U.S. patent application number 11/091671 was filed with the patent office on 2005-08-04 for fabric treatment for stain release.
This patent application is currently assigned to THE CLOROX COMPANY. Invention is credited to Casella, Victor M., DeLeo, Malcolm, Kaaret, Thomas Walter, Mills, Scott C., van Buskirk, Gregory.
Application Number | 20050166333 11/091671 |
Document ID | / |
Family ID | 32710971 |
Filed Date | 2005-08-04 |
United States Patent
Application |
20050166333 |
Kind Code |
A1 |
Kaaret, Thomas Walter ; et
al. |
August 4, 2005 |
Fabric treatment for stain release
Abstract
A fabric treatment composition that includes at least one zeta
potential modifier and a hydrophobic agent with a melting point or
glass transition temperature below 100.degree. C. that imparts
fabric protection benefits, including improved stain resistance,
oil repellency, water repellency, softness, wrinkle and damage
resistance, and better handfeel to treated fabrics. Particularly
preferred compositions include at least one zeta potential modifier
in an amount sufficient to adjust the zeta potential of the
composition to be positive and greater than zero millivolts.
Particularly preferred compositions also include a fluoropolymer.
The composition can be used as a pretreatment prior to washing,
through soaking or direct spray application, or added to the wash
or rinse cycle of an automatic washing machine, or used prior to or
during the drying cycle of an automatic drying machine or refresher
machine, or used prior to or in conjunction with an ironing device.
The fabric treatment is complete when the fabric is cured by drying
and/or heating.
Inventors: |
Kaaret, Thomas Walter;
(Alamo, CA) ; DeLeo, Malcolm; (Castro Valley,
CA) ; Mills, Scott C.; (Livermore, CA) ;
Casella, Victor M.; (Martinez, CA) ; van Buskirk,
Gregory; (Danville, CA) |
Correspondence
Address: |
Charles H. Jew
FLIESLER MEYER LLP
Fourth Floor
Four Embarcadero Center
San Francisco
CA
94111-4156
US
|
Assignee: |
THE CLOROX COMPANY
|
Family ID: |
32710971 |
Appl. No.: |
11/091671 |
Filed: |
March 28, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11091671 |
Mar 28, 2005 |
|
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10338350 |
Jan 8, 2003 |
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60371452 |
Apr 9, 2002 |
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Current U.S.
Class: |
8/115.51 |
Current CPC
Class: |
D06M 15/227 20130101;
D06M 2200/11 20130101; D06M 23/06 20130101; D06M 2200/12 20130101;
D06M 2200/20 20130101; D06M 15/263 20130101; D06M 13/428 20130101;
D06M 15/3562 20130101; D06M 13/285 20130101; D06M 13/463 20130101;
D06M 13/46 20130101; D06M 15/277 20130101; D06M 13/252 20130101;
D06M 2200/50 20130101; D06M 15/61 20130101; D06M 13/325 20130101;
D06M 13/388 20130101; D06M 13/236 20130101 |
Class at
Publication: |
008/115.51 |
International
Class: |
D06M 010/00 |
Claims
What is claimed is:
1. A method of non-durably imparting transient stain resistance and
oil repellency properties to a fabric that is laundered that
comprises the steps of: (a) immerging the fabric in a bath
containing wash liquor and a detergent; (b) removing wash liquor
from the bath and thereafter; (c) adding sufficient water to the
bath to immerse the fabric in an aqueous composition wherein the
aqueous composition contains a fluoropolymer that comprises 0.5 to
60 weight % of the aqueous composition and a hydrophobic agent
having a melting point or glass transition temperature of less than
100.degree. C. wherein said hydrophobic agent comprises 0.5 to 60
weight % of the aqueous composition; and (d) curing the fabric at a
temperature above ambient temperature but less than 100.degree. C.
to form a treated fabric whereby the fluoropolymer and the
hydrophobic agent are reversibly cured onto the treated fabric such
that the treated fabric exhibits greater stain resistance and
higher oil repellency relative to an identical, but non-treated
fabric and wherein the transient stain resistance and oil
repellency properties are lost from the treated fabric following
three subsequent laundering operations each of which comprises
steps (a) and (b) but not step (c).
2. The method of claim 1 wherein the aqueous composition comprises
an effective amount of a zeta potential modifier so that the
aqueous composition has a zeta potential that is positive and
greater than zero millivolts; and step (d) comprises (i) removing
water from the bath and (ii) then curing the fabric at a
temperature above ambient temperature but less than 100.degree.
C.
3. The method of claim 1 wherein the fluoropolymer is 5 to 30
weight % of the aqueous composition.
4. The method of claim 1 wherein the hydrophobic agent is 5 to 30
weight % of the aqueous composition.
5. The method of claim 2 wherein the zeta potential modifier is 0.1
to 30 weight % of the aqueous composition.
6. The method of claim 2 wherein the zeta potential modifier is a
cationic material.
7. The method of claim 6 wherein the cationic material is a
cationic surfactant selected from the group consisting of mono and
di-methyl fatty amines, alkyl trimethyl ammonium salts, dialkyl
dimethyl ammonium salts, alkyl amine acetates, trialkylammonium
acetates, alkyldimethylbenzyl ammonium salts, dialkylmethylbenzyl
ammonium salts, alkylpyridinium halide and alkyl (alkyl
substituted) pyridinium salts, alkylthiomethylpyridinium salts,
alkylamidomethylpyridinium salts, alkylquinolinium salts,
alkylisoquinolinium salts, N,N-alkylmethylpyrollidinium salts,
1,1-dialkylpiperidinium salts, 4,4-dialkylthiomorpholinium salts,
4,4-dialkylthiomorpholinium-1-oxide salts, methyl bis(alkyl
ethyl)-2-alkyl imidazolinium methyl sulfate, methyl bis(alkylamido
ethyl)-2-hydroxyethyl ammonium methyl sulfate,
alkylamidopropyl-dimethylbenzyl ammonium salts,
carboxyalkyl-alkyldimethy- l ammonium salts, alkylamine oxides,
alkyldimethyl amine oxides, poly(vinylmethylpyridinium) salts,
poly(vinylpyridine) salts, polyethyleneimines, trialkyl phosphonium
bicarbonates, trialkylmethyl phosphonium salts,
alkylethylmethylsulfonium salts, and alkyldimethylsulfoxonium
salts.
