafted polyolefin waxes, paraffin, other hydrocarbon waxes and
vegetable waxes such as carnauba and candelillia. Preferred
emulsifiable waxes include polyethylene, polypropylene, oxidized
polyethylene, oxidized polypropylene, ethylene acrylic copolymers,
and maleic grafted polyolefins. Preferred emulsifiable waxes
include polyolefins that are partially modified to contain
functional groups improving dispersibility of the waxes, such
functional groups include alkoxyl, carboxyl, amide, alkylamide,
sulfonic, phosphonic or mixtures thereof. Suitable emulsifiable
waxes also include waxes containing chemical groups, which
facilitate emulsification, such as carboxylic or related groups.
Examples of emulsifiable waxes include oxygen-containing wax or
oxidized waxes as illustrated by those described in the following
patents: natural waxes such as candelillia, carnauba, beeswax,
coconut wax, montan wax, as well as oxidized petroleum waxes as
illustrated by U.S. Pat. No. 2,879,237 to Groote, et al., U.S. Pat.
No. 2,879,238 to Groote, et al., U.S. Pat. No. 2,879,239 to Groote,
et al., U.S. Pat. No. 2,879,240 to Groote, et al., and U.S. Pat.
No. 2,879,241 to Groote, et al., U U.S. Pat. No. 3,163,548 to
Stark, and U.S. Pat. No. 4,004,932 to Bienvenu, which are
incorporated herein by reference. Other examples of suitable waxes
include carboxylic adducts such as maleic and related anhydrides
added to waxes such as those described in the following: U.S. Pat.
No. 3,933,511 to Heintzelman, et al., and U.S. Pat. No. 3,933,512
to Heintzelman, et al., which are incorporated herein by reference.
Typical examples are esters, amides, and ester-amides of
compositions of one or more of the formulas disclosed in U.S. Pat.
Nos. 3,933,511 and 3,933,512 which are incorporated herein by
reference. Some of these waxes are sold by Petrolite Corporation
under the name CERAMER.
[0103] Other preferred waxes include alkylmethycone AMS-C30
available from Dow Corning, natural candelillia (Candelillia)
available from Frank B. Ross, stearoxytrimethylsilane 580 available
from Dow Corning, cetyl palmitate DUB PC Stearine available from
Dubois, microcrystalline petrolatum MULTIWAX B710 available from
Witco, Scale paraffin available from Strahl and Pitsch, natural
beeswax available from Frank B. Ross, microcrystalline wax from
Ultraflex Petrolite, microcrystalline Ross wax 132911 from Frank B.
Ross, microcrystalline Multiwax 110X from Witco, paraffin Altafin
135/140, petrolatum as Petrolatum Snow from Penreco, refined
paraffin from Strahl and Pitsch, and paraffin Altafin 125/130.
Preferably, the low melting point wax is selected from
microcrystalline Multiwax W145A available from Witco, paraffin
Altafin140/145 from Astor-Durachem, and microcrystalline Rosswax
1365 from Frank B. Ross. Highly preferred materials of this class
of hydrophobic agents are those that do not cause any significant
color change, nor impart any discoloration, such as graying or
yellowing, to the fabrics to which they are applied, either during
treatment, after drying and/or curing, or after the drying and/or
curing step followed by normal exposure to the elements, such as
air, moisture or sunlight.
Liquid Carrier
[0104] The liquid carrier is preferably an aqueous system. The
carrier can also contain a low molecular weight organic solvent
that is highly soluble in water, e. g., C.sub.1 to C.sub.4
monohydric alcohols, C.sub.2 to C.sub.6 polyhydric alcohols, such
as alkylene glycols and polyalkylene glycols, alkylene carbonates,
and mixtures thereof. Examples of these water-soluble solvents
include ethanol, propanol and isopropanol. Water is a preferred
liquid carrier due to its low cost, availability, safety, and
environmental compatibility. The water can be distilled, deionized,
or tap water.
[0105] Highly preferred materials of this class of liquid carriers
are those that do not cause any significant color change, nor
impart any discoloration, such as graying or yellowing, to the
fabrics to which they are applied, either during treatment followed
by drying and/or curing, or after the drying and/or curing step
followed by normal exposure to the elements, such as air, moisture
or sunlight exposure. When a concentrated composition is used, the
level of liquid carrier can typically be from about 20% to about
80% of the composition, preferably from about 30% to about 70%, and
more preferably from about 40% to about 60% of the composition.
When a dilute composition is used, for instance in a rinse added
maintenance or spray application, the amount of liquid carrier can
be greater. For rinse added maintenance applications, the liquid
carrier may typically range from about 50% to about 99% of the
composition, preferably from about 60% to about 98%, and more
preferably from about 80% to about 95% of the composition. For
direct applications, employing the compositions described herein in
"neat form", that is to say, undiluted form and such as for spray
and aerosol applications, the liquid carrier can typically range
from about 70% to about 99.9%, by weight of the composition,
preferably from about 80% to about 99.5%, and more preferably from
about 90% to about 99% of the composition. When used in direct
treatment, that is in the form of an undiluted composition or a
"neat composition" that does not require any subsequent dilution
for use, levels of the compositions described herein are
necessarily reduced to the required level for effectiveness.
Zeta Potential Modifier
[0106] Compositions of the instant disclosure include
fluoropolymers and hydrophobic agents that become covalently and/or
non-covalently attached to the surface of fabrics upon being cured
at elevated temperatures. There is a wide range of phenomena, which
can influence the fundamental interactions at the molecular and
colloidal level. One of these factors is the electrokinetics. In
this regard, the term, zeta potential, applies to the electrical
charges existing in fine dispersions. Specifically, a solid
particle, e.g., insoluble polymer, that is suspended in an aqueous
system is surrounded by a dense layer of ions having a specific
electrical charge. This layer is surrounded by another layer, more
diffuse than the first, that has an electrical charge of its own.
The bulk of the suspended liquid also has its own electrical
charge. The difference in electrical charge between the dense layer
of ions surrounding the particle and the bulk of the suspended
liquid is the zeta potential, usually measured in millivolts. The
zeta potential, .xi., is defined by the Equation I:
.xi.=4.pi..delta.q/D Equation I
where q is the charge on the particle, .delta. is the thickness of
the zone of influence of the charge on the particle, and D is the
dielectric constant of the liquid.
[0107] Without being bound by theory, it is believed that the
fluoropolymers are attracted to the fabric surface owing to a
combination of van der Waals attractive forces and electrostatic
interactions. In the case of treating fabrics containing cellulose
fibers, for example cotton, the surface of the fabric is negatively
charged due to the presence of the carboxylic groups of the
cellulose. In the case of treating fabrics containing synthetic
fibers, such as polyester, nylon, polyamide and other synthetic
polymers or blends, adsorbed materials such as negative compounds
or negatively charged surface active materials, e.g., anionic
surfactants found in detergents, can result in the surface of the
fabric becoming negatively charged due the presence of these
materials on the fabric surface. Without being bound by theory, it
is believed that the existence of negatively charged groups or
adsorbed negatively charged materials on the fabric surface may
inhibit the attraction of the fluoropolymers to the fabric surface
to at least to some extent.
[0108] It is believed that the adverse effect of any negative
surface charge present on fabrics to be treated, regardless of the
cause or source of said negative surface charge, can be reduced or
avoided by introducing an appropriate amount of zeta potential
modifier to adjust the zeta potential of the treatment liquor to a
positive value greater than zero. Typically sufficient zeta
potential modifier is added so that the zeta potential of the
treatment liquor is positive and greater than zero millivolts.
Preferably the zeta potential of the treatment liquor ranges from a
positive value of zero to about +150 millivolts and preferably is
less than about +100 millivolts. When at least one zeta potential
modifier is employed, it will typically range from 0.1 to 30% of
the composition. It has been found that exceeding this level leads
to decreased performance. Without being bound by theory, it is
believed that exceeding this level of zeta potential modifier leads
to interference in depositing the desired repelling species. This
discovery distinguishes the invention from prior art that employs
zeta potential modifiers, given that the levels in the instant
invention are dictated by efficacy of the treatment liquor, not for
stabilization of the composition.
[0109] Suitable zeta potential modifiers are cationic agents
including, for example, cationic monomers, polymers, and copolymers
comprising cationic monomers, wherein the cationic monomer is
present at least to an extent sufficient to provide an overall net
cationic nature, i.e. overall positive charge, to the copolymer.
Preferred cationic agents include cationic surfactants, including,
but not limited to, mono and di-methyl fatty amines, alkyl
trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl
amine acetates, trialkylammonium acetates, alkyldimethylbenzyl
ammonium salts, dialkymethylbenzyl ammonium salts, alkylpyridinium
halide and alkyl (alkyl substituted) pyridinium salts,
alkylthiomethyl pyridinium salts, alkylamidomethyl pyridinium
salts, alkylquinolinium salts, alkylisoquinolinium salts,
N,N-alkylmethyl pyrollidonium salts, 1,1-dialkylpiperidinium salts,
4,4-dialkylthiamorpholinium salts,
4,4-dialkylthiamorpholinium-1-oxide salts, methyl
bis(alkylethyl)-2-alkyl imidazolinium methyl sulfate (and other
salts), methyl bis(alkyl amidoethyl)-2-hydroxyethyl ammonium methyl
sulfate (and other salts), alkyl amidopropyl-dimethylbenzyl
ammonium salts, carboxyalkyl-alkyldimethyl ammonium salts,
alkylamine oxides, alkyl dimethyl amine oxides, poly(vinylmethyl
pyridinium) salts, poly(vinyl pyridine) salts, polyethyleneimines,
trialkyl phosphonium bicarbonates (and other salts), trialkylmethyl
phosphonium salts, alkylethylmethyl sulfonium salts, and
alkyldimethyl sulfoxonium salts.
[0110] Suitable zeta potential modifiers further include cationic
(i.e. bearing one or more positive charges) and cationically
modified materials, including, for example, cationic and
cationically modified organic polymers, cationic and cationically
modified biopolymers, and cationic and cationically modified
inorganic materials, including, for example, cationic and
cationically modified clays, cationic and cationically modified
silicas, cationic and cationically modified metal oxides and
cationic and cationically modified composite materials.
[0111] Suitable organic cationic polymers include, but are not
limited to, cationic cellulose derivatives, such as, for example, a
quaternized hydroxyethyl cellulose which is available under the
name Polymer JR 400.RTM. from Amerchol, cationic starch, copolymers
of diallylammonium salts and acrylamides, quaternized
vinylpyrrolidone/vinylimidazole polymers, such as, for example,
Luviquat.RTM. (BASF), condensation products of polyglycols and
amines, quaternized collagen polypeptides, such as, for example,
lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat.RTM.
L/Grunau), quaternized wheat polypeptides, polyethyleneimines
cationic silicone polymers, such as, for example, amodimethicones,
copolymers of adipic acid and dimethylaminohydroxypropyldiethylene
triamine (Cartaretins.RTM. from Sandoz), copolymers of acrylic acid
with dimethyldiallylammonium chloride (Merquat D550I from
Chemviron), polyaminopolyamides, as described, for example, in FR
2252840 A, and their crosslinked water-soluble polymers,
condensation products of dihaloalkyls, such as, for example,
dibromobutane with bisdialkylamines, such as, for example,
bisdimethylamino-1,3-propane, cationic guar gum, such as, for
example, Jaguar.RTM. CBS, Jaguar.RTM. C-17, Jaguar.RTM. C-16 from
Celanese, guar guar (e.g. guarhydroxypropyltrimethylammonium
chloride); Cosmedia Guar C 261; Cognis GmbH; guar flour; Cosmedia
Guar U, Cognis GmbH), quaternized ammonium salt polymers, such as,
for example, Mirapol.RTM.A-15, Mirapol.RTM.AD-1, Mirapol.RTM. AZ-1
from Miranol, and cationically modified starches, as for example,
Softgel BDA and Softgel BD, both from Avebe.
[0112] Additional cationic compounds suitable for use as zeta
potential modifiers include amine acid salts;
polyacrylamidopropyltrimonium chloride; betaines, such as but not
limited to, alkyl betaines, alkyl amido betaines, imidazolinium
betaines; quaternized poly(vinylpyridine); amidoamine acid salts;
poly(imine) acid salts; polyethylene imine acid salts; cationic
acrylamides; poly(vinylamine) acid salts; cationic ionene polymers;
poly(vinylimidazolinium salts); quatemized silicone compounds, such
as but not limited to, the diquaternary polydimethyl siloxanes;
poly(vinyl alcohol) quaternary materials;
polydimethyldiallylammonium chloride; cationic exchange resins;
anionic exchange resins; copolymers of vinylpyrrolidone and
methyacrylamidopropyltrimethylammonium chloride; acidified
polyvinylpolypyrrolidones; acidified copolymers of vinylpyrrolidone
and vinylacetate; acidified copolymers of vinylpyrrolidone and
dimethylaminoethylmetacrylate; copolymers of vinylpyrrolidone and
methacrylamidopropyl trimethylammonium chloride; copolymers of
quaternized vinylpyrrolidone and dimethylaminoethyl methacrylate;
acidified copolymers of vinylpyrrolidone and styrene; acidified
copolymers of vinylpyrrolidone and acrylic acid, and cationic
polyelectrolyte polymers.
[0113] Suitable organic cationic inorganic materials suitable for
use as zeta potential modifiers include, but are not limited to
cationic clay, such as for example, sodium montmorillonite,
hydrotalcite, vermiculite, kaolinite; clays reacted with quaternary
compounds, such as, tetramethylammonium chloride; polyquarternized
amines; acidified n-alkyl-2-pyrrolidones; polyacrylic acid
polymers; alkyl C.sub.8 to alkyl C.sub.24 organic acids, such as
but not limited to, lauric acid, satiric acid; and combinations
thereof.
[0114] Suitable metal oxides and composites include cationically
modified metal oxides and layered metal oxide composites, for
example, but not limited to, oxides of silicon, germanium,
selenium, chromium, titanium, aluminum, gallium, nickel, iron,
copper, silver, gold, platinum, magnesium and calcium, and mixtures
and/or layered composites thereof.
[0115] Suitable zeta potential modifiers further include
cationically modified silicas, such as those disclosed in U.S. App.
No. 20030157804, which is incorporated herein by reference.
[0116] Suitable zeta potential modifiers further include chitosans,
which are cationic biopolymers under the pH conditions, and
cationic chitin derivatives, such as, for example, quatemized
chitosan, optionally in microcrystalline distribution. Examples are
disclosed in Ullmann's Encyclopedia of Industrial Chemistry,
5.sup.th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, p. 231-232,
which is incorporated herein by reference.
[0117] Preferred forms of the zeta potential modifiers described
herein include water soluble, water dispersible and water insoluble
suspensions, dispersions or emulsions of these zeta potential
modifiers. Preferred forms of the inorganic and polymeric based
zeta potential modifiers include fine particulates for improved
dispersibility in the compositions of the instant disclosure.
Preferred forms of the inorganic and polymeric zeta potential
modifiers include particulates having particle sizes in the micron
and nanometer size ranges. Preferred sizes of particulates, for
example, include particle sizes of about 1 nanometer to about 100
microns, most preferred being particle sizes in the range of about
1 nanometer to about 1 microns.
[0118] It should be noted that the source of the zeta potential
modifiers is not critical. Thus, as further demonstrated herein,
commercially available fabric softeners that include cationic
surfactants can be employed as a source of zeta potential
modifiers. Thus, the fabric softener serves multiple functions
including facilitating the attachment of the fluoropolymers and
hydrophobic agents to the fabric surface. Further, multivalent
cationic salts, including cations of the alkaline earth metals
(Group IA), transition metals (Groups IIB, IVB, VB, VIB, VIIB,
VIIIB, IB, IIB, IIA, IVA) and non-metal elements (Groups IVA, VA)
may be appropriate for use as zeta potential modifiers alone,
combined together, or in combination with other zeta potential
modifiers described herein.
[0119] It should further be noted that the zeta potential modifiers
are included as optional ingredients of the laundry additive
compositions as discussed herein. Thus when a composition is
formulated for use as a treatment not in the presence of another
treatment aid, for example a detergent containing anionic
surfactants, or when the composition is formulated for use as a
direct fabric treatment, then the zeta potential modifiers are
deemed optional in that they are not needed to counteract the
negatively charged species, such as anionic surfactants found in
commercial detergents, that might otherwise interfere to some
extent with the attraction of the fluoropolymer to a fabric
surface.
[0120] Highly preferred materials of this class of zeta potential
modifiers are those that do not cause any significant color change,
nor impart any discoloration, such as graying or yellowing, to the
fabrics to which they are applied, either during treatment followed
by drying and/or curing, or after the drying and/or curing step
followed by normal exposure to the elements, such as air, moisture
or sunlight exposure.
[0121] In general, a suitable range for zeta potential modifiers in
the laundry additive compositions presented herein is 0.1 to 30
weight %, more preferably 0.1 to 20 weight % and most preferably
0.1 to 5 weight % of the laundry additive composition. The amount
of zeta potential modifier that may be acceptable for use in a
second laundry additive composition remains about the same, in
order to maintain the zeta potential in the treatment liquor.
Antimicrobials
[0122] Antimicrobial actives that are used with the compositions
and methods described herein are typically present at levels from
0.5 to 60 weight %, more preferably 1 to 40 weight %, and most
preferably 5 to 30 weight % of the entire composition. It is
desired that the amount of residual antimicrobial compound that
remains on a fabric or on a washing machine surface after
completion of a washing cycle is from 10 to 200 ppm. This amount,
from 10 to 200 ppm, has been determined to be an acceptable
quantity of antimicrobial in order to realize microbiocidal
properties. As will be readily understood by those skilled in the
relevant art, however, lower levels of antimicrobial active may be
acceptable for purposes of microbiostasis on either fabrics or
washing machine surfaces. To attain a state of residual
microorganism kill or stasis, it is foreseen that deposition of a
polymer with embedded or associated microbiocide or
microbiostat--particularly silver, copper, or zinc species--needs
to be sufficient to be present following the laundering
process.
[0123] Without being bound by theory, it is postulated that
following deposition of an antimicrobially-active compound or
compounds, an embedded or associated microbiocide or microbiostat
is released from the deposited material when organisms land on, or
try to form on, the surface of a fabric or washing machine surface.
In the case of antimicrobials that comprise silver-, copper, or
zinc-polymer actives, ions of silver, copper, or zinc are released
from the polymer, which in turn can cause microbial death or
stasis. Ideally, there should be enough antimicrobial active
material deposited such that as the microbiocide or microbiostat is
consumed by their interaction with microbes, additional
antimicrobial active is released from the laundry additive residue
and the process continues.
[0124] Suitable antimicrobials for use with the laundry additives
of the instant specification are those that contain metal ions such
as silver, copper, zinc, and combinations of the foregoing, as well
as their metal oxides. One family of antimicrobials that is
acceptable for use with the antimicrobial laundry additive products
described herein is available from Dow Chemical Company (Midland,
Mich.) and sold under the Silvadur.TM. trade name. Examples of
especially acceptable Silvadur.TM. products include Silvadur.TM.
900 (acrylic polymer, ethanol, isopropanol, ammonium hydroxide,
silver ion, butanol, and ammonium nitrate in water), Silvadur.TM.
930 (silver ion, ethanol, ammonium hydroxide, and polymer in
water), and Silvadur.TM. 961 (silver nitrate, nitric acid, and
acrylic polymer in water). Another antimicrobial that is suitable
for use with the antimicrobial laundry additive products described
herein is available from Cupron, Inc. (Richmond, Va.). Cupron sells
a copper-oxide based material that can be incorporated into a
polymer matrix for deposition into or onto fabrics and so-called
touch surfaces (that is, surfaces that are contacted by human hands
and thus prone to contamination). Yet another suitable material is
Fosshield.RTM., available from Foss Manufacturing Company, LLC
(Hampton, N.H.), containing a combination of silver and copper
ions, which can be admixed with a suitable polymer or polymer blend
and incorporated herein. Lonza Group Ltd., with locations
worldwide, provides a zinc pyridinethione, which can likewise be
admixed with a suitable polymer or polymer blend and incorporated
herein.
[0125] Highly preferred antimicrobials are those that do not cause
any significant color change, nor impart any discoloration, such as
graying or yellowing, to the fabrics or washing machine surfaces to
which they are applied, either during treatment followed by drying,
or after the drying step followed by normal exposure to the
elements, such as air, moisture or sunlight exposure.
Optional Ingredients
Emulsifiers
[0126] The fluoropolymers and hydrophobic agents mentioned above
may require the use of emulsifiers, such as ethoxylated fatty
alcohols, fatty amides, fatty acids and alkylphenols and fatty
amines or salts thereof. Other preferred emulsifiers include
quaternary ammonium or protonated amine cationic surfactants such
as trimethyl-dodecylammonium chloride, trimethyl-hexadecylanimonium
chloride, dimethyl-dicocoammonium chloride, and
dimethyl-octadecylammonium acetate. Preferred nonionic emulsifiers
include the etherification products of ethylene oxide and/or
propylene oxide with glycerol monooleate, oleic acid, cetyl
alcohol, pelargonic acid, stearyl alcohol, sorbitan monooleate,
sorbitan monostearate.
[0127] Highly preferred materials of this class of emulsifiers are
those that do not cause any significant color change, nor impart
any discoloration, such as graying or yellowing, to the fabrics to
which they are applied, either during treatment followed by drying,
or after the drying step followed by normal exposure to the
elements, such as air, moisture or sunlight exposure.
pH Adjusters
[0128] The pH of a solution of compositions of this invention may
be adjusted to be in the range from about 2 to about 11. Adjustment
of pH may be carried out by including a small quantity of an acid
in the formulation. Because no strong pH buffers need be present,
only small amounts of acid may be required. The pH may be adjusted
with inorganic or organic acids, for example hydrochloric acid or
alternatively with monobasic or dibasic organic acids, such as
acetic acid, maleic acid or in particular glycolic acid. Additional
acids that can be used include, but are not limited to, methyl
sulfonic, hydrochloric, sulfuric, phosphoric, citric, maleic, and
succinic acids. Adjustment of pH may be carried out by including a
small quantity of a base in the formulation. Because no strong pH
buffers need be present, only small amounts of base may be
required. The pH may be adjusted with inorganic bases, including,
but not limited to, alkali metal or alkaline earth metal salts of
hydroxides, carbonates, bicarbonates, borates, sulfonates,
phosphates, phosphonates and silicates. The pH may be adjusted with
organic bases, including, but not limited to, salts of
monocarboxylic acids, salts of dicarboxylic acids, salts of citric
acid and other suitable organic acids with water soluble conjugate
bases presented previously herein. The pH may be adjusted with
organic bases such as the alkanolamines including methanol, ethanol
and propanol amines, including dimethanol, diethanol and dipropanol
amines, and including trimethanol, triethanol and tripropanol
amines.
[0129] Highly preferred materials of this class of pH adjusters are
those that do not cause any significant color change, nor impart
any discoloration, such as graying or yellowing, to the fabrics to
which they are applied, either during treatment followed by drying
and/or curing, or after the drying and/or curing step followed by
normal exposure to the elements, such as air, moisture or sunlight
exposure.
Silicones
[0130] An optional silicone component can be used in an amount from
about 0.1% to about 6% of the composition, preferably from 0.1 to
3% of the composition. These optional ingredients include silicones
and organopolysiloxanes. In addition to the known
dialkylpolysiloxanes, it is possible to use, in particular,
hydrophilizing silicones, such as dimethylpolysiloxanes which
contain incorporated epoxy groups and/or polyethoxy or polypropoxy
or polyethoxy/propoxy groups. Preferred siloxanes include
aminoethylaminopropyl dimethyl siloxane, hydroxy terminated
dimethyl siloxane also known as dimethiconol, and modified hydrogen
alkyl polysiloxanes. Preferred silicones comprise cationic and
amphoteric silicones, polysiloxanes, and polysiloxanes having
hydrogen-bonding functional groups consisting of amino, carboxyl,
hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and
thiol groups. Such polysiloxanes include, but are not limited to,
polyether-modified polysiloxanes, amino-modified polysiloxanes,
epoxy-modified polysiloxanes, polyhydrido-modified polysiloxanes,
phenol derivative-modified polysiloxanes, ABA-type polysiloxanes,
including those available from Osi Specialties, Inc. (a division of
Witco Corporation), under the SILWET, NUWET, NUDRY, NUSOF,
MAGNASOFT trade names. Preferred silicones may include
polydimethylsiloxanes of viscosity from about 100 centistokes (cs)
to about 100,000 cs, and preferably from about 200 cs to about
60,000 cs and/or silicone gums. These silicones can be used in
emulsified form, which can be conveniently obtained directly from
the suppliers. Examples of these pre-emulsified silicones are the
60% emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning
Corporation under the trade name DOW CORNING 1157 Fluid and the 50%
emulsion of polydimethylsiloxane (10,000 cs) sold by General
Electric Company under the trade name GENERAL ELECTRIC 2140
silicones. Silicone foam suppressants can also be used. These are
usually not emulsified and typically have viscosities from about
100 cs to about 10,000 cs, and preferably from about 200 cs to
about 5,000 cs. Very low levels can be used, typically from about
0.01% to about 1%, and preferably from about 0.02% to about 0.5%.
Another preferred foam suppressant is a silicone/silicate mixture,
for example, DOW CORNING ANTIFOAM A.
[0131] Highly preferred materials of this class of silicones are
those that do not cause any significant color change, nor impart
any discoloration, such as graying or yellowing, to the fabrics to
which they are applied, either during treatment followed by drying
and/or curing, or after the drying and/or curing step followed by
normal exposure to the elements, such as air, moisture or sunlight
exposure.
Nonionic Surfactants
[0132] The composition can contain a nonionic surfactant. When a
nonionic surfactant is added to the composition, it can typically
be added at a level from about 0.05% to about 30%, preferably from
about 0.05% to about 20%, and more preferably from about 0.1% to
about 10% of the composition.
[0133] Suitable nonionic surfactants include addition products of
alkoxylating agents such as ethylene oxide (EO), propylene oxide
(PO), isopropylene oxide (IPO), or butylene oxide (BO), or a
mixture thereof, with fatty alcohols, fatty acids, and fatty
amines. Any of the alkoxylated materials of the particular type
described hereinafter can be used as the nonionic surfactant.
Preferably, the nonionic surfactant is selected from the group
consisting of alkylether carboxylate, alcohol ethoxylate or
secondary alcohol ethoxylate, and alkyl phenyl ethoxylate or alkyl
aryl ethoxylate. These nonionic surfactants may also contain a
mixture of ethoxylate and propoxylate. Suitable
alkylpolysaccharides for use herein are disclosed in U.S. Pat. No.
4,565,647 to Llenado and incorporated herein by reference, having a
hydrophobic group containing from about 6 to about 30 carbon atoms,
preferably from about 10 to about 16 carbon atoms and a
polysaccharide, e.g., a polyglycoside, hydrophilic group. Further
examples of suitable surfactants are described in McCutcheon's Vol.
1: Emulsifiers and Detergents, North American Ed., McCutcheon
Division, MC Publishing Co., 1995, which is incorporated herein by
reference.
[0134] Highly preferred materials of this class of nonionic
surfactants are those that do not cause any significant color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
Cationic Surfactants
[0135] The composition of the instant disclosure can contain a
cationic surfactant. When a cationic surfactant is added to the
composition of the instant disclosure, it can typically be added at
a level from about 0.05% to about 30%, preferably from about 0.05%
to about 20%, and more preferably from about 0.1% to about 10% of
the composition.
[0136] The cationic surfactant can optionally be one or more fabric
softener actives. Preferred fabric softening actives according to
the instant disclosure include amines and quaternized amines. The
following are examples of preferred softener actives:
N,N-di(tallowyl-oxy-ethyl)N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl,
N-(2-hydroxyethyl) ammonium methyl sulfate;
N,N-di(tallowylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
methyl sulfate; N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride; N,N-di(2-canolyloxy-2-oxo-ethyl)N,N-dimethyl
ammonium chloride;
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride; N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl
ammonium chloride;
N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride, N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium
chloride; N,N,N-tri(canolyl-oxyethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium
chloride; N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl
ammonium chloride;
1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride; and
mixtures of the above actives. Particularly preferred is
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where
the tallow chains are at least partially unsaturated and
N,N-di(canoloyl-oxy-ethyl)-N,N-dimethyl ammonium chloride,
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl,
N-(2-hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.
Additional fabric softening agents useful herein are described in
U.S. Pat. No. 5,643,865 to Mermelstein, et al.; U.S. Pat. No.
5,622,925 to de Buzzaccarini, et al.; U.S. Pat. No. 5,545,350 to
Baker, et al.; U.S. Pat. No. 5,474,690 to Wahl, et al.; U.S. Pat.
No. 5,417,868 to Turner, et al.; U.S. Pat. No. 4,661,269 to Trinh,
et al.; U.S. Pat. No. 4,439,335 to Burns; U.S. Pat. No. 4,401,578
to Verbruggen; U.S. Pat. No. 4,308,151 to Cambre; U.S. Pat. No.
4,237,016 to Rudkin, et al.; U.S. Pat. No. 4,233,164 to Davis; U.S.
Pat. No. 4,045,361 to Watt, et al.; U.S. Pat. No. 3,974,076 to
Wiersema, et al.; U.S. Pat. No. 3,886,075 to Bernadino; U.S. Pat.
No. 3,861,870 Edwards, et al.; and European Patent Application
publication No. 472,178, to Yamamura, et al.; all of said documents
being incorporated herein by reference.
[0137] Other suitable cationic surfactants include ethoxylated
quaternary ammonium surfactants. Some preferred ethoxylated
quaternary ammonium surfactants include PEG-5 cocoammonium
methosulfate; PEG-15 cocoammonium chloride; PEG-15 oleoammonium
chloride; and bis(polyethoxyethanol) tallow ammonium chloride.
Further examples of suitable surfactants are described in
McCutcheon's Vol. 1: Emulsifiers and Detergents, North American
Ed., McCutcheon Division, MC Publishing Co., 1995, which is
incorporated herein by reference.
[0138] The counterion to these cationic surfactants may be
selected, without limitation, from the group consisting of
fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide,
hypophosphite, phosphite, phosphate, carbonate, formate, acetate,
lactate, and other carboxylates, oxalate, methyl sulfate, ethyl
sulfate, benzoate, and salicylate, and the like. Highly preferred
materials of this class of cationic surfactants and their
counterions are those that do not cause any significant color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
Amphoteric and Zwitterionic Surfactants
[0139] The composition of the instant disclosure can contain
amphoteric and/or zwitterionic surfactants. When an amphoteric or
zwitterionic surfactant is added to the composition of the instant
disclosure, it can typically be added at a level from about 0.05%
to about 30%, preferably from about 0.05% to about 20%, and more
preferably from about 0.1% to about 10% of the composition.
[0140] Suitable amphoteric surfactants include amine oxides having
the formula (R.sub.1)(R.sub.2)(R.sub.3)NO wherein each of R.sub.1,
R.sub.2 and R.sub.3 is independently a saturated substituted or
unsubstituted, linear or branched hydrocarbon chains of from 1 to
30 carbon atoms. Preferred amine oxide surfactants to be used
according to the instant disclosure include amine oxides having the
formula (R.sub.1)(R.sub.2)(R.sub.3)NO wherein R.sub.1 is a
hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably
from 6 to 20, more preferably from 8 to 16, further preferably from
8 to 12, and wherein R.sub.2 and R.sub.3 are independently
substituted or unsubstituted, linear or branched hydrocarbon chains
comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon
atoms, and more preferably are methyl groups. R.sub.1 may be a
saturated substituted or unsubstituted, linear or branched
hydrocarbon chain. Suitable amine oxides for use herein are, for
instance, naturally derived hydrocarbon blends of C.sub.8-C.sub.10
amine oxides as well as C.sub.12-C.sub.16 amine oxides commercially
available from Hoechst.
[0141] Suitable zwitterionic surfactants may contain both cationic
and anionic hydrophilic groups on the same molecule at a relatively
wide pH range. A typical cationic group is a quaternary ammonium
group, although other positively charged groups like phosphonium,
imidazolium and sulfonium groups can be used. Typical anionic
hydrophilic groups are carboxylates and sulfonates, although other
groups like sulfates, phosphonates, and the like can be used. A
generic formula for some zwitterionic surfactants that can be used
herein is R.sub.1--N'(R.sub.2)(R.sub.3)R.sub.4X-- wherein R.sub.1
is a hydrophobic group; R.sub.2 and R.sub.3 are each
C.sub.1-C.sub.4 alkyl, hydroxy alkyl or other substituted alkyl
group which can also be joined to form ring structures with the N;
R.sub.4 is a moiety joining the cationic nitrogen atom to the
hydrophilic group and is typically an alkylene, hydroxy alkylene,
or polyalkoxy group containing from 1 to 10 carbon atoms; and X is
the hydrophilic group which is preferably a carboxylate or
sulfonate group. Preferred hydrophobic groups R.sub.1 are alkyl
groups containing from 1 to 24, preferably less than 18, and more
preferably less than 16 carbon atoms. The hydrophobic group can
contain unsaturation and/or substituents and/or linking groups such
as aryl groups, amido groups, ester groups and the like. In
general, the simple alkyl groups are preferred for cost and
stability reasons. Examples of amphoteric surfactants include
alkylamphoglycinates, and alkyl imino propionate. Highly preferred
zwitterionic surfactants include betaine and sulphobetaine
surfactants, derivatives thereof or mixtures thereof. The betaine
or sulphobetaine surfactants are preferred herein as they are
particularly suitable for the cleaning of delicate materials,
including fine fabrics such as silk, wool and other naturally
derived textile materials. Betaine and sulphobetaine surfactants
are also extremely mild to the skin and/or fabrics to be treated
that come in contact with the user's skin.