8. The method of claim 1 wherein the hydrophobic agent is at least
partly insoluble in water at a temperature of about 20.degree.
C.
9. The method of claim 1 wherein the hydrophobic agent is selected
from the group consisting of hydrophobic waxes, polymers produced
from ethylenically unsaturated monomers, low molecular weight
polyethylene, low density polyethylene, polypropylene, polyolefin,
polyurethane, ethyl vinyl acetate, polyvinyl chloride, co-polymers,
and emulsifiable waxes.
10. The method of claim 1 wherein the aqueous composition comprises
an aqueous liquid carrier that includes a low molecular weight
organic solvent.
11. The method of claim 10 wherein the aqueous liquid carrier is
between 20% and 80% weight of the composition.
12. The method of claim 1 wherein the aqueous composition further
comprises an additive selected from the group consisting of
emulsifiers, pH adjusters, silicones, non-ionic surfactants,
cationic surfactants, amphoteric surfactants, zwitterionic
surfactants, anionic surfactants, soil release agents, soil release
polymers, antistatic agents, fragrances, fragrance extenders,
antimicrobial actives, preservatives, dyes, colorants, viscosity
control agents, antifoaming agents, pearlizing agents, opacifying
agents, antioxidants, sunscreens, dye transfer inhibitors, dye
fixative agents, dispersants, chlorine scavengers, wetting agents,
electrolytes, enzymes, bleaching agents, brighteners, heavy metal
chelating agents, fabric softener actives, soil suspending agents,
soil release agents, and mixtures thereof.
13. The method of claim 1 wherein the hydrophobic agent has a
melting point or glass transition temperature between 45.degree. C.
and 100.degree. C.
14. The method of claim 1 wherein the aqueous composition
comprises: (i) 5 to 30 weight % of a fluoropolymer; (ii) 5 to 30
weight % of the hydrophobic agent; and (iii) a liquid carrier.
15. The method of claim 1 wherein the fabric is made of cotton.
16. The method of claim 1 wherein the step (d) produces a cured
fabric that exhibits greater stain resistance and higher oil
repellency relative to an identical fabric that had been subject to
steps (a), (b), and (c) but which had been cured by excessive
heating above 100.degree. C.
17. The method of claim 1 wherein the fabric is cured by heating
the fabric to a temperature that is less than the melting point or
glass transition temperature of the hydrophobic agent.
18. A method of reversibly imparting transient stain resistance and
oil repellency properties to a fabric that comprises the steps of:
(a) applying a composition onto the fabric wherein the composition
comprises a fluoropolymer and a hydrophobic agent having a melting
point or glass transition temperature of less than 100.degree. C.;
and (b) curing the fabric at a temperature above ambient
temperature but less the hydrophobic agent's melting point or glass
transition temperature to form a treated fabric whereby the
fluoropolymer and the hydrophobic agent are reversibly cured onto
the treated fabric such that the treated fabric exhibits greater
stain resistance and higher oil repellency relative to an
identical, but non-treated fabric and wherein the transient stain
resistance and oil repellency properties are lost from the treated
fabric following three subsequent laundering operations each of
which comprises the steps of (i) immerging the fabric in a bath
containing wash liquor bath and (ii) removing wash liquor from the
bath.
19. The method of claim 18 wherein the composition comprises a zeta
potential modifier.
20. The method of claim 19 wherein the zeta potential modifier is a
cationic material.
21. The method of claim 19 wherein the cationic material is a
cationic surfactant selected from the group consisting of mono and
di-methyl fatty amines, alkyl trimethyl ammonium salts, dialkyl
dimethyl ammonium salts, alkyl amine acetates, trialkylammonium
acetates, alkyldimethylbenzyl ammonium salts, dialkylmethylbenzyl
ammonium salts, alkylpyridinium halide and alkyl (alkyl
substituted) pyridinium salts, alkylthiomethylpyridinium salts,
alkylamidomethylpyridinium salts, alkylquinolinium salts,
alkylisoquinolinium salts, N,N-alkylmethylpyrollidinium salts,
1,1-dialkylpiperidinium salts, 4,4-dialkylthiomorpholinium salts,
4,4-dialkylthiomorpholinium-1-oxide salts, methyl bis(alkyl
ethyl)-2-alkyl imidazolinium methyl sulfate, methyl bis(alkylamido
ethyl)-2-hydroxyethyl ammonium methyl sulfate,
alkylamidopropyl-dimethylbenzyl ammonium salts,
carboxyalkyl-alkyldimethy- l ammonium salts, alkylamine oxides,
alkyldimethyl amine oxides, poly(vinylmethylpyridinium) salts,
poly(vinylpyridine) salts, polyethyleneimines, trialkyl phosphonium
bicarbonates, trialkylmethyl phosphonium salts,
alkylethylmethylsulfonium salts, and alkyldimethylsulfoxonium
salts.
22. The method of claim 18 wherein the hydrophobic agent is at
least partly insoluble in water at a temperature of about
20.degree. C.
23. The method of claim 18 wherein the hydrophobic agent is
selected from the group consisting of hydrophobic waxes, polymers
produced from ethylenically unsaturated monomers, low molecular
weight polyethylene, low density polyethylene, polypropylene,
polyolefin, polyurethane, ethyl vinyl acetate, polyvinyl chloride,
co-polymers, and emulsifiable waxes.
24. The method of claim 18 wherein the composition further
comprises an additive selected from the group consisting of
emulsifiers, pH adjusters, silicones, non-ionic surfactants,
cationic surfactants, amphoteric surfactants, zwitterionic
surfactants, anionic surfactants, soil release agents, soil release
polymers, antistatic agents, fragrances, fragrance extenders,
antimicrobial actives, preservatives, dyes, colorants, viscosity
control agents, antifoaming agents, pearlizing agents, opacifying
agents, antioxidants, sunscreens, dye transfer inhibitors, dye
fixative agents, dispersants, chlorine scavengers, wetting agents,
electrolytes, enzymes, bleaching agents, brighteners, heavy metal
chelating agents, fabric softener actives, soil suspending agents,
soil release agents, and mixtures thereof.
25. The method of claim 18 wherein the hydrophobic agent has a
melting point or glass transition temperature between 45.degree. C.
and 100.degree. C.
26. The method of claim 18 wherein the fabric is made of
cotton.
27. The method of claim 18 wherein the composition is sprayed onto
the fabric.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of U.S.
application Ser. No. 10/338,350, filed Jan. 8, 2003, entitled
FABRIC TREATMENT FOR STAIN RELEASE (Atty. Docket No.:
CLORX-01000US0) which claims the benefit of U.S. Provisional
application filed Apr. 9, 2002, Ser. No. 60/371,452.
FIELD OF THE INVENTION
[0002] The present invention relates to a fabric treatment
composition for imparting fabric protection benefits, including
stain resistance, oil repellency, water repellency, softness,
wrinkle and damage resistance, and improved handfeel. The
composition can be used as a pretreatment prior to washing, through
soaking or direct spray application, or added to the wash or rinse
cycle of an automatic washing machine, or used prior to or during
the drying cycle of an automatic drying machine or refresher
machine, or used prior to or in conjunction with an ironing device.
The fabric treatment is complete when the fabric is cured by drying
and/or heating.
BACKGROUND OF THE INVENTION
[0003] 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 (substantially above 100.degree. C.) often in
commercial drying ovens. For example, U.S. Pat. No. 6,251,210 to
Bullock et al. discloses a dual system consisting of a first
treatment with at least 5 weight % fluorochemical textile agent
followed by at least one secondary treatment with at least 4 weight
% fluorochemical textile agent. 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.
[0004] 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.
[0005] 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. 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.
[0006] 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.
[0007] 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.
[0008] 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.
[0009] 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.
[0010] U.S. Pat. No. 6,180,740 to Fitzgerald describes an aqueous
emulsion containing a fluorocopolymer 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.
[0011] U.S. Pat. No. 6,379,753 to Soane et al. describes methods
for modifying textile materials to render them, for example, water
repellant 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.
[0012] As can be seen there is a need for a product that offers the
controlled and even coating of commercial treatment operations with
the convenience and ease of home use. Additionally the coating
should be cured at temperatures that are attainable in commonly
available residential dryers as curing at high temperatures makes
the coating excessively durable typically resulting in an
unfavorable handfeel owing to excessive build up over numerous
treatment cycles. Furthermore, the reduced temperature curing
results in not only improved handfeel, it allows for an easily
reversible and/or removable coating. Such a transient coating
reduces coating build up over multiple applications or treatments
that result in poor handfeel, and also reduces the potential for
leaving a visible residue or causing an undesirable changes in
appearance, 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, including clothes.
SUMMARY OF THE INVENTION
[0013] The present invention is based in part on the discovery that
compositions containing at least one zeta potential modifier and a
hydrophobic agent when applied to fabrics and cured by drying
and/or heating will impart numerous fabric protection benefits,
including stain resistance, oil repellency, water repellency,
softness, wrinkle and damage resistance, and improved handfeel.
Fabric protection benefits include minimizing fiber wear (e.g.,
retaining fiber tensile strength), maintaining fabric appearance by
reducing fiber pilling, and/or reducing color loss, and/or
inhibiting the deposition of fugitive dyes onto the fabric during a
washing process. These benefits, individually and collectively,
increase the useful longevity of the treated garment or fabric.
Preferred fabric treatment compositions also include a
fluoropolymer. In one aspect, the invention is directed to a method
of increasing the fabric protection properties of a fabric that
includes the steps of:
[0014] (a) depositing a composition onto the fabric wherein the
composition comprises at least one zeta potential modifier and a
hydrophobic agent having a melting point or glass transition
temperature of less than 100.degree. C.; and
[0015] (b) curing said fabric at a temperature above ambient but
less than 100.degree. C. In another aspect, the invention is
directed to a fabric work that is laundered in a treatment cycle,
wherein the fabric work is placed into treatment liquor including a
composition for textile treatment that includes:
[0016] a fluoropolymer;
[0017] a hydrophobic agent having a melting point or glass
transition temperature of less than 100.degree. C.; and
[0018] an effective amount of at least one zeta potential modifier
so that the composition has a zeta potential that is positive and
greater than zero millivolts.
[0019] In a further aspect, the invention is directed to a
composition for textile treatment that includes:
[0020] a fluoropolymer;
[0021] a hydrophobic agent having a melting point or glass
transition temperature of less than 100.degree. C.; and
[0022] an effective amount of at least one zeta potential modifier
so that the composition has a zeta potential that is positive and
greater than zero millivolts.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Fabric treatment compositions of the present invention
generally comprise (i) a fluoropolymer, (ii) a hydrophobic agent
having a melting point or glass transition temperature of less than
100.degree. C., and (iii) an effective amount of at least one zeta
potential modifier so that the composition has a zeta potential
that is positive and greater than zero millivolts. Preferred
compositions are aqueous systems that may include an organic
solvent.