[0142] Suitable betaine and sulphobetaine surfactants to be used
herein include the betaine/sulphobetaine and betaine-like
detergents wherein the molecule contains both basic and acidic
groups which form an inner salt giving the molecule both cationic
and anionic hydrophilic groups over a broad range of pH values.
Some common examples of these detergents are described in U.S. Pat.
No. 2,082,275 to Daimler, et al., U.S. Pat. No. 2,702,279 to
Funderburk, et al., and U.S. Pat. No. 2,255,082 to Orthner, et al.,
which are incorporated herein by reference. Further examples of
suitable surfactants are described in McCutcheon's Vol. 1:
Emulsifiers and Detergents, North American Ed., McCutcheon
Division, MC Publishing Co., 1995, which is incorporated herein by
reference.
[0143] Highly preferred materials of this class of amphoteric and
zwitterionic surfactants are those that do not cause any
significant color change, nor impart any discoloration, such as
graying or yellowing, to the fabrics to which they are applied,
either during treatment followed by drying and/or curing, or after
the drying and/or curing step followed by normal exposure to the
elements, such as air, moisture or sunlight exposure.
Anionic Surfactants
[0144] The composition can contain an anionic surfactant. When an
anionic surfactant is added to the composition of the instant
disclosure, it can typically be added at a level from about 0.05%
to about 15%, preferably from about 0.05% to about 5%, and more
preferably from about 0.1% to about 1% of the composition.
[0145] Suitable anionic surfactants include C.sub.8-C.sub.18 alkyl
sulfonates, C.sub.10-C.sub.14 linear or branched alkyl benzene
sulfonates, C.sub.10-C.sub.14 alkyl sulfates and ethoxysulfates
(e.g., STEPANOL AMC from Stepan), and C.sub.9-C.sub.15 alkyl ethoxy
carboxylates (NEODOX surfactants available from Shell Chemical
Corporation). Suitable commercially available sulfonates are
available from Stepan under the trade name BIO-TERGE PAS-88 as well
as from the Witco Corporation under the trade name WITCONATE NAS-8,
and Hostapur SAS from Hoechst Aktiengesellschaft, D-6230 Frankfurt,
Germany. Anionic surfactants may be paired with organic counterions
or multivalent counterions in order to prevent interference with
cationic species. Further examples of suitable surfactants are
described in McCutcheon's Vol. 1: Emulsifiers and Detergents, North
American Ed., McCutcheon Division, MC Publishing Co., 1995, which
is incorporated herein by reference.
[0146] Highly preferred materials of this class of anionic
surfactants are those that do not cause any significant color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
Soil Release Agents
[0147] The laundry additive compositions described herein can also
include a soil release agent, which is present from about 0% to
about 5%, preferably from about 0.05% to about 3%, and more
preferably from about 0.1% to about 2% of the composition.
Polymeric soil release agents useful in the instant disclosure
include co-polymeric blocks of terephthalate and polyethylene oxide
or polypropylene oxide, and the like. A preferred soil release
agent is a copolymer having blocks of terephthalate and
polyethylene oxide. More specifically, these polymers may be
comprised of repeating units of ethylene terephthalate and
polyethylene oxide terephthalate at a molar ratio of ethylene
terephthalate units to polyethylene oxide terephthalate units from
about 25:75 to about 35:65, and the polyethylene oxide
terephthalate containing polyethylene oxide blocks having molecular
weights from about 300 to about 2000. The molecular weight of this
type of polymeric soil release agent can be in the range from about
5,000 to about 55,000. Suitable soil release agents are disclosed
in U.S. Pat. No. 4,702,857 to Gosselink, U.S. Pat. No. 4,711,730 to
Gosselink, et al., and U.S. Pat. No. 4,713,194 to Gosselink; U.S.
Pat. No. 4,877,896 to Maldonado, et al.; U.S. Pat. No. 4,956,447
Gosselink, et al.; and U.S. Pat. No. 4,749,596 to Po, et al.; all
of which are incorporated herein by reference. Especially desirable
optional ingredients are polymeric soil release agents comprising
block copolymers of polyalkylene terephthalate and polyoxyethylene
terephthalate, and block copolymers of polyalkylene terephthalate
and polyethylene glycol. The polyalkylene terephthalate blocks may
preferably comprise ethylene and/or propylene groups. Many such
soil release polymers are nonionic, for example, the nonionic soil
release polymer described in U.S. Pat. No. 4,849,257 to Borcher,
Sr., et al., which is incorporated herein by reference. The
polymeric soil release agents useful in the instant disclosure can
include anionic and cationic polymeric soil release agents.
Suitable anionic polymeric or oligomeric soil release agents are
disclosed in U.S. Pat. No. 4,018,569 to Chang, which is
incorporated herein by reference. Other suitable polymers are
disclosed in U.S. Pat. No. 4,808,086 to Evans, et al., which is
incorporated herein by reference.
[0148] Highly preferred materials of this class of soil release
polymers are those that do not cause any significant color change,
nor impart any discoloration, such as graying or yellowing, to the
fabrics to which they are applied, either during treatment followed
by drying and/or curing, or after the drying and/or curing step
followed by normal exposure to the elements, such as air, moisture
or sunlight exposure.
Antistatic Agents
[0149] The composition can include antistatic agents, which can be
present at a level from about 0% to about 5%, preferably from about
0.005% to about 5%, more preferably from about 0.05% to about 2%,
and further preferably from about 0.2% to about 1% of the
composition. Preferred antistatic agents of the instant disclosure
include cationic surfactants, including quaternary ammonium
compounds such as alkyl benzyl dimethyl ammonium chloride; dicoco
quaternary ammonium chloride; coco dimethyl benzyl ammonium
chloride; soya trimethyl quaternary ammonium chloride; hydrogenated
tallow dimethyl benzyl ammonium chloride; and methyl dehydrogenated
tallow benzyl ammonium chloride. Other preferred antistatic agents
of the instant disclosure are alkyl imidazolinium salts. Other
preferred antistatic agents are the ion pairs of, e.g., anionic
detergent surfactants and fatty amines, or quaternary ammonium
derivatives thereof, e.g., those disclosed in U.S. Pat. No.
4,756,850 to Nayar, which is incorporated herein by reference.
Other preferred antistatic agents are ethoxylated and/or
propoxylated sugar derivatives. Preferred antistatic agents include
monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl
dimethyl ammonium chloride (available from Henkel Corporation under
the trade name DEHYQUART E), and ethyl bis(polyethoxyethanol) alkyl
ammonium ethyl sulfate (available from Witco Corporation under the
trade name VARIQUAT 66), polyethylene glycols, polymeric quaternary
ammonium salts (such as those available from Rhone-Poulenc
Corporation under the MIRAPOL trade name), quaternized
polyethyleneimines, vinylpyrrolidone/methacrylamidopropyl
trimethylammonium chloride copolymer (available from GAF
Corporation under the trade name GAFQUAT HS-100), triethonium
hydrolyzed collagen ethosulfate (available from Maybrook Inc. under
the trade name QUAT-PRO E), and mixtures thereof. Highly preferred
materials of this class of antistatic agents are those that do not
cause any significant color change, nor impart any discoloration,
such as graying or yellowing, to the fabrics to which they are
applied, either during treatment followed by drying and/or curing,
or after the drying and/or curing step followed by normal exposure
to the elements, such as air, moisture or sunlight exposure.
Fragrance
[0150] Perfumes or fragrance materials may be added to the
composition. The selection of the perfume or perfumes maybe based
upon the application, the desired effect on the consumer, and
preferences of the formulator. The perfume selected for use in the
compositions and formulations of the instant disclosure may contain
ingredients with odor characteristics which are preferred in order
to provide a fresh impression on the surface to which the
composition is directed, for example, those which provide a fresh
impression for fabrics. Such perfume may be preferably present at a
level from about 0.01% to about 5%, preferably from about 0.05% to
about 3%, and more preferably from about 0.1% to about 2% of the
total composition.
[0151] Preferably, the perfume may be composed of fragrance
materials selected from the group consisting of aromatic and
aliphatic esters having molecular weights from about 130 to about
250; aliphatic and aromatic alcohols having molecular weights from
about 90 to about 240; aliphatic ketones having molecular weights
from about 150 to about 260; aromatic ketones having molecular
weights from about 150 to about 270; aromatic and aliphatic
lactones having molecular weights from about 130 to about 290;
aliphatic aldehydes having molecular weights from about 140 to
about 200; aromatic aldehydes having molecular weights from about
90 to about 230; aliphatic and aromatic ethers having molecular
weights from about 150 to about 270; and condensation products of
aldehydes and amines having molecular weights from about 180 to
about 320; and mixtures thereof. Examples of such perfumes or
fragrance materials include, but are not limited to: adoxal
(2,6,10-trimethyl-9-undecen-1-al), allyl amyl glycolate, allyl
cyclohexane (allyl-3-cyclohexylpropionate), amyl acetate
(3-methyl-1-butanol), amyl salicylate, anisic aldehyde
(4-methoxybenzaldehyde), aurantiol (condensation product of methyl
anthranilate and hydroxycitronellal), bacdanol
(2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol),
benzaldehyde, benzophenone, benzyl acetate, benzyl salicylate,
damascene (1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one,
3-hexen-1-ol, buccoxime
(1,5-dimethyl-oximebicyclo[3,2,1]octan-8-one), cedrol
(octahydro-3,6,8,8-tetramethyl-1H-3A,-7-methanoazulen-6-ol),
cetalox (dodecahydro-3A,6,-6,9A-tetramethylnaphtho[2,1]furan),
cis-3-hexenyl acetate, cis-3-hexenyl salicylate, citronellol
(3,7-dimethyl-6-octenol), citronellyl nitrile (geranyl nitrile),
clove stem oil, coumarin, cyclohexyl salicylate, cymal
(2-methyl-3-(p-isopropylphenyl)-propionaldehyde), decyl aldehyde,
damascene (1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one),
dihydromyrcenol (2,6-dimethyl-7-octan-2-ol), dimethyl benzyl
carbonyl acetate, ethyl vanillin, ethyl-2-methyl butyrate, ethylene
brassylate (ethylene tridecan-1,13-dioate), eucalyptol
(1,8-epoxy-p-menthane), eugenol (4-allyl-2-methoxyphenol),
exaltolide (cyclopentadecanolide), for acetate
(dihydronorcyclopentadienyl acetate), florhydral
(3-(3-isopropylphenyl)butanal), frutene (dihydronorcyclopentadienyl
propionate), galaxolide
(1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopent-gamma-2-benzopyran-
e), gamma-decalactone (4-N-heptyl-4-hydroaldehyde), cinnamic
aldehyde, hexyl salicylate, hydroxyambran (2-cyclododecylpropanol),
hydroxycitronellal, ionone
(4-(2,6,6-trimethyl-1-cyclohexenyl-1-yl)-3-buten-2-one), ionone
(4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-3-butene-2-one), ionone
(4-(2,6,6-trimethyl-2-methylcyclohexyl-1-yl)-3-methyl-3-buten-2-one),
7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene,
isoeugenol (2-methoxy-4-(1-propenyl)-phenol), isojasmone
(2-methyl-3-(2-pentenyl)-2-cyclopenten-1-one), koavone (acetyl
diisoamylene), lauric aldehyde, lavandin, lavender, natural lemon
(major component d-limonene), d-limonene/orange terpenes
(1-methyl-4-isopropenyl-1-cyclohexene), linalool
(3-hydroxy-3,7-dimethyl-1,6-octadiene), linalyl acetate
(3-hydroxy-3,7-dimethyl-1,6-octadiene acetate), Irg.TM. 201
(2,4-dihydroxy-3,6-dimethyl benzoic acid methyl ester), lyral
(4-(4-hydroxy-4methyl-pentyl)-3-cyclohexene-1-carboxaldehyde),
majantol (2,2-dimethyl-3-(3-methylphenyl)propanol), mayol
(4-(1-methylethyl)-cyclohexanemethanol), methyl anthranilate
(methyl-2-aminobenzoate), methyl-alpha-naphthyl ketone, methyl
cedrylone (methyl cedrenyl ketone), methyl chavicol
(1-methyloxy-4,2-propen-1-yl benzene), methyl dihydrojasmonate,
methyl nonyl acetaldehyde, musk indanone
(4-acetyl-6-tert-butyl-1,1-dimethylindane), nerol
(2-cis-3,7-dimethyl-2,6-octadien-1-ol), nonalactone
(4-hydroxynonanoic acid lactone), norlimbanol
(1-(2,2,6-trimethyl-cyclohexyl)-3-hexanol), orange CP (major
component d-limonene), para-tert-bucinal
(2-methyl-3-(p-tert-butylphenyl)-propionaldehyde),
p-hydroxyphenylbutanone, patchouli, phenyl acetaldehyde
(1-oxo-2-phenylethane), phenyl acetaldehyde, dimethyl acetal,
phenyl ethyl acetate, p-menth-1-en-8-ol, p-menth-1-en-1-ol,
terpinyl acetate p-menth-1-en-8-yl acetate), tetrahydrolinalool
(3,7-dimethyl-3-octanol), tetrahydromyrcenol
(2,6-dimethyl-2-octanol), tonalid/musk plus
(7-acetyl-1,1,3,4,4,6-hexamethyltetralin), undecalactone
(4-N-heptyl-4-hydroxybutanoic acid lactone), undecavertol
(4-methyl-3-decen-5-ol), undecanal, undecylenic aldehyde, vanillin
(4-hydroxy-3-methoxybenzaldehyde), verdox (2-tert-butyl cyclohexyl
acetate), vertenex (4-tertbutyl cyclohexyl acetate), and mixtures
thereof.
[0152] The selection of such perfumes and fragrance materials is
well-known to those of skill in the art, both for desired scent and
appropriate scent impact. For example, when high initial perfume
odor impact on fabrics is desired, it can be preferable to select a
perfume containing perfume ingredients which are not too
hydrophobic. The degree of hydrophobicity of a perfume ingredient
can be correlated with its octanol/water partitioning coefficient
P, the ratio between its equilibrium concentration in octanol and
in water. Thus, a perfume ingredient with a greater partitioning
coefficient P is more hydrophobic and a perfume ingredient with a
smaller partitioning coefficient P is more hydrophilic; a selection
based on the application and intended effect may be made
accordingly. For example, in a fabric application, the preferred
perfume ingredients may have an octanol/water partitioning
coefficient P of about 1,000 or smaller.
[0153] Highly preferred materials of this class of fragrances and
perfumes are those that do not cause any significant color change,
nor impart any discoloration, such as graying or yellowing, to the
fabrics to which they are applied, either during treatment followed
by drying and/or curing, or after the drying and/or curing step
followed by normal exposure to the elements, such as air, moisture
or sunlight exposure.
Preservatives
[0154] Optionally, preservatives can be added to the laundry
additive compositions of the instant disclosure. In order to
provide good biocidal effectiveness, typical concentrations of
these compounds may range from about 0.001% to about 0.8% by
weight, preferably from about 0.005% to about 0.3% by weight, and
more preferably from about 0.01% to 0.2% by weight of the laundry
additive composition. The corresponding concentrations for the
compositions herein are from about 0.003 wt. % to about 2 wt. %,
preferably from about 0.006 wt. % to about 1.2 wt. %, and more
preferably from about 0.1 wt. % to about 0.8 qr. % of the
concentrated compositions.
[0155] Preservatives are especially preferred when organic
compounds that are subject to attack by microorganisms, for example
surfactants, polymers, fragrances, etc. are added to the
antimicrobial laundry additive products disclosed herein,
especially when they are used in aqueous compositions. When such
compounds are present, long term and even short-term storage
stability of the compositions and formulations becomes an important
issue since contamination by certain microorganisms with subsequent
microbial growth often results in an unsightly and/or malodorous
solution. While the antimicrobial incorporated into the formulation
in fact may kill many microorganisms that could contaminate a
formula, it is foreseen that the antimicrobial of the instant
disclosure instant disclosure may be incapable of eliminating all
possible microorganisms that may contaminate the formulation, or
possibly may not be available for antimicrobial action until
diluted in a treatment liquor. Therefore, because microbial growth
in these compositions and formulations is highly objectionable when
it occurs, it may be preferable to include a solubilized
water-soluble, antimicrobial preservative, which is effective for
inhibiting and/or regulating microbial growth in order to increase
storage stability of the preferably clear and often aqueous
compositions and formulations of the instant disclosure.
[0156] Typical microorganisms that can be found in laundry products
include bacteria, for example, Bacillus thurigensis (cereus group)
and Bacillus sphaericus, and fungi, for example, Aspergillus ustus.
Bacillus sphaericus is one of the most numerous members of Bacillus
species in soils. In addition, microorganisms such as Escherichia
coli and Pseudomonas aeruginosa are found in some water sources,
and can be introduced during the preparation of aqueous solutions
of the instant disclosure. It is preferable to use a broad spectrum
preservative, for example, one that is effective on both bacteria
(both Gram positive and Gram negative) and fungi. A limited
spectrum preservative, for example, one that is only effective on a
single group of microorganisms, for example, fungi, can be used in
combination with a broad spectrum preservative or other limited
spectrum preservatives with complimentary and/or supplementary
activity. A mixture of broad-spectrum preservatives can also be
used. Antimicrobial preservatives useful in the instant disclosure
can be biocidal compounds, that is, substances that kill
microorganisms, or biostatic compounds, that is, substances that
inhibit and/or regulate the growth of microorganisms. Preferred
antimicrobial preservatives include those that are water-soluble
and are effective at low levels. In general, the water-soluble
preservatives that may be used include organic sulfur compounds,
halogenated compounds, cyclic organic nitrogen compounds, low
molecular weight aldehydes, quaternary compounds, dehydroacetic
acid, phenyl and phenoxy compounds, and mixtures thereof. Examples
of preservatives useful in the instant disclosure include, but are
not limited to, the short chain alkyl esters of p-hydroxybenzoic
acid (commonly known as parabens);
N-(4-chlorophenyl)-N-(3,4-dichlorophenyl) urea (also known as
3,4,4-trichlorocarbanilide or triclocarban);
2,4,4-trichloro-2'-hydroxydiphenyl ether, commonly known as
Triclosan.RTM.); a mixture of about 77%
5-chloro-2-methyl-4-isothiazolin-3-one and about 23%
2-methyl-4-isothiazolin-3-one, a broad spectrum preservative
available from the Rohm and Haas Company as a 1.5% aqueous solution
under the trade name KATHON CG; 5-bromo-5-nitro-1,3-dioxane,
available from Cognis Corporation under the trade name BRONIDOX L;
2-bromo-2-nitropropane-1,3-diol, available from Inolex Chemical
Company under the trade name BRONOPOL;
1,1-hexamethylenebis(5-p-(chlorophenyl)biguanide) (commonly known
as chlorhexidine) and its salts, for example, with acetic and
digluconic acids; a 95:5 mixture of
1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and
3-butyl-2-iodopropynyl carbamate, available from Lonza Inc. under
the trade name GLYDANT Plus;
N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'-bis(hydroxy-met-
hyl) urea, commonly known as diazolidinyl urea, available from
Sutton Laboratories, Inc. under the trade name GERMALL II;
N,N''-methylenebis-[N'-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea-
] (commonly known as imidazolidinyl urea), available, for example,
from 3V-Sigma under the trade name ABIOL, from Induchem under the
trade name UNICIDE U-13, and from Sutton Laboratories, Inc. under
the trade name GERMALL 115; polymethoxy bicyclic oxazolidine,
available from Huls America Inc. under the trade name NUOSEPT;
formaldehyde; glutaraldehyde; polyaminopropyl biguanide, available
from ICI Americas, Inc. under the trade name COSMOCIL CQ or from
Brooks Industries Inc. under the trade name MIKROKILL dehydroacetic
acid; and mixtures thereof. In general, however, the preservative
can be any organic preservative material that is appropriate for
applying to a fabric. With respect to the embodiments presented
herein, such preservative(s) will preferably not cause damage to a
fabric appearance, for example, through discoloration, coloration,
or bleaching of the fabric. If the antimicrobial preservative is
included in the compositions and formulations of the instant
disclosure, it is preferably present in an effective amount,
wherein an "effective amount" means a level sufficient to prevent
spoilage or prevent growth of inadvertently added microorganisms
for a specific period of time. Preferred levels of preservative are
from about 0.0001% to about 0.5%, more preferably from about
0.0002% to about 0.2%, further preferably from about 0.0003% to
about 0.1%, of the composition. Optionally, the preservative can be
used at a level that provides an antimicrobial effect on the
treated fabrics.
[0157] The composition may optionally use a further water-soluble
antimicrobial active, useful in providing additional protection of
the formula against microorganisms. Some of the more robust
antimicrobial halogenated compounds which can function as
disinfectants/sanitizers as well as finish product preservatives,
and are useful in the compositions of the instant disclosure
include 1,1'-hexamethylene bis(5-(p-chlorophenyl)biguanide),
commonly known as chlorhexidine, and its salts, e.g., with
hydrochloric, acetic and gluconic acids. The digluconate salt is
highly water-soluble, about 70% in water, and the diacetate salt
has a solubility of about 1.8% in water. When chlorhexidine is used
as a sanitizer in the instant disclosure it can typically be
present at a level from about 0.001% to about 1.0%, preferably from
about 0.002% to about 0.3%, and more preferably from about 0.01% to
about 0.1%, by weight of the usage composition. In some cases, a
level from about 1% to about 2% may be needed for virucidal
activity. Other useful biguanide compounds include COSMOCI, CQ,
VANTOCIL IB, including poly (hexamethylene biguanide)
hydrochloride. Other useful cationic antimicrobial agents include
the bis-biguanide alkanes. Usable water soluble salts of the above
are chlorides, bromides, sulfates, alkyl sulfonates such as methyl
sulfonate and ethyl sulfonate, phenylsulfonates such as
p-methylphenyl sulfonates, nitrates, acetates, gluconates, and the
like. Non-limiting examples of useful quaternary compounds include:
(1) benzalkonium chlorides and/or substituted benzalkonium
chlorides such as commercially available BARQUAT (available from
Lonza), MAQUAT (available from Mason), VARIQUAT (available from
Evonik Industries), and HYAMINE (available from Lonza); (2) dialkyl
quaternary such as BARDAC products of Lonza, (3)N-(3-chloroallyl)
hexaminium chlorides such as DOWICIDE and DOWICIL available from
Dow; (4) benzethonium chloride such as HYAMINE 1622 from Lonza; (5)
methylbenzethonium chloride represented by HYAMINE 10X supplied by
Lonza, (6) cetylpyridinium chloride such as Cepacol chloride
available from of Merrell Labs.
[0158] Preferred antimicrobial compounds for use herein include
quaternary ammonium compounds containing alkyl or substituted alkyl
groups, alkyl amide and carboxylic acid groups, ether groups,
unsaturated alkyl groups, and cyclic quaternary ammonium compounds,
which can be chlorides, dichlorides, bromides, methylsulphates,
chlorophenates, cyclohexyl sulphamates or salts of the other acids.
Among the useful cyclic quaternary ammonium compounds are the
following: alkylpyridinium chlorides and/or sulphates, the alkyl
group being preferably cetyl, dodecyl or hexadecyl group;
-alkylisoquinolyl chlorides and/or bromides, the alkyl group being
preferably dodecyl group. Particularly suitable quaternary ammonium
compounds for use herein include alkyldimethylbenzyl ammonium
chloride, octyl decyl dimethylammonium chloride, dioctyl dimethyl
ammonium chloride, didecyl dimethyl ammonium chloride, alkyl
dimethyl ammonium saccharinate, cetylpyridinium and mixtures
thereof.
[0159] Highly preferred materials of this class of antimicrobials
and preservatives are those that do not cause any significant color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
Dyes and Colorants
[0160] Optionally, dyes and colorants can be added to the instant
disclosure. Typical concentrations of these compounds may range
from about 0.001% to about 0.8%, preferably from about 0.005% to
about 0.3%, and more preferably from about 0.01% to 0.2% of the
usage composition.
[0161] Colorants and dyes, especially bluing agents, can be
optionally added to the compositions of the instant disclosure for
visual appeal and performance impression. When colorants are used,
they may be used at extremely low levels to avoid fabric staining.
Preferred colorants for use in the present compositions include
highly water-soluble dyes, for example, LIQUITINT dyes available
from Milliken Chemical Company. Non-limiting examples of suitable
dyes are LIQUITINT Blue HP, LIQUITINT Blue 65, LIQUITINT Patent
Blue, LIQUITINT Royal Blue, LIQUITINT Experimental Yellow 8949-43,
LIQUITINT Green HMC, LIQUITINT Yellow II, and mixtures thereof. Any
dye can be used in the compositions of the instant disclosure, but
nonionic dyes are preferred to decrease interaction with the zeta
potential modifier and/or with the dye transfer inhibitor employed
in combination with the laundry additive compositions of the
instant disclosure. Useful acid dyes include: Polar Brilliant Blue
and D&C Yellow #10, both supplied by Hilton Davis Chemical
Company. Nonionic LIQUITINT dyes supplied by Milliken Chemical
Company are also useful.
[0162] Suitable colors include, but are not limited to, Acid Black
1, Acid Blue 3, Acid Blue 9 Aluminum Lake, Acid Blue 74, Acid Green
1, Acid Orange 6, Acid Red 14 Aluminum Lake, Acid Red 27, Acid Red
27 Aluminum Lake, Acid Red 51, Acid Violet 9, Acid Yellow 3, Acid
Yellow 3 Aluminum Lake, Acid Yellow 73, Aluminum Powder, Basic Blue
6, Basic Yellow 11, Carotene, Brilliant Black 1, Bromocresol Green,
Chromium Oxide Greens, Curry Red, D&C Blue No. 1 Aluminum Lake,
D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 3
Aluminum Lake, D&C Green No. 5, D&C Orange No. 4 Aluminum
Lake, D&C Red No. 6, D&C Red No. 6 Aluminum Lake, D&C
Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 11, D&C
Blue No. 1, FD&C Yellow No. 5 Aluminum Lake, iron oxides,
Pigment Orange 5, Pigment Red 83, Pigment Yellow 73, Solvent Orange
1, Solvent Yellow 18, ultramarines, and zinc stearate.
[0163] Highly preferred materials of this class of dyes and
colorants are those that do not effectively bind to or permanently
dye or color fabrics treated by use of the invention compositions,
nor cause any significant color change, nor impart any
discoloration, such as graying or yellowing, to the fabrics to
which they are applied, either during treatment followed by drying
and/or curing, or after the drying and/or curing step followed by
normal exposure to the elements, such as air, moisture or sunlight
exposure.
Viscosity Control Agents
[0164] Optionally added viscosity control agents can be organic or
inorganic in nature and may either lower or raise the viscosity of
the formulation. Examples of organic viscosity modifiers to lower
viscosity are aryl carboxylates and sulfonates (for example
including, but not limited to benzoate, 2-hydroxybenzoate,
2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate,
2-aminobenzenesulfonate), fatty acids and esters, fatty alcohols,
and water-miscible solvents such as short chain alcohols. Examples
of inorganic viscosity control agents are water-soluble ionizable
salts. A wide variety of ionizable salts can be used. Examples of
suitable salts are the halides and acetates of ammonium ion and the
group IA and IIA metals of the Periodic Table of the Elements, for
example, calcium chloride, lithium chloride, sodium chloride,
potassium chloride, magnesium chloride, ammonium chloride, sodium
bromide, potassium bromide, calcium bromide, magnesium bromide,
ammonium bromide, sodium iodide, potassium iodide, calcium iodide,
magnesium iodide, ammonium iodide, sodium acetate, potassium
acetate, or mixtures thereof. Calcium chloride is preferred. The
ionizable salts are particularly useful during the process of
mixing the ingredients to make the compositions herein, and later
to obtain the desired viscosity. The amount of ionizable salts used
depends on the amount of active ingredients used in the
compositions and can be adjusted according to the desire of the
formulator. Typical levels of salts used to control the composition
viscosity are from 0 to about 10%, preferably from about 0.01% to
about 6%, and more preferably from about 0.02% to about 3% of the
composition.
[0165] Viscosity modifiers or thickening agents can be added to
increase the ability of the compositions to stably suspend
water-insoluble articles, for example, perfume microcapsules. Such
materials include hydroxypropyl substituted guar gum (such as that
available from Rhone-Poulenc Corporation under the trade name
JAGUAR HP200), polyethylene glycol (such as that available from
Union Carbide Corporation under the trade name CARBOWAX 20M),
hydrophobically modified hydroxyethylcellulose (such as that
available from the Aqualon Company under the trade name NATROSOL
Plus), and/or organophilic clays (for example, hectorite and/or
bentonite clays such as those available from Rheox Company under
the name BENTONE 27, 34 and 38 or from Southern Clay Products under
the trade name BENTOLITE L; and those described in U.S. Pat. No.
4,103,047 to Zaki, et al., which is herein incorporated by
reference). These viscosity raisers or thickeners can typically be
used at levels from about 0.5% to about 30% by weight, preferably
from about 1% to about 5%, more preferably from about 1.5% to about
3.5%, and further preferably from about 2% to about 3% by weight,
of the composition.
[0166] Highly preferred materials of this class of thickeners and
viscosity control and viscosity modifiers are those that do not
cause any significant color change, nor impart any discoloration,
such as graying or yellowing, to the fabrics to which they are
applied, either during treatment followed by drying and/or curing,
or after the drying and/or curing step followed by normal exposure
to the elements, such as air, moisture or sunlight exposure.
Pearlizing and Opacifying Agents
[0167] Examples of pearlizing oropacifying agents that can
optionally be added to the compositions of this invention include,
but are not restricted to, glycol distearate, propylene glycol
distearate, and glycol stearate. Some of these products are
available from Witco Corporation under the KEMESTER trade name.
[0168] Highly preferred materials of this class of pearlizing and
opacifying agents are those that do bind to treated fabrics, nor
cause any significant color change nor impart any discoloration,
such as whitening, graying or yellowing, to the fabrics to which
they are applied, either during treatment followed by drying and/or
curing, or after the drying and/or curing step followed by normal
exposure to the elements, such as air, moisture or sunlight
exposure.
Antioxidants and Sunscreen Materials
[0169] Examples of antioxidants that can optionally be added to the
compositions of this invention are propyl gallate, available from
Eastman Chemical Products, Inc. under the trade names TENOX PG and
TENOX S-1, and dibutylated hydroxytoluene, available from UOP Inc.
under the trade name SUSTANE BHT. Also preferred are antioxidants
for providing sun-fade protection for fabrics treated with the
composition of the instant disclosure, such antioxidants being
described in EP0773982, and incorporated herein by reference.
Preferred antioxidants include
2-(N-methyl-N-cocoamino)ethyl-3',5'-di-tert-butyl-4'-hydroxybenzoate;
2-(N,
N-dimethyl-amino)ethyl-3',5'-di-tert-butyl-4'-hydroxybenzoate;
2-(N-methyl-N-cocoamino)ethyl-3',4',5'-trihydroxybenzoate; and
mixtures thereof, more preferably
2-(N-methyl-N-cocoamino)ethyl-3',5'-di-tert-butyl-4'-hydroxy
benzoate. Of these compounds, the butylated derivatives are
preferred in the compositions of the instant disclosure because
tri-hydroxybenzoates have a tendency to discolor upon exposure to
light. The antioxidant compounds of the instant disclosure
demonstrate light stability in the compositions of the instant
disclosure. "Light stable" means that the antioxidant compounds in
the compositions of the instant disclosure do not discolor when
exposed to either sunlight or simulated sunlight for approximately
2 to 60 hours at a temperature of from about 25.degree. C. to about
45.degree. C. Antioxidant compounds and free radical scavengers can
generally protect dyes from degradation by first preventing the
generation of single oxygen and peroxy radicals, and thereafter
terminating the degradation pathways. Not to be limited by theory,
a general discussion of the mode of action for antioxidants and
free radical scavengers is disclosed in Kirk-Othmer Encyclopedia of
Chemical Technology, Volume 3, pages 128-148, Third Edition (1978)
which is incorporated herein by reference.
[0170] Compositions of the instant disclosure may comprise an
organic sunscreen. Suitable sunscreens can have UVA absorbing
properties, UVB absorbing properties, or a combination of both. The
compositions of the instant disclosure may preferably comprise a
UVA absorbing sunscreen actives that absorb UV radiation having a
wavelength from about 320 nm to about 400 nm. Suitable UVA
absorbing sunscreen actives include dibenzoylmethane derivatives,
anthranilate derivatives such as methylanthranilate and
homomethyl-1-N-acetylanthranilate, and mixtures thereof. Examples
of dibenzoylmethane sunscreen actives are described in U.S. Pat.
No. 4,387,089 to De Polo; and in Sunscreens: Development,
Evaluation, and Regulatory Aspects edited by N. J. Lowe and N. A.
Shaath, Marcel Dekker, Inc (1990), which are incorporated herein by
reference. The UVA absorbing sunscreen active is preferably present
in an amount to provide broad-spectrum UVA protection either
independently, or in combination with, other UV protective actives
that may be present in the composition. Preferred UVA sunscreen
actives include dibenzoylmethane sunscreen actives and their
derivatives. They include, but are not limited to, those selected
from 2-methyldibenzoylmethane, 4-methyldibenzoylmethane,
4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,
2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,
4,4'-diisopropylbenzoylmethane,
4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane,
2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
2,4-dimethyl-4'-methoxydibenzoylmethane,
2,6-dimethyl-4'-tert-butyl-4'-methoxydibenzoylmethane, and mixtures
thereof. Preferred dibenzoyl sunscreen actives include those
selected from 4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane,
4-isopropyldibenzoylmethane, and mixtures thereof. A more preferred
sunscreen active is
4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane, which is also
known as butylethoxydibenzoylmethane or Avobenzone, is commercially
available under the names of PARSOL 1789 from Givaudan Roure
(International) S. A. (Basel, Switzerland) and EUSOLEX 9020 from
Merck & Co., Inc (Whitehouse Station, N.J.). The sunscreen
4-isopropyldibenzoylmethane, which is also known as
isopropyldibenzoylmethane, is commercially available from Merck
under the name of EUSOLEX 8020. The compositions of the instant
disclosure may preferably further comprise a UVB sunscreen active
that absorbs UV radiation having a wavelength of from about 290 nm
to about 320 nm. The compositions may preferably comprise an amount
of the UVB sunscreen active that is safe and effective to provide
UVB protection either independently, or in combination with, other
UV protective actives that may be present in the compositions. The
compositions preferably comprise from about 0.1% to about 16%, more
preferably from about 0.1% to about 12%, and further preferably
from about 0.5% to about 8% by weight, of UVB absorbing organic
sunscreen. A wide variety of UVB sunscreen actives are suitable for
use herein. Non-limiting examples of such organic sunscreen actives
are described in U.S. Pat. No. 5,087,372 to Toyomot and U.S. Pat.