[0024] As further described herein the presence of at least one
zeta potential modifier is preferred when the composition is used
in conjunction with or following laundering with detergent.
However, the potential modifier is not necessary when the fabric
treatment composition is used to pretreat or treat a fabric by
direct application or through a treatment liquor in which the
inventive fabric treatment composition is used in the absence of
any other treatments such as a presoak composition, laundry
additive or detergent. Hence, the zeta potential modifier is not
necessary under these preceding conditions to impart the desirable
fabric protection benefits, including stain resistance, oil
repellency, water repellency, softness, wrinkle and damage
resistance, and improved handfeel. All percentages specified herein
are based on weight unless noted otherwise.
[0025] Fluoropolymer
[0026] According to the present invention, the fluoropolymers as
prepared may contain some amount of surfactants, especially
mixtures of cationic and nonionic surfactants, but usually the
amounts are small. A preferred range for fluoropolymers is 0.5 to
60%, more preferred is 1 to 40%, and further preferred is 5 to
30%.
[0027] The fluoropolymers employed in the invention can be water
insoluble oily soil repellents and have one or more fluoroaliphatic
radicals, typically one or more perfluoroalkyl radicals. They can
be nonionic in that they do not contain an ionized functional group
such as a quaternary ammonium group. Useful classes of the
fluoropolymers are the fluorocarbonylimino biurets, the
fluoroesters, the fluoroester carbamates, and the fluoropolymers.
The class of fluorocarbonylimino biurets 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 antisoilant 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 ethyl
acrylate, optionally with small amounts of other monomers.
[0028] 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.
Additional useful fluoropolymers include ZONYL 7950, ZONYL 5180,
ZONYL 5180, ZONYL 6885, ZONYL 7910, ZELAN 338, ZONYL 6700, ZONYL
8300, ZONYL 6991, ZONYL 310 and ZONYL NWG, all from Dupont. 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 perfluoropolyether 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 NUVA 5006, NUVA LB Liquid, NUVA LC
Liquid (available from Clariant Corporation, Charlotte, N.C.),
fluoropolymer REPEARL F-45 (available from Mitsubishi International
Corporation, NY N.Y.) and MYAFIX WS and MYAFIX EX.WS (available
from Peach State Labs, Rome, Ga.). Other examples include NUVA FT
fluorochemical acrylate polymer (available from Hoeschst Celanse,
Charlotte, N.C.), SHAWGUARD 353 fluoroalkyl acrylate copolymer
(available from Shaw Industries, Inc.) and BARTEX TII, BARTEX MAC,
both fluoroalkyl acrylate polymers (available from Trichromatic
Carpets, Inc., Quebec, Canada).
[0029] 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.
[0030] Hydrophobic Agent
[0031] A preferred range for hydrophobic agents is 0.5 to 60%, more
preferred is 1 to 40%, and further preferred is 5 to 30%.
[0032] 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 below 100.degree. C. Suitable hydrophobic agents
include hydrophobic polymer, 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 (DTA), as
described in "The Analyst" 87 (1962), 420, and/or by their
solidification point. This is understood to be the temperature at
which the wax changes from a liquid into a solid state through slow
cooling. According to the invention, both paraffins can be
completely liquid at room temperature, i.e. those with a
solidification point below 25.degree. C., and paraffins solid at
room temperature may 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 may be obtained, for example, under the name of
LUNAFLEX from Fuller and under the name of DEAWAX from DEA
Mineralol AG.
[0033] 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.8 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 polymers 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.8 alcohols and/or methacrylic acid with C.sub.4 to C.sub.8
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 C.sub.1 to
C.sub.3 alcohols or styrene. Examples of such polymers include the
following commercial products that are available as dispersions:
SYNTRAN 1501 (Interpolymer), PRIMAL 644 (Rohm & Haas), NEOCRYL
A 1049 (ICI). Other preferred polymers include low molecular weight
(below 500,000) polyethylene, low density polyethylene,
polypropylene, polyolefin, polyurethane, ethyl vinyl acetate,
polyvinyl chloride, and co-polymers.
[0034] 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 maleic grafted polyolefin
waxes, paraffin, other hydrocarbon waxes and vegetable waxes such
as carnauba and candelillia. Preferred emulsifiable waxes include
oxidized polyethylene, ethylene acrylic copolymers, and maleic
grafted polyolefins. These 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 candellila, 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.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 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.
[0035] Other preferred waxes may be, for example, alkyl methycone
AMS-C30 (Dow Corning), natural candelilla (Candellila from Frank B.
Ross), stearyoxyytrimethylsilane 580 wax (Dow Corning), cetyl
palmitate DUB PC Stearine (Dubois), microcrystalline/petrolatum
MULTIWAX B710 (Witco), Scale paraffin (Strahl and Pitsch), natural
beeswax (Frank B. Ross), microcrystalline (Ultraflex Petrolite),
microcrystalline Ross wax 1329/1 (Frank B. Ross), microcrystalline
Multiwax 110X (Witco), paraffin (Altafin 135/140), petrolatum
(Petrolatum Snow from Penreco), refined paraffin (Strahl and
Pitsch), and paraffin Altafin 125/130. Preferably, the low melting
point wax is selected from microcrystalline Multiwax W145A (Witco),
paraffin (Altafin 140/145 from Astor-Durachem), and
microcrystalline Ross wax 1365 (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 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.
[0036] Liquid Carrier
[0037] 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.
[0038] 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.
[0039] 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, 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.
[0040] Zeta Potential Modifier
[0041] Compositions of the present invention 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 tern, 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:
.xi.=4.pi..delta.q/D
[0042] 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.
[0043] 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, e.g., 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.
[0044] 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.