Nos. 5,073,371 and 5,073,372 both to Turner, et al., which are
incorporated herein by reference. Preferred UVB sunscreen actives
are selected from 2-ethylhexyl-2-cyano-3,3-diphenylacrylate
(referred to as octocrylene), 2-phenyl-benzimidazole-5-sulphonic
acid (PBSA), cinnamates and their derivatives such as
2-ethylhexyl-p-methoxycinnamate and octyl-p-methoxycinnamate, TEA
salicylate, octyldimethyl PABA, camphor derivatives and their
derivatives, and mixtures thereof. Preferred organic sunscreen
actives include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (commonly
named octocrylene), 2-phenyl-benzimidazole-5-sulphonic acid (PBSA),
octyl-p-methoxycinnamate, and mixtures thereof. Salt and acid
neutralized forms of the acidic sunscreens are also useful.
[0171] An agent may also be added to any of the compositions useful
in the instant disclosure to stabilize the UVA sunscreen and to
prevent it from photo-degrading on exposure to UW radiation and
thereby maintaining its UVA protection efficacy. Wide ranges of
compounds have been cited as providing these stabilizing properties
and should be chosen to compliment both the UVA sunscreen and the
composition as a whole. Suitable stabilizing agents include, but
are not limited to, those described in U.S. Pat. No. 5,972,316 to
Robinson; U.S. Pat. No. 5,968,485 to Robinson; U.S. Pat. No.
5,935,556 to Tanner, et al.; and U.S. Pat. No. 5,827,508 Tanner, et
al., which are incorporated herein by reference. Preferred examples
of stabilizing agents for use in the instant disclosure include
2-ethylhexyl-2-cyano-3,3-diphenylacrylate (referred to as
octocrylene), ethyl-2-cyano-3,3-diphenylacrylate,
2-ethylhexyl-3,3-diphenylacrylate, ethyl-3,3-bis
(4-methoxyphenyl)acrylate, and mixtures thereof.
[0172] Highly preferred materials of this class of antioxidants and
sunscreen actives are those that do not cause any significant color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
[0173] The composition of the instant disclosure may preferably
deposit from about 0.1 mg/g fabric to about 5 mg/g fabric of the
sun-fade actives to reduce the sun fading of the fabric. Treatment
of fabric with compositions of the instant disclosure repeatedly,
may result in higher deposition levels, which contributes even
further to the sun-fading protection benefit.
Dye Transfer Inhibitors and Dye Fixatives
[0174] The composition can comprise from about 0.001% to about 20%,
preferably from about 0.5% preferably to about 10%, and more
preferably from about 1% to about 5% of one or more dye transfer
inhibitors or dye fixing agents.
[0175] Compositions and formulations of the instant disclosure can
contain ethoxylated amines, amphoterics, betaines, polymers such as
polyvinylpyrrolidone, and other ingredients that inhibit dye
transfer. Optional dye fixing agents can be cationic, and based on
quaternized nitrogen compounds or on nitrogen compounds having a
strong cationic charge which is formed in situ under the conditions
of usage. Cationic fixatives are available under various trade
names from several suppliers. Representative examples include:
CROSCOLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF
(January 1988, Code No. 8544) ex Crosfield; INDOSOL E-50 (Feb. 27,
1984, Ref. No. 6008.35.84; polyethyleneamine-based) ex Sandoz;
SANDOFIX TPS, ex Sandoz, is a preferred dye fixative for use
herein. Additional non-limiting examples include SANDOFIX SWE (a
cationic resinous compound) from Sandoz, REWIN SRF, REWIN SRF-O and
REWIN DWR Crochet-Beitlich GMBH; Tinofix ECO, Tinofix FRD and
Solvent from Ciba-Geigy. Other cationic dye fixing agents are
described in "After treatments for Improving the Fastness of Dyes
on Textile Fibres", Christopher C. Cook, Rev. Prog. Coloration,
Vol. XH, (1982). Dye fixing agents suitable for use in the instant
disclosure include ammonium compounds such as fatty acid-diamine
condensates, inter alia, the hydrochloride, acetate, methosulphate
and benzyl hydrochloride salts of diamine esters. Non-limiting
examples include oleyldiethyl aminoethylamide, oleylmethyl
diethylenediamine methosulphate, and monostearylethylene
diaminotrimethylammonium methosulphate. In addition, the N-oxides
of tertiary amines; derivatives of polymeric alkyldiamines,
polyamine-cyanuric chloride condensates; and aminated glycerol
dichlorohydrins are suitable for use as dye fixatives in the
compositions of the instant disclosure.
[0176] Highly preferred materials of this class of dye transfer
inhibitors and dye fixatives are those that do not cause any
significant color change, nor impart any discoloration, such as
graying or yellowing, to the fabrics to which they are applied,
either during treatment followed by drying and/or curing, or after
the drying and/or curing step followed by normal exposure to the
elements, such as air, moisture or sunlight exposure.
Chlorine Scavengers
[0177] The compositions of the instant disclosure may optionally
comprise from about 0.01%, preferably from about 0.02%, more
preferably from about 0.25% to about 15%, further preferably to
about 10%, and yet more preferably to about 5% of a chlorine
scavenger. In cases wherein the cation portion and the anion
portion of the non-polymeric scavenger each react with chlorine,
the amount of scavenger can be adjusted to fit the needs of the
formulator. Suitable chlorine scavengers include ammonium salts
having the formula: [I.sub.3R'N]X wherein each R is independently
hydrogen, C.sub.1-C.sub.4 alkyl, --C.sub.1-C.sub.4 substituted
alkyl, and mixtures thereof; preferably R is hydrogen or methyl,
more preferably hydrogen; R' is hydrogen C.sub.1-C.sub.10 alkyl,
C.sub.1-C.sub.10 substituted alkyl, and mixtures thereof.
Preferably R is hydrogen and X is a compatible anion. Non-limiting
examples include chloride, bromide, citrate, and sulfate;
preferably X is chloride. Non-limiting examples of preferred
chlorine scavengers include ammonium chloride, ammonium sulfate,
and mixtures thereof, preferably ammonium chloride. Other chlorine
scavengers include reducing agents such as thiosulfate.
[0178] Highly preferred materials of this class of chlorine
scavengers are those that do not cause any significant color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
Wetting Agents
[0179] The instant disclosure may contain as an optional ingredient
from about 0.005% to about 3.0%, and more preferably from about
0.03% to 1.0% of a wetting agent. Such wetting agents may be
selected from polyhydroxy compounds. Examples of water soluble
polyhydroxy compounds that can be used as wetting agents in the
instant disclosure include glycerol, polyglycerols having a
weight-average molecular weight from about 150 to about 800, and
polyoxyethylene glycols and polyoxypropylene glycols having a
weight-average molecular weight from about 200 to about 4000,
preferably from about 200 to about 1000, and more preferably from
about 200 to about 600. Polyoxyethylene glycols having a
weight-average molecular weight from about 200 to about 600 are
especially preferred. Mixtures of the above-described polyhydroxy
compounds may also be used. A particularly preferred polyhydroxy
compound is polyoxyethylene glycol having a weight-average
molecular weight of about 400, available from Union Carbide
Corporation under the trade name PEG-400.
[0180] Highly preferred materials of this class of wetting agents
are those that do not cause any significant color change, nor
impart any discoloration, such as graying or yellowing, to the
fabrics to which they are applied, either during treatment followed
by drying and/or curing, or after the drying and/or curing step
followed by normal exposure to the elements, such as air, moisture
or sunlight exposure.
Electrolytes
[0181] Suitable inorganic salts for use as an optional electrolyte
in the present compositions include MgI.sub.2, MgBr.sub.2,
MgCl.sub.2, Mg(NO.sub.3).sub.2, Mg.sub.3(PO.sub.4).sub.2,
Mg.sub.2P.sub.2O.sub.7, MgSO.sub.4, magnesium silicate, NaI, NaBr,
NaCl, NaF, Na.sub.3PO.sub.4, Na.sub.2SO.sub.3, Na.sub.2SO.sub.4,
NaNO.sub.3, Na.sub.4P.sub.2O.sub.5, sodium silicate, sodium
metasilicate, sodium tetrachloroaluminate, sodium tripolyphosphate
(STPP), Na.sub.2S.sub.3O.sub.7, sodium zirconate, CaF.sub.2,
CaCl.sub.2, CaBr.sub.2, CaI.sub.2, CaSO.sub.4, Ca(NO.sub.3).sub.2,
KI, KBr, KCl, KF, KNO.sub.3, KIO.sub.3, K.sub.2SO.sub.4,
K.sub.2SO.sub.3, K.sub.3PO.sub.4, K.sub.4(P.sub.2O.sub.7),
potassium pyrosulfate, potassium pyrosulfite, LiI, LiBr, LiCl, LiF,
LiNO.sub.3, AlF.sub.3, AlCl.sub.3, AlBr.sub.3, AlI.sub.3,
Al.sub.2(SO.sub.4).sub.3, Al(PO.sub.4), Al(NO.sub.3).sub.3,
aluminum silicate; including hydrates of these salts and including
combinations of these salts or salts with mixed cations e.g.
potassium aluminum AlK(SO.sub.4).sub.2 and salts with mixed anions,
e.g. potassium tetrachloroaluminate and sodium
tetrafluoroaluminate. Salts incorporating cations from groups
Groups IIIA, IVA, VA, VIA, VIII, IB and IIB on the periodic chart
with atomic numbers greater than are also useful in reducing
dilution viscosity but less preferred due to their tendency to
change oxidation states and thus they can adversely affect the odor
or color of the formulation or lower weight efficiency. Salts with
cations from Group IA or IIA with atomic numbers greater than 20 as
well as salts with cations from the lanthanide or actinide series
are useful in reducing dilution viscosity, but less preferred due
to lower weight efficiency or toxicity. Mixtures of above salts are
also useful.
[0182] Also preferred are quaternary ammonium salts, quaternary
alkyl ammonium salts, quaternary dialkyl ammonium salts, quaternary
trialkyl ammonium salts and quaternary tetraalkyl ammonium salts
wherein the alkyl substituent comprises a methyl, ethyl, propyl,
butyl or higher C.sub.5-C.sub.12 linear alkane radical, or
combinations thereof. Organic salts useful in this invention
include, magnesium, sodium, lithium, potassium, zinc, and aluminum
salts of the carboxylic acids including formate, acetate,
proprionate, pelargonate, citrate, gluconate, lactate, aromatic
acids e.g. benzoates, phenolate and substituted benzoates or
phenolates, such as phenolate, salicylate, polyaromatic acids
terephthalates, and polyacids e.g. oxylate, adipate, succinate,
benzenedicarboxylate, benzenetricarboxylate. Other useful organic
salts include carbonate and/or hydrogen carbonate
(HCO.sub.3.sup.-1) when the pH is suitable, alkyl and aromatic
sulfates and sulfonates, e.g., sodium methyl sulfate, benzene
sulfonates and derivatives such as xylene sulfonate, and amino
acids when the pH is suitable.
[0183] Electrolytes can comprise mixed salts of the above, salts
neutralized with mixed cations such as potassium/sodium tartrate,
partially neutralized salts such as sodium hydrogen tartrate or
potassium hydrogen phthalate, and salts comprising one cation with
mixed anions.
[0184] Highly preferred materials of this class of inorganic and
organic electrolytes are those that do not cause any significant
color change, nor impart any discoloration, such as graying or
yellowing, to the fabrics to which they are applied, either during
treatment followed by drying and/or curing, rafter the drying
and/or curing step followed by normal exposure to the elements,
such as air, moisture or sunlight exposure.
[0185] Generally, inorganic electrolytes are preferred over organic
electrolytes for better weight efficiency and lower costs. Mixtures
of inorganic and organic salts can be used. Typical levels of
electrolyte in the present compositions can be less than about 10%,
preferably from about 0.5% to about 5%, more preferably from about
0.75% to about 2.5%, and further preferably from about 1% to about
2% of the laundry additive compositions described herein.
Enzymes
[0186] Additional desirable adjuncts may be enzymes (although it
may be preferred to also include an enzyme stabilizer), including,
but not limited to hydrolases, hydroxylases, cellulases,
peroxidases, laccases, mannases, amylases, lipases and proteases.
Proteases are one especially preferred class of enzymes. Typical
examples of proteases include Maxatase and Maxacal from Genencor
International, Alcalase, Savinase, and Esperase, all available from
Novozymes North America, Inc. See also U.S. Pat. No. 4,511,490 to
Stanislowski, et al., incorporated herein by reference. Further
suitable enzymes are amylases, which are carbohydrate-hydrolyzing
enzymes. It may also be preferred to include mixtures of amylases
and proteases. Suitable amylases include Termamyl from Novozymes,
North America Inc, and Maxamyl from Genencor International Co.
Still other suitable enzymes are cellulases, such as those
described in U.S. Pat. No. 4,479,881 to Tai; U.S. Pat. No.
4,443,355 to Murata, et al.; U.S. Pat. No. 4,435,307 to
Barbesgaard, et al.; and U.S. Pat. No. 3,983,082 to Ohya, et al.,
incorporated herein by reference. Yet other suitable enzymes are
lipases, such as those described in U.S. Pat. No. 3,950,277 to
Silver; U.S. Pat. No. 4,707,291 to Thorn, et al.; U.S. Pat. Nos.
5,296,161 and 5,030,240 both to Wiersema, et al.; and U.S. Pat. No.
5,108,457 to Poulose, et al., incorporated herein by reference. The
hydrolytic enzyme may be present in an amount of about 0.01-5%,
more preferably about 0.01-3%, and further preferably about 0.1-2%
by weight of the detergent. Mixtures of any of the foregoing
hydrolases are desirable, especially protease/amylase blends.
[0187] Highly preferred materials of this class of enzymes are
those that do not cause any significant residual odor or color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
Bleaching Agents
[0188] (0190-Publ) The compositions of the instant disclosure may
optionally comprise from about 0.01%, preferably from about 0.02%,
more preferably from about 0.25% to about 15%, further preferably
to about 10%, and yet more preferably to about 5% of a bleaching
agent. Suitable bleaching agents include chlorine-releasing agents
and peroxygen and peroxide-releasing compounds. Alkali metal
hypochlorites, including sodium or potassium hypochlorite, are
preferred chlorine releasing agents. Peroxygen compounds include
alkali metal salts of percarbonate, perborate and
peroxymonosulfate. Peroxide compounds, including hydrogen peroxide
and compounds generating hydrogen peroxide in solution, peroxyacids
and precursors to peroxyacids and peroxyimidic acids, and metal
based oxidants are also suitable. Suitable bleaching agents include
preformed peracids and organic peroxides, including alkonyl and
acyl peroxides such as tertiary butyl peroxide and benzoyl
peroxide, and related alkonyl and acyl peroxide and superoxide
derivatives of alkyls and arenes. Additionally, an appropriate
bleach activator for the active oxygen source or peroxide may be
present, such those found in Arbogast, et al., U.S. Pat. Nos.
5,739,327 and 5,741,437; Alvarez, et al.; U.S. Pat. No. 5,814,242,
Deline, et al.; U.S. Pat. Nos. 5,877,315; and 5,888,419 to Casella,
et al., which relate to cyanonitrile derivatives; U.S. Pat. Nos.
4,959,187 and 4,778,816 to Fong, et al.; U.S. Pat. Nos. 5,112,514
and 5,002,691 to Bolkan, et al., and U.S. Pat. No. 5,269,962 to and
Brodbeck, et al., which relate to alkanoyloxyacetyl derivatives;
and U.S. Pat. Nos. 5,234,616, 5,130,045 and 5,130,044 to Mitchell,
et al., all of which relate to alkanoyloxyphenyl sulfonates; all of
which are incorporated herein by reference.
[0189] Highly preferred materials of this class of bleaching agents
are those that do not cause any significant fabric damage or color
change, nor impart any discoloration, such as graying or yellowing,
to the fabrics to which they are applied, either during treatment
followed by drying and/or curing, or after the drying and/or curing
step followed by normal exposure to the elements, such as air,
moisture or sunlight exposure.
Brighteners
[0190] Optical brighteners, also referred to as fluorescent
whitening agents or FWAs, have long been used to impart whitening
to fabrics during the laundering process. These fluorescent
materials act by absorbing ultraviolet wavelength of light and
emitting visible light, generally in the color blue wavelength
ranges. The FWAs settle out or deposit onto fabrics during the wash
cycle. These include the stilbene, styrene, and naphthalene
derivatives, which upon being impinged by ultraviolet light, emit
or fluoresce light in the visible wavelength. These FWAs or
brighteners are useful for improving the appearance of fabrics,
which have become dingy through repeated soilings and washings. Due
to the cationic nature of the composition, it is preferred that the
FWAs not be explicitly anionic but rather either nonionic;
cationic; amphoteric; or neutralized, ion-paired moieties of
anionic FWAs as described in Petrin, et al., U.S. Pat. No.
5,057,236. Preferred anionic FWAs for ion-pairing according to
Petrin, et al., '236 are Blankophor BBH, RKH and BHC, from Bayer
Corporation; and Tinopal 5BMX-C, CBS-X and RBS, from Ciba-Geigy
A.G. Fluorescent whiteners most currently used in common laundry
compositions generally fall into a category referred to in the art
as diaminostilbene disulfonic acid-cyanuric chloride brighteners or
DASC-brighteners. These compounds have the following general
structure (I):
##STR00001##
[0191] Examples of such DASC fluorescent whiteners include those
sold by the Ciba-Geigy Corporation under the trade name "Tinopal",
which are substituted stilbene 2,2'-disulfonic acid products, e.g.,
disodium 4,4'-bis-((4-anilino-6-morpholino-1,3,5-triazin-2-yl)
amino)stilbene-2,2'-disulfonate (sold as Tinopal AMS); disodium
4,4'-bis-((4-anilino-6-(N-2-hydroxyethyl-N-methyl
amino)-1,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfonate (sold as
Tinopal 5BM); disodium 4,4'bis-((4-anilino-6-(bis
(2-hydroxyethyl)amino)-1,3,5-triazin-2-yl)
amino)stilbene-2,2'-disulfonate (sold as Tinopal UNPA). Another
example sold by Bayer Corporation is disodium
4,4'-bis-((4-anilino-6-methylamino)-1,3,5-triazin-2-yl)
amino)stilbene-2,2'-disulfonate (sold as Phorwite HRS).
[0192] Examples of suitable FWAs can be found in U.K. Patent Nos.
1,298,577; 2,076,011; 2,026,054; 2,026,566; 1,393,042; and U.S.
Pat. No. 3,951,960 to Heath, et al., U.S. Pat. No. 4,298,290 to
Barnes, et al., U.S. Pat. No. 3,993,659 to Meyer, U.S. Pat. No.
3,980,713 to Matsunaga, et al., and U.S. Pat. No. 3,627,758 to
Weber, et al., incorporated herein by reference. See also, U.S.
Pat. No. 4,900,468 to Mitchell, et al., column 5, line 66 to column
6, line 27, incorporated herein by reference.
[0193] As stated above, most preferred are cationic, nonionic, and
amphoteric FWAs, such as those cited in U.S. Pat. Nos. 4,433,975,
4,432,886, 4,384,121, all to Meyer and U.S. Pat. No. 4,263,431 to
Weber, et al., and incorporated herein by reference. Further
examples of suitable FWAs are described in McCutcheon's Vol. 2:
Functional Materials, North American Ed., McCutcheon Division, MC
Publishing Co., 1995, and Encyclopedia of Chemical Technology, 11th
volume, John Wiley & Sons, 1994, both of which are incorporated
herein by reference. Other examples of fluorescent brightening
materials suitable for the invention may be found in U.S. Pat. No.
6,251,303 to Bawendi, et al.; U.S. Pat. No. 6,127,549 to Hao, et
al.; U.S. Pat. No. 6,133,215 to Zeiger, et al.; U.S. Pat. No.
6,117,189 to Reinehr, et al.; U.S. Pat. No. 6,120,704 to Martini;
and U.S. Pat. No. 6,162,869 to Sharma, et al., incorporated herein
by reference.
[0194] Highly preferred materials of this class of brighteners are
those that do not cause any significant color change, nor impart
any discoloration, such as graying or yellowing, to the fabrics to
which they are applied, either during treatment followed by drying
and/or curing, or after the drying and/or curing step followed by
normal exposure to the elements, such as air, moisture or sunlight
exposure.
[0195] In selecting the various components for the laundry additive
compositions described herein, most preferred are those that do not
cause any significant damage to treated fabrics or cause any
significant color change, nor impart any discoloration, such as
whitening, graying or yellowing, to the fabrics to which they are
applied, either during treatment followed by curing and/or drying,
or after the curing and/or drying step followed by normal exposure
to the elements, such as air, moisture or sunlight exposure. In
particular, dye and colorants should not undergo any significant
change from their original color and not stain or discolor the
fabrics to which they are applied. Finally, bleaching agents should
also not interfere with the function of stain release and/or fabric
treatment of the laundry additive.
Formulation
[0196] The compositions of the instant disclosure and/or products
incorporating the compositions may be in any form known to those
skilled in the art. For example, the compositions and/or products
may be in the form of an aerosol, liquid, granular, powder, tablet,
solid, paste, foam and/or bar compositional form, or their
encapsulated or coated forms. These compositions and/or products
may be neat or releasably absorbed or adsorbed on to a substrate,
such as a woven or non-woven filament substrate or packaged within
a suitable article of manufacture for convenient handling and
dispensing. In this aspect of the disclosure, an article of
manufacture maybe provided that comprises the laundry additive
compositions and a spray dispensing device, an aerosol dispensing
device, a standard bottle, a device to release the composition into
the rinse water, or a water soluble or water-insoluble sachet or
package, or a water soluble or water-insoluble tablet or powder
which enables release of the composition. A suitable film coating
or encapsulate may also be employed with either a liquid or solid
form to provide for release of the composition.
[0197] The spray dispenser can be any of the manually activated
means for producing a spray of liquid droplets as is known in the
art, e.g., trigger-type, pump-type, electrostatic spray device,
non-aerosol self-pressurized, and aerosol-type spray devices.
Regardless of the specific spray means employed, it is preferred
that at least about 70%, more preferably, at least about 80%, and
further preferably at least about 90% of the droplets have a
particle size smaller than about 200 microns. Generally in
instances where the potential for inhalation by users may occur, it
is most preferred that at least about 70%, more preferably, at
least about 80%, and further preferably at least about 90% of the
droplets have a particle size larger than about 5 microns.
[0198] Suitable trigger-type and pump-type spray devices are
disclosed in U.S. Pat. No. 4,161,288 to McKinney; U.S. Pat. No.
4,558,821 to Tada, et al.; U U.S. Pat. No. 4,434,917 to Saito, et
al; and U.S. Pat. No. 4,819,835 to Tasaki, all of said patents
being incorporated herein by reference. Particularly preferred to
be used herein are spray-type dispensers, such as T 8500
commercially available from Continental Spray International, or
other manufactures commonly known in the trade. In such a
dispenser, the liquid composition can be divided in fine liquid
droplets resulting in a spray that is directed onto the fabric
surface to be treated. Suitably fine droplet sizes are achieved in
such spray-type dispensers owing to the mechanism of operation in
which the composition contained in the body of the dispenser is
directed through the spray-type dispenser bead via energy
communicated to a pumping mechanism by the user as the composition
is forced against an obstacle, such as a screen grid or a cone or
the like, which provides sufficient shock to the stream of the
ejected liquid composition to atomize the liquid composition and
provide the formation of liquid droplets of sufficiently small
size.
[0199] Preferably, the aerosol-dispensing device of the instant
disclosure can be any of the manually activated devices employing a
pressurized propellant as known in the art. The aerosol dispenser
may comprise a container, which can be constructed of any of the
conventional materials employed in fabricating aerosol containers.
The dispenser should be capable of withstanding internal pressure
in the range of about 20 to about 120 psig, and preferably from
about 20 to about 80 psig. An important characteristic concerning
the dispenser is that it be provided with a valve member, which can
permit the composition of the instant disclosure to be dispensed in
the form of a spray of very fine, or finely divided, particles or
droplets. The aerosol dispenser is a pressurized sealed container
from which the composition of the instant disclosure can be
dispensed through a special actuator/valve assembly under pressure.
The aerosol dispenser is pressurized by incorporating therein a
gaseous component generally known as a propellant. Common aerosol
propellants, e.g., gaseous hydrocarbons such as isobutene, mixed
halogenated hydrocarbons, compressed air, nitrogen, inert gases,
and carbon dioxide, are suitable. Highly preferred are those
propellants that do not present environmental concerns, such as
compressed air, nitrogen, inert gases and carbon dioxide. A more
complete description of commercially available aerosol-spray
dispensers appears in U.S. Pat. No. 3,436,772, to Stebbins and U.S.
Pat. No. 3,600,325 to Kaufman, et al., which are incorporated
herein by reference.
[0200] The spray dispenser can be a self-pressurized non-aerosol
container having a convoluted liner and an elastomeric sleeve. The
self-pressurized dispenser can be comprised of an assembly
containing a liner and a sleeve comprising a thin, flexible
radially expandable convoluted plastic liner of about 0.010 (0.25
mm) to about 0.020 (0.50 mm) inch thick, inside an essentially
cylindrical elastomeric sleeve. The liner and sleeve assembly can
be capable of holding a substantial quantity of the composition of
the instant disclosure and of causing the product to be dispensed.
A description of such self-pressurized spray dispensers can be
found in U.S. Pat. No. 5,111,971 to Winer and U.S. Pat. No.
5,232,126 to Winer, which are incorporated herein by reference.
Another suitable type of aerosol spray dispenser is one in which a
barrier membrane separates the composition of the instant
disclosure from the propellant, as is disclosed in U.S. Pat. No.
4,260,110 to Werding, which is incorporated herein by reference.
Such a dispenser is available from EP Spray Systems, East Hanover,
N.J.
[0201] Compositions of the instant disclosure can be introduced
into an automatic washing machine prior to or during the main wash
cycle of the machine in any suitable form as described herein. Some
commercial washing machines provide a presoaking cycle into which
compositions of the instant disclosure can be introduced. The
presoaking or soaking cycle generally provides for treatment of
clothing prior to introduction of a detergent or other additives
prior to the main wash cycle. The compositions of the instant
disclosure may be employed alone as a sole treatment and may be
employed in combination with other laundry additive products, such
as liquid or powdered detergents, laundry additives or laundry
booster products that are commonly in use. Additionally, the
compositions of the instant disclosure can be introduced subsequent
to a detergent using a delayed release packaging material or device
or similar means. Some commercial washing machines, for example,
provide a means to automatically dispense an additive to the main
wash water (the "wash liquor") after a short delay following the
initiation of a wash cycle. Other "drop in" dosing and dispensing
devices known to the art can also be employed for releasing the
compositions described herein into the main wash cycle. Delayed
release packaging can also be employed to hold and subsequently
release the compositions of the instant disclosure at a
predetermined time during the wash cycle. When such delayed release
packaging material is employed, it is desirable for the release of
the novel compositions described herein to delayed in such a manner
that sufficient time remains within the cycle time of the wash for
the composition of the instant disclosure to act upon the clothing
in order to provide effective treatment thereupon. All of these
approaches provide a means to treat articles, for example textiles,
clothing, garments and the like, according to the methods of the
instant disclosure. Also suitable are methods in which articles are
treated with the compositions and methods of the instant disclosure
in an aqueous liquor, such as washing by hand, washing in a tub,
bucket or sink, as is commonly done with single articles, so-called
delicates and fine items of clothing and textiles that are not
typically machined washed.
[0202] It is also envisioned that the compositions can be
formulated so as to assume the primary role of detergent in
addition to imparting stain and soil resistance. Such compositions
are especially preferred, in that in practice the consumer needs to
purchase and use only a single all-in-one product, which imparts
cleaning, stain and soil resistance. In such a case, the
composition used according to the methods of the instant disclosure
would preferably be formulated to include optional adjuncts, such
as surfactants, builders, fluorescent whitening agents, enzymes,
and the like in appropriate levels to achieve the desired cleaning
effect without having any effective impact on the hydrophobic
agent, the zeta potential modifier or the optional fluoropolymer of
the instant disclosure in regards to the methods presented herein
for imparting stain and soil resistance to the desired materials.
Considerations enumerated above, especially careful adjustment of
zeta potential modifier so that the wash liquor exhibits zeta
potential greater than zero, result in compositions that are
effective in cleaning, as well as in imparting stain and soil
resistance as achieved by the methods of the instant
disclosure.
[0203] Compositions of the instant disclosure can be introduced
into an automatic washing machine during the rinse cycle of the
machine using rinse water additive dispensers that are well known
in the art. Examples include U.S. Pat. No. 5,768,918 to McKibben;
U.S. Pat. No. 5,267,671 to Baginski, et al.; U.S. Pat. No.
4,835,804 to Arnau-Munoz, et al.; U U.S. Pat. No. 3,888,391 to
Merz; and U.S. Pat. No. 3,108,722 to Torongo, Jr., et al.
Centrifugal force applied to a weight inside the dispenser during a
spin cycle of an automatic clothes washer can cause a dispenser
valve to become unseated so that additive from the dispenser may
spill out of the dispenser and mix with rinse water that is added
to the washer after the spin cycle. The dispenser can be normally
inserted into the washer before the wash cycle begins. It should
remain closed during the agitation of the wash cycle, yet reliably
open during the first spin cycle at the conclusion of the wash
cycle in order to deliver the composition of the instant disclosure
at a point in time at which it will be most effective.
[0204] Compositions of the instant disclosure may be packaged in
sachet form for convenient dosing and handling by the user. The
sachet may be of any suitable shape and construction. Highly
convenient shapes from the viewpoints of both manufacture and
packing are square and rectangular, but any other desired shape is
also suitable.
[0205] Preferred sachets may contain one, two, or more
compartments. In a two-compartment sachet, the compartments may,
for example, be side-by-side, joined by a common seal, or
back-to-back, joined by a common wall. The former arrangement is
more suitable if the two compartments are to be very different in
size, and is also easier to make. Other multi-compartment
arrangements are disclosed in EP 236136A, which is incorporated
herein by reference. The relative sizes of a single or
multi-compartment sachet can be tailored to match the proportions
of the total contents to be accommodated in each, and the optimum
shape of the sachet chosen accordingly. For example, a single
compartment or first compartment of a two-compartment sachet can
contain a relatively larger dosage of the composition of the
current invention for first treatment purposes, while the second
compartment of a two-compartment sachet can contain a relatively
smaller dosage for second or subsequent treatments, e.g.,
maintenance treatment purposes. The individual compartments of a
two or multi-compartment sachet can be easily separated from one
another by the user for dosage control when the contents comprise
the same composition, enabling one, two or multiple compartments of
the sachet to be used simultaneously, depending on the quantity of
composition required. The second compartment of a two-compartment
sachet may also contain ingredients other than the novel laundry
additive compositions described herein, such as typical adjuncts,
e.g., other non-interfering ingredients being packed together with
the composition of the current invention to provide a secondary
benefit. The total amount of the composition of the current
invention to be packaged in the sachet product may vary, for
example, from 10 to 150 g for a half dose (20 to 300 g for a single
dose), depending on the type and size of washing machine in which
it is intended to be used, and the amount of fabric that is
intended to be treated. It is generally preferred that the sachet
system be designed such that the contents will be released at or
very shortly after the time of addition to the wash liquor or the
rinse water (the "rinse liquor"), depending upon which cycle of the
wash the sachet containing the composition is added.
[0206] In an alternate embodiment, substantially complete delivery
of the contents is delayed to occur after at most 30 minutes, and
more preferably at most 25 minutes from the time of addition to the
wash liquor so that the contents of the sachet, which is introduced
during the wash cycle of the washing machine, are not substantially
released until at least the beginning of the rinse cycle of the
washing machine. In this latter embodiment, it may be sometimes be
desirable for the sachet systems to be designed such that at least
one compartment or sachet thereof gives a delayed or controlled
release of the contents. Suitable sachet structures are described
in EP236136A, Anderson, et al., which is incorporated herein by
reference.
[0207] In another embodiment, a water-insoluble sachet may be
employed to hold the laundry additive composition. Such a
water-insoluble sachet in accordance with this embodiment for
delivery of the composition may be of the closed, water-permeable
type that relies on leaching out by the wash liquor for release of
its contents. Alternatively, the sachet may be provided with a seal
that will open under washing machine conditions, by the action of
water or of mechanical agitation or both; for example, as disclosed
in EP312277A, Newbold, et al., which is incorporated herein by
reference. Opening sachets may be of either water-permeable or
water-impermeable material, with water-permeable material being
preferred. Suitable materials include paper, woven and non-woven
fabrics, films of natural or synthetic origin, or combinations
thereof having a base weight between 1 and 100 g/m2. Examples of
these are disclosed, for example, in EP246897A, Newbold, et al.,
which is incorporated herein by reference, and include polyamide,
polyester, polyacrylate, cellulose acetate, polyethylene, polyvinyl
chloride, polypropylene, cellulosic fibers, regenerated cellulosic
fibers, and mixtures thereof. Preferred materials include
cellulose/polyester mix fabrics, and Manila/viscose non-woven
paper. It is especially preferred that the seals are composed of a
water-labile component and a heat-sealable component, as described
in the before referenced EP246897A. These seals are sensitive at
wash temperatures to the combination of water and mechanical
agitation encountered in the washing machine environment, and open
to release the sachet contents. It is preferable for the sachet
substrate itself to be one that dissolves or disintegrates in the
wash or rinse liquor. Especially preferred are sachets of
water-soluble film. Such film materials are well-known in the art
and include polyvinyl alcohols and partially hydrolyzed polyvinyl
acetates, alginates, cellulose ethers such as
carboxymethylcellulose and methyl cellulose, polyacrylates,
polyethylene oxide, and combinations of these.