[0045] Preferred 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,
alkylthiomethylpyridinium salts, alkylamidomethylpyridinium salts,
alkylquinolinium salts, alkylisoquinolinium salts,
N,N-alkylmethylpyrollidonium salts, 1,1-dialkylpiperidinium salts,
4,4-dialkylthiamorpholinium salts,
4,4-dialkylthiamorpholinium-1-oxide salts, methyl bis (alkyl
ethyl)-2-alkyl imidazolinium methyl sulfate (and other salts),
methyl bis(alkylamido ethyl)-2-hydroxyethyl ammonium methyl sulfate
(and other salts), alkylamidopropyl-dimethylbenzyl ammonium salts,
carboxyalkyl-alkyldimethyl ammonium salts, alkylamine oxides,
alkyldimethyl amine oxides, poly(vinylmethylpyridinium) salts,
poly(vinylpyridine) salts, polyethyleneimines, trialkyl phosphonium
bicarbonates (and other salts), trialkylmethyl phosphonium salts,
alkylethylmethylsulfonium salts, and alkyldimethylsulfoxonium
salts.
[0046] 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 IIA), 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.
[0047] It should further be noted that the zeta potential modifiers
are included as optional ingredients of the fabric treatment
composition as discussed herein. Thus when the 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 the fabric
surface.
[0048] 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.
[0049] Optional Ingredients
[0050] Emulsifiers
[0051] The above fluoropolymers and hydrophobic agents 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-hexadecylammonium
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 monosearate.
[0052] 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.
[0053] pH Adjusters
[0054] The pH of a 10% 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.
[0055] 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.
[0056] Silicones
[0057] 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 (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 namess. 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 preemulsified 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.
[0058] 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.
[0059] Nonionic Surfactant
[0060] 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.
[0061] 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.
[0062] 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.
[0063] Cationic Surfactants
[0064] The composition of the present invention can contain a
cationic surfactant. When a cationic surfactant is added to the
composition of the present invention, 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.
[0065] The cationic surfactant can optionally be one or more fabric
softener actives. Preferred fabric softening actives according to
the present invention 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-me- thyl,
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-dim-
ethyl ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-et-
hyl)-N,N-dimethyl ammonium chloride,
N,N,N-tri(tallowyl-oxy-ethyl)-N-methy- l ammonium chloride;
N,N,N-tri(canolyl-oxy-ethyl)-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-me- thyl,
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 Bemadino, U.S. Pat. No.
3,861,870 Edwards et al., and European Patent Application
publication No. 472,178, by Yamamura et al., all of said documents
being incorporated herein by reference.
[0066] 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.
[0067] 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.
[0068] Amphoteric and Zwitterionic Surfactants
[0069] The composition of the present invention can contain
amphoteric and/or zwitterionic surfactants. When an amphoteric or
zwitterionic surfactant is added to the composition of the present
invention, 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.
[0070] 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 present invention include amine oxides having the
formula (R.sub.1)(R.sub.2)(R.su- b.3)NO wherein R.sub.1 is an
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.
[0071] 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
alkylampho glycinates, 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 users skin.
[0072] 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.
[0073] 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.
[0074] Anionic Surfactants
[0075] The composition can contain an anionic surfactant. When an
anionic surfactant is added to the composition of the present
invention, 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.
[0076] 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., STEPANOLAMC 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(8), and Hostapur SAS(E) 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.
[0077] 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.
[0078] Soil Release Agents
[0079] The composition can 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 present
invention include copolymeric 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.; 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 present invention 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. 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.
[0080] Antistatic Agents
[0081] 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 present invention
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 dihydrogenated
tallow benzyl ammonium chloride. Other preferred antistatic agents
of the present invention 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 Rhne--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.
[0082] 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.
[0083] Fragrance
[0084] Perfumes or fragrance materials may be added to the
composition. The selection of the perfume or perfumes may be 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 present invention 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.
[0085] 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-trimethy- l-3-cyclopenten-1-yl)-2-buten-1-ol),
benzaldehyde, benzophenone, benzyl acetate, benzyl salicylate,
damascone (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-methanoazul- en-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-isopropyl- phenyl)-propionaldehyde), decyl aldehyde,
damascone (1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one),
dihydromyrcenol (2,6-dimethyl-7-octan-2-ol), dimethyl benzyl
carbinyl 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), floor 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-hexamethylcycl-
opent-gamma-2-benzopyrane), 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-1,1,6,7tetramethylnaphthalene,
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
CP (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 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-tert-butyl cyclohexyl acetate), and mixtures
thereof.
[0086] 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.
[0087] 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.
[0088] Antimicrobials and Preservatives
[0089] Optionally, antimicrobials or preservatives can be added to
the present invention. Typical concentrations for biocidal
effectiveness 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. The
corresponding concentrations for the concentrated compositions are
from about 0.003% to about 2%, preferably from about 0.006% to
about 1.2%, and more preferably from about 0.1% to about 0.8% of
the concentrated compositions.
[0090] Preservatives are especially preferred when organic
compounds that are subject to microorganisms are added to the
compositions of the present invention, 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. Therefore,
because microbial growth in these compositions and formulations is
highly objectionable when it occurs, it is 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 present
invention.
[0091] 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 present invention. 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 present invention
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 present invention 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); 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 Henkel Corporation under the trade name BRONIDOX L;
2-bromo-2-nitropropane-1,3-d- iol, 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-imidazol- idinedione 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-i-
midazolidinyl]-N,N'-bis(hydroxy-methyl) 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
which is appropriate for the application, for example, in a laundry
application such preservative will preferably not cause damage to
fabric appearance, for example, discoloration, coloration, or
bleaching of the fabric. If the antimicrobial preservative is
included in the compositions and formulations of the present
invention, 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 which provides an antimicrobial effect on the treated
fabrics.