[0208] Also within the scope of the instant disclosure are
essentially dry means of delivery of the compositions, including
granular, powder and tablet forms of delivery, which may comprise
the present composition and a suitable inert carrier in which the
composition is reversibly compounded such that the composition can
be effectively released to the water when the granular, powder or
tablet delivery means is brought into contact with water, e.g.,
introduced into the wash water. In general, granular compositions
in accordance with the instant disclosure can be made via a variety
of methods including dry mixing, spray drying, agglomeration and
granulation. Tablets suitable for delivery of the composition of
the invention are well known in the art. Preferred are tablets of a
size that are convenient for dosing in a washing machine. A
preferred size is from 5 g to 200 g, more preferably from 5 g to
100 g, and the size can be selected in accordance with the intended
wash load and the design of the washing machine, which is to be
used. Also suitable are tablets containing two or more
compositional zones, in which one zone may comprise materials of
the instant disclosure and a second zone may comprise a carrier
comprising, but not limited to, adjunct materials described herein
as suitable optional additives.
Methodology
[0209] As further described herein, laundry additive compositions
of the instant disclosure can be deposited onto fabrics by a number
of methods. Regardless of the technique employed, it is important
that the hydrophobic agent and fluoropolymer become deposited on
the fabric surface. Subsequent heating above ambient temperatures
but below 100.degree. C. reversibly cures the composition onto the
fabric. However, excessive heating above 100.degree. C. is to be
avoided, as the resulting coating is then bound to the fabric too
tenaciously, leading to decreased overall performance of the
coating. Without being bound by theory, it is believed that the
coating should be reversibly bound to effect release of stains and
soils during subsequent laundering of the fabric.
[0210] In one embodiment, use of the laundry additive compositions
described herein includes introducing the composition during home
laundering of soiled garments in conventional home washing machines
that have a 25 to 90 liter capacity when filled. Such machines
typically have a fill/wash cycle of about 12 to 18 minutes duration
during which time the initial volume of water is added, a rinse
cycle of about 2 to 5 minutes during which sufficient water is
added to disperse the soil and detergent and other laundry
additives, and a spin cycle of about 10 to 20 minutes. Between the
wash, rinse and spin cycles, the introduced water is drained. These
individual cycles are to be understood to comprise an overall
laundering process or laundering cycle. A laundering cycle
therefore comprises one or more individual wash, rinse and spin
cycles or steps in the complete laundering process provided by a
conventional home automatic washing machine.
[0211] When detergent is used, the novel laundry additive
compositions described herein preferably include at least one zeta
potential modifier. In one embodiment, a laundry additive
composition containing a fluoropolymer, hydrophobic agent, and zeta
potential modifier is added to a fabric any time during the wash
cycle, that is, the period in which a detergent is added during the
overall laundering process. Alternatively, the fabric treatment
composition may be added whenever a fabric softener is routinely
added to the washing machine, as during a rinse cycle.
[0212] If desired, according to an embodiment, a laundry additive
product consistent with the instant disclosure may be formulated
that includes a detergent in addition to the hydrophobic agent,
fluoropolymer and zeta potential modifier of the instant laundry
additive compositions, to provide a method for imparting stain and
soil resistance to a fabric. Such a formulated product may also
contain additional adjuncts such as surfactants, builders,
fluorescent whitening agents, enzymes and the like. Such adjuncts
should be selected such they have minimal impact on the active
ingredients that impart fabric protective properties such as stain
and soil resistance. Such a formulated composition can be added
during the initial fill/wash cycle of a washing machine in which
the cleaning and protective methods of the current invention may be
practiced. This method is especially preferred, as the consumer
does not need to further intervene during the automated laundering
process.
[0213] An effective amount of the composition of the instant
disclosure can be sprayed or applied directly onto fabrics,
particularly clothing. When the composition is sprayed or applied
directly onto a fabric, an effective amount that can be deposited
onto the fabric without causing saturation of the fabric is
typically from about 10 to about 85 weight %, preferably from about
15 to about 65 weight %, and more preferably from about 20 to about
50 weight % of the fabric. The amount of active that can be
typically sprayed or applied directly onto the fabric is from about
0.1 to about 4 weight %, preferably from about 0.2 to about 3
weight %, and more preferably from about 0.3 to about 2 weight % of
the fabric.
[0214] According to a method in alternate embodiment, a fabric
treated with a laundry additive composition described herein can be
tumble-dried in a standard household clothes dryer and/or be ironed
at normal ironing temperatures to effect curing of the composition
onto the fabric. Inadvertent excessive curing or heating of a
fabric that has been treated with the composition is to be avoided,
especially where absorbency of the fabric is desired. Excessive
heating of a treated fabric as during a drying or curing cycle
could cause semi-permanent affixing of the treatment to the fabric.
Accordingly, the temperature of the dryer should be set to a range
of lower drying temperatures. Preferred drying temperatures that
should be use to effect curing of the laundry additive compositions
presented herein are less than 150.degree. C., more preferably less
than 125.degree. C. and most preferably less than 100.degree. C.
For sensitive fabrics, drying temperatures less than about
70.degree. C. are especially preferred.
[0215] In yet another embodiment, treated fabrics can be allowed to
dry at ambient temperature, and the curing effected subsequently by
a post-dry heating in a standard clothes dryer and/or by ironing at
temperatures preferably less than 150.degree. C., more preferably
less than 125.degree. C. and most preferably less than 100.degree.
C. Alternatively, the treated fabric can be subjected to radiant
energy, such as from the sun, or infrared generating heat source,
or exposure to microwave energy such as from a microwave dryer or
microwave generating device, to effect curing of the laundry
additive composition. The treated fabric may simultaneously be
dried and heated in one step to effect curing of the composition on
the fabric, or these operations may optionally be conducted in
sequence, providing that the heating step is performed subsequent
to the drying step.
[0216] Similarly, an effective amount of the composition can be
aerosolized and applied onto fabrics, particularly clothing, by
means of a clothes revitalizing device, such as the Whirlpool
PERSONAL VALET system distributed by the Whirlpool Corporation,
located at 2000 N. M-63, Benton Harbor, Mich. 49022-2692. or via a
system that delivers a sprayed or aerosolized composition into the
dryer itself. When used in such devices, the present composition
can be combined with the revitalizing solution normally employed in
the device, being combined in any desired ratio by volume, or
substituted entirely in place of the a revitalizing or other
treatment solution in order to effect treatment by use of
composition of the instant disclosure. An effective amount of the
composition can be automatically metered and aerosolized to effect
its deposition onto the clothes contained within the devices. A
drying step subsequently performed by the revitalizing device
equipped with an air blower and source of heat, or a source of
heated air in the dryer automatically follows--or is simultaneous
with--the deposition step in order to complete treatment of the
fabrics treated therein by the composition.
[0217] An effective amount of the present composition can also be
soaked with fabric and then optionally washed before tumble drying,
ironing or tumble-drying with optional ironing. In this aspect of
the invention, an acceptable method of delivery is to add the
composition to a separate soak or treatment cycle performed in a
washing machine or other suitable container with or without
agitation, such as hand-soaking of fabrics performed in a sink,
bucket or other such container, in which the composition of the
instant disclosure is added to water present with sufficient
agitation to uniformly mix the composition with the water to insure
effective dispersal or dissolution of the composition to create a
uniform dispersion or solution for subsequent treatment of the
fabrics. The order of mixing can be in any order, that is, the
composition can be added to water to effect dilution or water can
be added to the composition to effect dilution after the
composition is first introduced into a washing machine or other
suitable container. In this aspect of the invention, it is
preferable that the composition is first mixed with water to effect
dilution in either scenario described above before fabrics are
exposed to the diluted composition in order to effect the most
uniform treatment possible. Subsequent agitation of the diluted
composition and the fabrics is not generally required, although if
preformed in a washing machine such agitation is generally provided
during the wash cycle. Some newer washing machines, however,
provide for a timed soaking cycle with no agitation or with
intermittent agitation. Following such treatments, fabrics can be
drained of excess fluid and then dried at a temperature less than
100.degree. C. or optionally ironed at appropriate heat settings.
An available option is to rinse with freshwater and/or wash the
soaked fabrics, followed by tumble drying at less than 100.degree.
C. or optionally ironing at appropriate heat settings.
[0218] In a further aspect of the invention, an effective amount of
the composition can be added to the standard wash cycle of an
automatic washing machine and/or tumble-dried with optional
ironing. It is also a further option to add the invention to the
standard wash cycle and optionally rinse the fabrics prior to
drying at less than 100.degree. C. with optional ironing. In these
aspects of the invention, the composition may be combined with any
laundry additive, a detergent, completely substitute the detergent,
or additional surfactant and builders added to replace the
detergent. In still another aspect of the invention, an effective
amount of the composition can be added to the standard rinse or
separate part of the rinse cycle and/or tumble-dried with optional
ironing. In this aspect of the invention, the composition may be
combined with fabric softener or other rinse additive. When added
to the wash or rinse cycle, a variety of addition devices may also
be used. Many washing machines contain additive dispensers for
laundry additives such as bleach or fabric softener. Other devices
are known in the art to add liquids to the wash cycle and/or to
release them into the rinse cycle. In addition, water soluble
pouches, nonwoven pouches, powders and tablets may be used.
[0219] According to another embodiment of the disclosure, non-woven
and/or woven carrier articles may be treated with the laundry
additive compositions presented herein. A further embodiment of the
methods disclosed herein is to add a fragrance to the carrier
article. The carrier article is maintained in a moist state until
added to the dryer with articles to be treated. It is preferred
that the carrier article remains moist to facilitate the transfer
of the composition to the treated garments. This method is
especially effective on delicate articles including, but not
limited to, silk, wool, linen where excessive heat may cause
unwanted effects. Furthermore, this method allows for the
economical treatment of limited article loads or those containing
articles that should not be immersed or exposed to large volumes of
liquid.
[0220] When the present composition is added to the water present
in a washing machine or water present in some other suitable
container for soaking or hand-washing of fabrics, an effective
amount can be present to effect deposition of the disclosed laundry
additive compositions onto the fabric. The effective amount for a
first treatment operation performed on a previously untreated
fabric is typically from about 0.01% to about 10%, preferably from
about 0.1% to about 5%, and more preferably from about 0.1% to
about 2% of the composition to weight of the fabric present,
wherein the ratio of the weight of dry fabric to the weight of
water can be within a value between a ratio of 1:100 and 1:1,
respectively, of the ratio of the dry fabric weight to water weight
present.
[0221] Regardless of the method of application employed to effect
treatment of textile articles in particular, a curing step is
employed to complete treatment according to the methods of the
instant disclosure. A suitable curing step includes drying the
fabric articles treated with compositions according to the instant
disclosure at a temperature above ambient, but less than about
100.degree. C. Also suitable is heated drying, that is heating the
article above ambient temperatures, by such means including, but
not limited to ironing, steaming, blow drying, drying under a heat
lamp, drying near a radiative source of heat, or machine drying in
a dryer of the treated articles following treatment with
compositions of the instant disclosure. Curing may also be effected
by drying, following by a heating step wherein the treated dried
articles are subsequently heated above ambient temperature for a
time sufficient to effect treatment according to the methods of the
instant disclosure.
[0222] Following a first treatment of a fabric with a dose of a
laundry additive according to the instant disclosure, a subsequent
or further treatment of the fabric at a later time may be carried
out by applying a second laundry additive composition. The second
treatment composition may be less than, the same as or greater than
the dosage amount that was used during the first treatment.
Furthermore, any one or several of the components of the second
laundry treatment composition may differ in amount relative to the
amount of the analogous component in the first laundry additive
composition. That is, at any time after an initial treatment event,
it is possible to again treat a fabric at the first treatment
level, at a higher level or a lower level. Moreover, the second
laundry additive composition may have varying amounts of components
as compared to the amount of active components in a first laundry
additive composition. A smaller dosing of laundry additive actives
may be desirable in subsequent wash treatments following a first
fabric treatment, for example, to replenish the total amount of
laundry additive composition deposited on the fabric. Some of the
first laundry additive composition that was initially deposited on
the fabric may become lost due to wear or subsequent untreated
washing after occurrence of the first treatment. Such a
replenishment of fabric protective properties on a fabric by use of
a subsequent treatment cycle is understood to refer to a
maintenance level. In other words, when treating an untreated
fabric, the amount of laundry additive composition that is required
to effectively treat a fabric in order to impart desirable fabric
protective properties such as stain repellency, antimicrobial
activity, etc., will in general be greater for a first treatment
than for fabrics or surfaces that have previously been treated.
Thus, subsequent, repeated treatments may generally require
significantly lower amounts of the laundry additive composition in
order to effectively replenish a treatment composition on the
fabric and to maintain a desired level of desired benefits. Higher
or lower maintenance levels of a laundry additive composition may
be used in subsequent wash treatments in order to maintain a
consistent level of benefits.
[0223] Following treatment of a fabric or a washing machine surface
with an initial amount of the laundry additive composition
sufficient to impart stain repellency and/or microbiocidal or
microbiostatic characteristics to the fabric or washing machine
surface, subsequent laundering of the fabric can be carried out
with amounts of laundry additive composition to water that are
typically from about 0.001% to about 5%, preferably from about
0.01% to about 2%, and more preferably from about 0.01% to about
1%, by weight of the composition to weight of the water present,
wherein the ratio of the weight of dry fabric to the weight of
water is preferably within a value between a ratio of 1:100 and
1:1, respectively, of the ratio of the dry fabric weight to water
weight present.
[0224] In still a further aspect of the invention, an effective
amount of the composition can be added to a standard tumble dryer
with optional ironing. The laundry additive composition may be used
alone in any dryer delivery device, such as a nonwoven or sponge,
or combined with fabric softener sheets, home dry cleaning devices,
or other dryer device. Thus, another product form is a composition
of the instant disclosure (for example, a paste) suitable for
coating onto, and delivery from, a substrate e.g. a flexible sheet
or sponge or a suitable dispenser (such as a container having
apertures therein, for example) during a tumble dryer cycle. A
method of use is to add or release the present composition into the
rinse water. When using an aqueous, solid, powder, foam, gel,
pouch, tablet or sheet composition for treating fabric in the rinse
step, an effective amount of active of the laundry additive
composition can optionally contain fabric softener actives,
perfume, electrolytes, chlorine scavenging agents, dye transfer
inhibiting agents, dye fixative agents, phase stabilizers, chemical
stabilizers including antioxidants, silicones, antimicrobial
actives and/or preservatives, chelating agents, aminocarboxylate
chelating agents, colorants, enzymes, brighteners, soil release
agents, or mixtures thereof.
[0225] In still a further aspect of the invention, textiles treated
with the compositions of the instant disclosure, particularly
delicate fabrics, fabrics composed of natural fibers including, but
not limited to fur, wool or silks, fabrics comprising inclusions,
panels, or mixed woven or non-woven compositions of heat sensitive
natural or synthetic fibers including, but not limited to
elastomeric materials such as rubber, Spandex, polyacetate, vinyl
and nylon, may be so treated with the compositions of the instant
disclosure by any of the means described herein and allowed to dry
under ambient conditions without the application of heat in order
to prevent shrinking, dimensional distortion, wrinkling, creasing
or other such deleterious effects that may be the result of
applying heat to the wet textiles or heating the wet textiles
sufficiently and for sufficient time to reduce them to an
essentially dry state. Advantageously, such fabrics treated by the
compositions of the instant disclosure and allowed to dry under
ambient conditions, may subsequently be exposed to a heat source to
effect curing of the composition in order to obtain the full
benefits of the treatment. Such dry fabrics subsequently exposed to
a heat source including, but not limited to heating in an automatic
dryer, or contact with steam, an iron, heated air from a blow dryer
or other heat source, will not suffer from the deleterious effects
noted herein that are commonly seen when such delicate fabrics are
dried by heating to dryness starting from a substantially wet
state. In this aspect of the invention, the time of exposure to a
heat source required by textiles treated by the composition of the
instant disclosure and allowed to dry under ambient conditions, may
be substantially reduced compared to the time of exposure to a heat
source required if such textiles treated by the composition are
brought to dryness directly from a wet state. Such reduced time of
exposure to a heat source is beneficial to reduce such deleterious
effects noted above for many textiles, particularly those labeled
as delicate or dry-clean only textiles.