[0092] The composition may suitably use an optional solubilized,
water-soluble antimicrobial active, useful in providing protection
against organisms that become attached to the treated material. The
free, uncomplexed antimicrobial, e.g., antibacterial, active
provides an optimum antibacterial performance. Sanitization of
fabrics can be achieved by the compositions of the present
invention containing, antimicrobial materials, e.g., antibacterial
halogenated compounds, quaternary compounds, and phenolic
compounds. 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 present invention 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 present invention
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
Witco/Sherex), 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 Rohm & Haas; (5) methylbenzethonium chloride represented
by HYAMINE 1O.times. supplied by Rohm & Haas, (6)
cetylpyridinium chloride such as Cepacol chloride available from of
Merrell Labs.
[0093] 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, cylcohexylsulphamates 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 alkyl dimethyl benzyl ammonium
chloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethyl
ammonium chloride, didecyl dimethyl ammonium chloride, alkyl
dimethyl ammonium saccharinate, cetylpyridinium and mixtures
thereof.
[0094] 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.
[0095] Dyes and Colorants
[0096] Optionally, dyes and colorants can be added to the present
invention. 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.
[0097] Colorants and dyes, especially bluing agents, can be
optionally added to the compositions of the present invention 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 present invention, 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 inventive compositions. 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.
[0098] 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.
[0099] 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.
[0100] Viscosity Control Agents
[0101] 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.
[0102] Viscosity modifiers (raising) 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 Rhne-Poulenc Corporation under the trade name JAGUAR
HP200), polyethylene glycol (such as that available from Union
Carbide Corporation under the trade name CARBOWAX 20M), hydrophobic
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 the Rheox Company under the trade 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 (thickeners) can typically be
used at levels from about 0.5% to about 30%, 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%, of the
composition.
[0103] 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.
[0104] Pearlizing and Opacifying Agents
[0105] Examples of pearlizing or opacifing 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.
[0106] 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.
[0107] Antioxidants and Sunscreen Materials
[0108] 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 present invention, 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-buty- l-4'-hydroxy
benzoate. Of these compounds, the butylated derivatives are
preferred in the compositions of the present invention because
tri-hydroxybenzoates have a tendency to discolor upon exposure to
light. The antioxidant compounds of the present invention
demonstrate light stability in the compositions of the present
invention. "Light stable" means that the antioxidant compounds in
the compositions of the present invention 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, The
Encyclopedia of Chemical Technology, Volume 3, pages 128-148, Third
Edition (1978) which is incorporated herein by reference.
[0109] Compositions of the present invention may comprise an
organic sunscreen. Suitable sunscreens can have UVA absorbing
properties, UVB absorbing properties, or a combination of both. The
compositions of the present invention 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-dimet-
hylethyl)-4'-methoxydibenzoylmethane,
2-methyl-5-isopropyl-4'-methoxydiben- zoylmethane,
2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
2,4-dimethyl-4'-methoxydibenzoylmethane,
2,6-dimethyl-4'-tert-butyl-4'-me- thoxydibenzoylmethane, and
mixtures thereof. Preferred dibenzoyl sunscreen actives include
those selected from 4-(1,1-dimethylethyl)-4'-methoxydiben-
zoylmethane, 4-isopropyldibenzoylmethane, and mixtures thereof. A
more preferred sunscreen active is
4-(1,1-dimethylethyl)-4'-methoxydibenzoylme- thane, 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 present
invention 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. Nonlimiting 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-diphenylacryla- te
(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.
[0110] An agent may also be added to any of the compositions useful
in the present invention to stabilize the UVA sunscreen and to
prevent it from photo-degrading on exposure to UV 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 present invention 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.
[0111] 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.
[0112] The composition of the present invention 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 present invention repeatedly,
may result in higher deposition levels, which contributes even
further to the sun-fading protection benefit.
[0113] Dye Transfer Inhibitors and Dye Fixatives
[0114] 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.
[0115] Compositions and formulations of the present invention 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 present
invention 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 present invention.
[0116] 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.
[0117] Chlorine Scavengers
[0118] The compositions of the present invention 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: [(R).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.
[0119] 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.
[0120] Wetting Agents
[0121] The present invention 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
present invention 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.
[0122] 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.
[0123] Electrolyte
[0124] 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, NaSO.sub.3, Na.sub.2SO.sub.4,
Na.sub.2SO.sub.3, 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 IIIa, IVa, Va, Vla, VIIa, VIII,
Ib, and IIb on the periodic chart with atomic numbers>13 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 la or Ila with
atomic numbers>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.
[0125] 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 hydrogencarbonate (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.
[0126] 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.
[0127] 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, or after the drying
and/or curing step followed by normal exposure to the elements,
such as air, moisture or sunlight exposure.
[0128] 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 inventive composition.
[0129] Enzymes
[0130] Additional desirable adjuncts may be enzymes (although it
may be preferred to also include an enzyme stabilizer). 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 Rapidase, from Societe
Rapidase, Milezyme from Miles Laboratory, and Maxamyl from
International BioSynthetics. 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 Thom 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.
[0131] 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.
[0132] Bleaching Agents
[0133] The compositions of the present invention 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. No. 5,877,315 and Casella et al., U.S.
Pat. No. 5,888,419 (which relate to cyanonitrile derivatives), Fong
et al., U.S. Pat. Nos. 4,959,187 and 4,778,816, Bolkan et al., U.S.
Pat. Nos. 5,112,514 and 5,002,691, and Brodbeck et al., U.S. Pat.
No. 5,269,962 (which relate to alkanoyloxyacetyl derivatives); and
Mitchell et al., U.S. Pat. Nos. 5,234,616, 5,130,045 and 5,130,044
(all of which relate to alkanoyloxyphenylsulfonates), all of which
are incorporated herein by reference.
[0134] 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.
[0135] Brighteners
[0136] Optical brighteners, also referred to as fluorescent
whitening agents or FWA's, have long been used to impart whitening
to fabrics during the laundering process. These fluorescent
materials act by absorbing ultraviolet wavelength light and
emitting visible light, generally in the color blue wavelength
ranges. The FWA's settle out or deposit onto fabrics during the
washing 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 FWA's or
brighteners are useful for improving the appearance of fabrics,
which have become dingy through repeated soilings and washings.
Preferred FWA's 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--or
DASC--brighteners. These compounds have the general formula 1
[0137] 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-hy-
droxyethyl-N-methylamino)-1,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfona-
te (sold as Tinopal 5BM); disodium
4,4'-bis-((4-anilino-6-(bis(2-hydroxyet-
hyl)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). Examples of suitable FWA's
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.
[0138] Also preferred are cationic, nonionic, and amphoteric FWA's,
such as those cited in U.S. Pat. Nos. 4,433,975, 4,432,886,
4,384,121, all to Meyer and 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, 11.sup.th 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 Zelger 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.
[0139] 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.
[0140] In selecting the various components for the fabric treatment
composition, 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 that do 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.
[0141] Formulation
[0142] The compositions of the present invention 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 invention, an article of
manufacture may be provided that comprises the inventive
composition 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 delays release of the composition. A suitable film coating or
encapsulate may also be employed with either a liquid or solid form
to provide for delayed release of the composition.
[0143] 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.
[0144] 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.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 head 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.
[0145] Preferably, the aerosol-dispensing device of the present
invention 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 present invention to be dispensed in
the form of a spray of very fine, or finely divided, particles or
droplets. The aerosol dispenser utilizes a pressurized sealed
container from which the composition of the present invention 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 isobutane,
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.
[0146] 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 present invention 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 present invention 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.
[0147] Compositions of the present invention 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.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 present invention at a point in time at
which it will be most effective.
[0148] Compositions of the present invention 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. 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 inventive
composition 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 liquor, depending upon which cycle of
the wash the sachet containing the composition is added.
[0149] 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.
[0150] In another embodiment, a water-insoluble sachet may be
employed to hold the fabric treatment 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/m.sup.2. 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 fibres, regenerated cellulosic
fibres, 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.
[0151] Also within the scope of the present invention 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 present invention 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 present invention and a second zone may comprises a carrier
comprising, but not limited to, adjunct materials described herein
as suitable optional additives.
[0152] Methodology
[0153] As further described herein, fabric treatment compositions
of the present invention (with or without at least one zeta
potential modifier) can be deposited onto fabrics by a number of
methods. Regardless of the technique employed, the critical feature
is that the fluoropolymers and hydrophobic agents become deposited
on the fabric surface. Subsequent heating above ambient
temperatures but below 100.degree. C. reversibly cures the
materials onto the fabric. However, excessive heating above
100.degree. C. is to be avoided as the coating is then bound too
tenaciously, leading to decreased overall performance. Without
being bound by theory, it is believed that the coating should be
reversibly bound to effect release of stains and soils in the
subsequent wash. One particularly preferred technique for consumers
is to use the composition during laundering of soiled garments in
conventional washing machines that have between a 25 to 90 liter
capacity when filled. The machines typically have a fill/wash cycle
of about 12 to 18 minutes duration (the initial volume of water is
added), a rinse cycle of about 2 to 5 minutes duration (sufficient
water added to disperse the soil and detergent and other laundry
additives, and a spin cycle of about 10 to 20 minutes duration.
Between the wash, rinse and spin cycles the introduced water is
drained. These selected cycles are to be distinguished from the
overall wash cycle itself, which encompasses all these sequential
cycles or steps in the complete wash process provided by a
conventional automatic washing machine.
[0154] When detergent is used, the inventive fabric treatment
composition preferably includes at least one zeta potential
modifier. In one variation, a composition containing the
fluoropolymer, hydrophobic agent, and zeta potential modifier is
added anytime during the wash, e.g., along with the detergent at
the washing cycle. Alternatively, a composition containing the
fluoropolymer and hydrophobic agent, but not a zeta potential
modifier, is added with the detergent at the wash stage and
thereafter, the zeta potential modifier, which is present in
commercial fabric softener which contains cationic surfactant,
becomes incorporated when the fabric softener is added to the
washing machine during the rinse cycle.
[0155] An effective amount of the composition of the present
invention can be sprayed or applied directly onto fabrics,
particularly clothing. When the composition is sprayed or applied
directly onto fabric, an effective amount can be deposited onto the
fabric without causing saturation of the fabric, typically from
about 10% to about 85%, preferably from about 15% to about 65%, and
more preferably from about 20% to about 50%, by 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%,
preferably from about 0.2% to about 3%, and more preferably from
about 0.3% to about 2% of the fabric. The treated fabric can then
be tumble-dried in a standard clothes dryer and/or be ironed at the
normal ironing temperature to effect curing. Alternatively, the
treated fabric can be allowed to dry at ambient temperature, and
the curing effected by a later heating step supplied by
tumble-drying in a standard clothes dryer and/or ironed at the
normal ironing temperature to effect curing. Alternatively, the
treated fabric can be subjected to radiant energy, such as from the
sun or infrared generating heat source, or to microwave energy,
such as from a microwave dryer or microwave generating device, to
effect curing of the applied 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 optionally
conducted in separate steps, providing that the heating step is
performed subsequent to the drying step if conducted
separately.
[0156] 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. When used
in such a revitalizing device, 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 revitalizing solution in order
to effect treatment by use of composition of the present invention.
An effective amount of the composition can be automatically metered
and aerosolized to effect its deposition onto the clothes contained
within the revitalizing device. A drying step subsequently
performed by the revitalizing device equipped with an air blower
and source of heat, or a source of heated air automatically follows
the deposition step in order to complete treatment of the fabrics
treated therein by the composition.