[0226] Drying is a function of both temperature and time. Effective
drying can be achieved either by exposing treated garments to
effectively higher drying temperatures for a shorter time, or
exposing treated garments to effectively longer drying times with
correspondingly lower drying temperatures. Preferred temperature
and drying times are typically provided by selected cycles of
commercially available automatic dryers under normal, permanent
press and delicate cycle selections. Highly preferred are cycle
selections that provide a short cooling down period with continued
tumbling to provide for reduced wrinkling of tumbled fabrics,
although this is not a requirement for treatment of fabrics treated
by the compositions of the instant disclosure. Drying the fabric at
a temperature above 45.degree. C. is preferred.
[0227] The compositions and articles of the instant disclosure
which contain a fabric improving active can be used to treat
fabrics, garments, and the like to provide at least one of the
following fabric care benefits: wrinkle removal and/or reduction,
fabric wear reduction, fabric pilling reduction, fabric color
fading reduction, fabric soiling reduction, fabric shape retention,
and/or fabric shrinkage reduction.
[0228] The compositions disclosed herein can be applied by any of
the above methods. In one method of use, a first composition can be
first applied at a high effective amount of the requisite actives
to give untreated fabrics the beneficial properties. Subsequent
treatment of the same fabrics can be applied at a lower maintenance
effective amount employing a second composition having requisite
actives at a lower level, and therefore more economical usage
benefit, but still effective at maintaining the beneficial
protective properties provided to the treated fabrics in a first
treatment step augmented by treatment in the second treatment step.
In another embodiment, a kit consisting of the two treatment
compositions as in the preceding embodiment may be employed, a
first treatment composition with a first effective level of a
hydrophobic agent, a fluoropolymer, and a zeta potential modifier,
and optionally one or more additives; and a second treatment
composition employed for subsequent and/or repeated treatment(s) to
maintain the fabric protective properties provided in the first
treatment step, where the second treatment composition has a second
effective level of a hydrophobic agent, a fluoropolymer, a zeta
potential modifier, and optionally one or more additives.
[0229] In one embodiment, a kit having a first laundry additive
composition and a second laundry additive composition is employed,
the kit having a first protective fabric treatment consisting of an
aqueous composition having: (a) about 5 to 10 weight % hydrophobic
agent; (b) about 5 to 30 weight % fluoropolymer; (c) about 0.1 to 5
weight % zeta potential modifier; (d) about 0.5 to 60 weight % of
an antimicrobial active; (e) optionally, about 0.01 to 10 weight %
bleaching agent; (f) optionally, about 0.1 to 10 weight %
surfactant; and (g) optionally, an additive; the kit also providing
a second protective fabric treatment consisting of a second aqueous
composition having (h) about 5 to 10 weight % hydrophobic agent;
(i) about 5 to 30 weight % fluoropolymer; and (j) about 0.1 to 5
weight % zeta potential modifier; (k) about 0.5 to 60 weight % of
an antimicrobial active; (1) optionally, 5 to 30 weight % of
fluoropolymer; (m) optionally, about 0.01 to 10 weight % bleaching
agent; (n) optionally, about 0.1 to 10 weight % surfactant; and (o)
optionally, an additive. In one embodiment, the kit is employed in
a first operation to first treat a fabric article, and then in a
second operation to restore a fabric protective benefit provided by
first use of the first laundry additive treatment. In another
embodiment, the kit is employed in a first operation to first
treat, and then in a second operation to maintain the first fabric
protective treatment benefit by a second and/or subsequent series
of second treatment steps employing the second treatment
composition of the kit. In yet another embodiment, the second
and/or subsequent series of second treatment operations may provide
an enhanced or different second fabric benefit differing from the
first fabric protective benefit provided in a first treatment
operation. In a particular embodiment, for example, a first
treatment composition has a hydrophobic agent, a fluoropolymer, a
zeta potential modifier, an antimicrobial active and a compatible
bleaching agent and surfactant to effect deep cleaning and stain
removal of residue on a soiled fabric article during a first
treatment operation, which provides a first fabric protective
benefit having stain and soil release characteristics of reduced
soiling; and in a second operation employing a second additive
composition, providing cleaning and maintenance of the protective
benefits and microbiocidal or microbiostatic properties provided by
the first additive composition.
[0230] In another embodiment, the kit includes instructions for use
of the first and second compositions for treating fabrics according
to the methods disclosed and described herein to deliver and
maintain the desired fabric protective properties, including
increased water repellency, increased oil repellency, soil and
stain release, improved handfeel, improved softness, improved
resistance to damage, residual antimicrobial efficacy, and any
combination thereof.
[0231] In other embodiments, concentrated compositions can be
employed, and used as is or further diluted prior to use.
Concentrated compositions comprise a higher level of fabric active,
typically from about 1% to about 99%, preferably from about 2% to
about 65%, and more preferably from about 3% to about 25%, by
weight of the concentrated fabric care composition. Concentrated
compositions are used in order to provide a less expensive product.
The concentrated product can be used undiluted or diluted by about
1,000,000%, more preferably by about 25,000%, and even more
preferably by about 5000% of the composition, by addition by weight
of water.
[0232] The compositions of the instant disclosure can also be used
as ironing aids. An effective amount of the composition can be
sprayed onto fabric and the fabric can be ironed at the normal
ironing temperature recommended by the fabric label instruction
guide. The fabric can be sprayed with an effective amount of the
composition, allowed to dry and then ironed, or sprayed and ironed
immediately to effect curing.
[0233] In a still further aspect of the invention, the present
composition can be sprayed and/or misted onto fabrics and/or entire
garments in need of de-wrinkling and/or other fabric care benefits
in a manner such that excessive amounts of the fabric/garment care
composition are prevented from being released to the open
environment, provided in association with instructions for use to
ensure that the consumer applies at least an effective amount of
fabric improving active and/or fabric care composition, to provide
the desired garment care benefit. Any spraying mechanism and/or
misting mechanism can be used to apply the fabric care composition
to fabrics and/or garments. One distribution of the garment care
composition can be achieved by using a fog form. The mean
particulate diameter size of the fabric care composition fog can be
from about 5 microns to about 200 microns, preferably from about 5
microns to about 100 microns, and more preferably from about 10
microns to about 50 microns. The wash or rinse water should contain
typically from 0.01 to 1 g of fluoropolymer per liter of wash water
and from 0.01 to 1 g of hydrophobic agent per liter of wash water.
Especially preferred levels of the fabric additive composition
described herein are from 0.01 to 0.5 g of fluoropolymer per liter
of wash water and from 0.01 to 0.5 g of hydrophobic agent per liter
of wash water. After treatment with an initial level of the
composition, a maintenance level of present composition may be
sufficient to maintain the properties. Desirable maintenance levels
of the laundry additive compositions can be from 0.01 to 0.2 g of
fluoropolymer per liter of wash water and from 0.01 to 0.2 g of
hydrophobic agent per liter of wash water. Especially preferred
levels of the laundry additive compositions disclosed herein are
from 0.01 to 0.1 g of fluoropolymer per liter of wash water and
from 0.01 to 0.1 g of hydrophobic agent per liter of wash
water.
[0234] The instant disclosure also relates to a method of using an
aqueous or solid, preferably powder or granular, composition to
treat the fabrics in the wash cycle, with such compositions
comprising the fabric protecting actives, and optionally,
surfactants, builders, perfume, chlorine scavenging agents, dye
transfer inhibiting agents, dye fixative agents, dispersants,
detergent enzymes, heavy metal chelating agents, suds suppressors,
fabric softener actives, chemical stabilizers including
antioxidants, silicones, antimicrobial actives and/or
preservatives, soil suspending agents, soil release agents, optical
brighteners, colorants, and the like, or mixtures thereof.
Depending on the selection of optional ingredients, such as the
level and type of surfactants, the present composition can be used
as a wash additive composition (when the surfactant level is low)
or as a laundry detergent, which also has additional fabric care
benefits. It is preferable that the treatment be performed in
accordance with the instructions for use, to ensure that the
consumer knows what benefits can be achieved, and how best to
obtain these benefits.
[0235] The instant disclosure also relates to a method for treating
fabric in the drying step, comprising an effective amount of the
fabric protecting actives of the instant disclosure and,
optionally, fabric softener actives, distributing agent, perfume,
fiber lubricants, fabric shape retention polymers, lithium salts,
potassium salts, phase stabilizers, chlorine scavenging agents, dye
transfer inhibiting agents, dye fixative agents, chemical
stabilizers including antioxidants, silicones, antimicrobial
actives and/or preservatives, heavy metal chelating agents,
aminocarboxylate chelating agents, enzymes, brighteners, soil
release agents, and mixtures thereof. The present composition can
take a variety of physical forms including liquid, foams, gel and
solid forms such as solid particulate forms. One method comprises
the treatment of fabric with a dryer-added fabric care composition
in combination with a dispensing means such as a flexible substrate
which effectively releases the fabric care composition in an
automatic tumble clothes dryer. Such dispensing means can be
designed for single usage or for multiple uses. Preferably, the
composition is applied onto a sheet substrate to form a dryer sheet
product.
[0236] Another method comprises the treatment of fabrics with a
fabric protection composition of the invention dispensed from a
sprayer at the beginning of and/or during the drying cycle. It is
preferable that the treatment be performed in accordance with the
instructions for use, to ensure that the consumer knows what
benefits can be achieved, and how best to obtain these
benefits.
[0237] The instant disclosure also relates to a fabric care method
of dipping and/or soaking fabrics before the fabrics are laundered,
with a pre-wash fabric care composition of the invention containing
an effective amount of fabric protecting active and, optionally,
surfactants, builders, perfume, chlorine scavenging agents, dye
transfer inhibiting agents, dye fixative agents, dispersants,
detergent enzymes, heavy metal chelating agents, fabric softener
actives, chemical stabilizers including antioxidants, silicones,
antimicrobial actives and/or preservatives, soil suspending agents,
soil release agents, optical brighteners, colorants, and the like,
or mixtures thereof. It is preferable that the treatment be
performed in accordance with the instructions for use, to ensure
that the consumer knows what benefits can be achieved, and how best
to obtain these benefits.
EXAMPLES
[0238] Experiments were conducted to demonstrate the desirable
effects of the antimicrobial laundry additive compositions
presented herein and various application techniques that can be
employed to effectively deliver the treatment compositions. Fabric
samples were analyzed for the ability to repel stains as well as
for antimicrobial activity.
[0239] For all studies, the antimicrobial laundry additive
composition that was used is shown below as Formula 1:
TABLE-US-00001 Formula 1: Laundry Additive Composition Ingredient
Percent Paraffin 12.0% Zeta potential modifier 7.5% Perfluorinated
polymer 4.5% Water to balance
Study 1: Effect of Delayed Release on Stain Removal
[0240] While it is foreseen that a laundry detergent can be
formulated to be compatible with cationic-based products as
described in U.S. Pat. No. 7,893,014 to van Buskirk, et al., and
continuations thereof, it is recognized, as discussed above, that
adding such compositions directly to a wash cycle that contains a
typical laundry detergent, i.e., one that contains anionic
surfactants, fluorescent whitening agents, enzymes and other
ingredients, can interfere with cleaning performance. In such
instances, it has surprisingly been found in the course of the
instant studies, that by delaying the release of the cationic-based
product into the same laundry solution by as little as a few
minutes can effect substantially improved cleaning performance.
Without being bound by theory, it is believed that the metal
ion-containing antimicrobial can degrade cation-containing cleaning
actives. Therefore, by delaying introduction of an antimicrobial
for some amount of time, optimized performance of a cleaning active
can be achieved in a laundry wash situation before the
antimicrobial is added. The amount of a time between introduction
of a washing active or actives to a wash liquor and introduction of
antimicrobial active or actives need not be very long. Time delays
on the order of a few minutes have been found to be sufficient, for
example delays of at least two minutes, preferably 5 minutes, more
preferably 10 minutes, and most preferably 15 minutes.
[0241] In one experiment described herein, three different
treatments were evaluated as shown in Table 1 below. First, as a
control study, fabrics having attached swatches of grass stains
were washed in a leading commercial liquid laundry detergent
containing anionic surfactants, fluorescent whitening agents, and
enzymes, designated as Sample 1 in Table 1 below. In a second
study, fabrics having attached swatches of grass stain were treated
with the same leading commercial liquid laundry and at the same
treated with the composition according to Formula 1, as shown by
Sample 2 below. In this second trial, the removal of grass stains
from the fabric swatch was significantly impaired. In a third
trial, labeled Sample 3 in Table 1 below, fabric with attached
swatches of grass stain were again treated with the same leading
commercial liquid laundry detergent plus the composition according
to Formula 1. In Sample 3, however, the addition of Formula 1 was
delayed by 15 minutes after the laundry detergent had been added to
the wash liquor. The results in this third case were rather
surprising: the grass stain removal was essentially identical to
that of the detergent alone, indicating that delayed addition of an
antimicrobial is key to maintaining cleaning performance. The
results of these three trials are shown below in Table 1 below.
TABLE-US-00002 TABLE 1 Timed Delay of Fabric Treatment During Wash
Cycle Delay Before Grass Stain Sample Addition of Fabric Removal
No. Treatment Treatment Efficacy.sup.a 1 Liquid Laundry Detergent
No added 10 antimicrobial 2 Liquid Laundry Detergent + 0 min. 4
Formula 1 (Simultaneous addition) 3 Liquid Laundry Detergent + 15
min. 9 Formula 1 (Delayed addition) Note to Table 1: .sup.aVisual
appearance: 10 = Grass stain completely removed, 0 = no grass stain
removal
Study 2: Effect of Order of Addition on Stain Repellency
[0242] The order in which an anionically-charged antimicrobial
additives can be added to a washing solution containing a
stain-repelling product according to Formula 1 may have profound
influences on stain repellency. To test this, the following was
performed:
Example 1
[0243] Example 1 consists of the following four steps, labeled (a)
through (d) below:
[0244] (a) Solutions containing Formula 1 and a typical
metal-polymer complex were added individually, together, and
serially to a top-loading household Kenmore Model 110 washing
machine with a low water level, using cool water. A swatch of 100%
cotton fabric was exposed to each solution for 15 minutes, spun to
remove most of the solution, and then dried for 25 minutes in a
household Kenmore Model 110 electric dryer;
[0245] (b) The fabrics were rated on a 0-3 scale for the ability to
repel drops of staining material (red wine or olive oil), as
follows: 3=bead sits on top of the fabric; 2=bead slightly spreads
on the fabric; 1=bead is slowly absorbed into the fabric; 0=bead is
readily absorbed into the fabric;
[0246] (c) The stain beads were then contacted with a facial tissue
in order to wick up any remaining stain material, and then rated on
a 0-3 scale as to the ability to remove the staining material:
3=stain was completely removed; 2=stain was mostly removed; 1=a
significant amount of the staining material was left behind; 0=most
or all of the stain material was left behind.
[0247] (d) The sum of these scores for both stains were then added
together for a total grade: a score of 12 would be ideal (fabric
repels both stains and comes completely clean), while a score of 0
would be what one would expect from an untreated fabric. The
results of this experiment are shown in TABLE 2 below.
TABLE-US-00003 TABLE 2 Effect of Order of Addition on Stain
Repellency Red wine Olive oil Stain Stain Stain Stain Total No.
Treatment repulsion residue repulsion residue score 1 Untreated
fabric 0 0 0 0 0 2 Formula 1, 100 grams 3 3 3 3 12 3 Silver/polymer
complex, 5 grams 1 0 0 0 1 4 Formula 1, 100 grams + 2 2 2 2 8
silver polymer complex, 5 grams 5 Formula 1, 100 grams, followed by
3 2 2 1 8 silver/polymer complex, 5 grams 6 Silver/polymer complex,
5 grams, 3 3 3 3 12 followed by Formula 1, 100 grams
Study 3: Effect of Order of Addition on Antimicrobial Efficacy
[0248] It has been surprisingly found that despite the anionic
nature of a metal/polymer complex, its antimicrobial properties can
be at least somewhat retained when added to a composition according
to Formula 1. Swatch samples from several treatments in Study 2
were placed in a Petri dish with active culture of Aspergillus
niger, incubated for a period of three days, and then evaluated for
their ability to retard the growth of Aspergillus niger. The
swatches were rated by the following basis: 3=swatch shows no
visible growth, 2=shows swatch some visible growth, 1=swatch shows
significant visible growth, and 0=swatch is totally covered with
microbe. The results are shown below in TABLE 3.
TABLE-US-00004 TABLE 3 Effect of Addition of Silver/Polymer Complex
Growth Rating Treatment against A. niger Untreated fabric 0 Formula
1, 100 grams 0 Formula 1, 100 grams + silver/polymer 2 complex, 5
grams Silver/polymer complex, 5 grams, followed 1 by Formula 1, 100
grams after 15 minutes elapsed time.
[0249] The instant disclosure presents information that has been
described in detail herein with reference to specific embodiments,
methods and examples. However, these specific embodiments should
not be construed as narrowing the scope of the formulations and
methods described herein, but rather construed as illustrative
examples. It is to be further understood that obvious embodiments,
modifications and equivalents thereof are anticipated and are
considered to be within the scope of the newly presented
formulations and methods, without departing from the broad spirit
contemplated herein. The subject matter of the instant disclosure
is further illustrated and described in the claims that follow.
* * * * *
References