[0157] 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
present invention 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 fresh water and/or wash the
soaked fabrics, followed by tumble-drying at less than 100.degree.
C. or optionally ironing at appropriate heat settings.
[0158] 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.
[0159] Another embodiment of this invention is to treat a non-woven
and/or woven carrier article with the inventive composition. A
further embodiment of this method 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.
[0160] 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 composition 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.
[0161] Following the first use of the composition of the present
invention to treat a fabric, subsequent treatment of the fabric may
be repeated in similar fashion by any or all means described above
using amounts of the composition at the preferred first treatment
level, or more preferably at a lower level, or maintenance level,
sufficient to replenish material on the fabric that may be lost due
to wear or subsequent washing after the first treatment. In
general, the level of the present composition required to
effectively treat a fabric in order to obtain desirable benefits
are greater for the first treatment using previously untreated
fabrics than for fabrics that have previously been treated using
the present composition. Thus, subsequent, repeated treatments may
generally require significantly lower amounts of the composition to
effectively replenish material present on the fabric and to
maintain the desirable benefits obtained with the first treatment
performed. Subsequent, or maintenance, levels of the composition to
be used to maintain the desired benefits exhibited by previously
treated fabric is 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.
[0162] 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 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
present invention (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 inventive 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.
[0163] In still a further aspect of the invention, textiles treated
with the compositions of the present invention, particularly
delicate fabrics, fabrics composed of natural fibers including, but
not limited to 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 present
invention 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 present invention 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
present invention 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.
[0164] 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 present invention. Drying the fabric at
a temperature above 45.degree. C. is preferred.
[0165] The inventive composition can be applied by any of the above
methods. In one method of use, the composition can be first applied
at a high effective amount to give untreated fabrics the beneficial
properties. Subsequent treatment of the same fabrics can be applied
at a lower maintenance effective amount. The compositions and
articles of the present invention 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.
[0166] 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.
[0167] The compositions of the present invention 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.
[0168] 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.
The especially preferred levels of the inventive composition 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
inventive composition 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
inventive composition might be 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.
[0169] The present invention 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.
[0170] The present invention also relates to a method for treating
fabric in the drying step, comprising an effective amount of the
fabric protecting actives of the present invention 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.
[0171] 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.
[0172] The present invention 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
[0173] Experiments were conducted to demonstrate the superior
effects of the fabric treatment composition and various application
techniques that can be employed to effectively deliver the
treatment composition. The data as presented in Tables 1-14 were
based on compositions that did not include addition of a zeta
potential modifier. Subsequent data in these examples were based on
compositions with at least one zeta potential modifier. As is
apparent, compositions with at least one zeta potential modifier
were also very effective in imparting the beneficial protective
properties to the fabrics treated.
[0174] The examples in Table 1 illustrate compositions of the
invention for addition to the laundry. The concentrations are based
on the addition of 200 g of the inventive compositions to 2.72 kg
of fabric in 69 liters of water in the wash or rinse cycle.
Appropriate levels in compositions can be determined for other
addition amounts, other levels of fabric, or other wash or rinse
volume levels. Examples are given in weight percent as is, i.e.,
weight percent of the materials as commercially supplied as
components in the final composition to achieve 100% by weight.
1 TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 ZONYL 6700.sup.a 34 5 63 27
4 50 20 3 37 15 NALAN GN.sup.b 34 63 5 27 50 4 20 37 3 15 Balance
water and q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.
minors.sup.c .sup.aCationic fluoropolymer emulsion from DuPont
Chemicals (20 weight % active) .sup.bCationic paraffin wax emulsion
from DuPont Chemicals (15 weight % active, melting point less than
75.degree. C.) .sup.cMinors include surfactants, fragrance,
fragrance extenders, preservatives, preservatives, antistatic
agents, dyes and colorants, viscosity control agents, antioxidants,
antifoaming agents, emulsifiers, brighteners, opacifiers,
freeze-thaw control agents, shrinkage control agents, and mixtures
thereof. (q.s. denotes "quantity sufficient" to achieve 100% by
weight of the finished composition in each example noted.)
[0175] For fabrics that already exhibit some oil or water
repellency, such as those treated with the above compositions, or
polyester, polyester/cotton, or other fabrics that are more
hydrophobic than cotton, a reduced level of the inventive
compositions can be used. The examples in Table 2 illustrate
maintenance compositions of the invention for addition to the
laundry. The concentrations are based on the addition 200 g of the
inventive compositions to 2.72 kg of fabric in 69 liters of water
in the wash or rinse cycle.
2 TABLE 2 Example 11 12 13 14 15 16 17 18 19 20 ZONYL 6700 7 3 11 5
1 9 4 1 7 .5 NALAN GN 7 11 3 5 9 1 4 7 1 .5 Balance water q.s. q.s.
q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. and minors
[0176] The examples in Table 3 illustrate compositions of the
invention with additional actives. The concentrations are based on
the addition of 200 g of the compositions to 2.72 kg of fabric in
69 liters of water in the wash or rinse cycle, or applying by one
of the other suggested methods, such as spray application, presoak,
or treatment in the dryer.
3 TABLE 3 Example 21 22 23 24 25 26 27 28 29 30 ZONYL 6700 10 10 10
10 10 10 3 5 5 20 Nalan GN 30 30 30 30 30 30 37 10 10 5 SURFONIC
L12-2.6.sup.d 5 TRITON N101.sup.e 10 Amphoterge K2.sup.f 5 ADOGEN
442.sup.g 10 AMMONYX LO.sup.h 2 Magnesium chloride 2 Sodium
Thiosulfate 0.6 Dibutylated 0.1 hydroxytoluene.sup.i Balance water
and q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. minors
.sup.dAlcohol ethoxylate, nonionic surfactant from Huntsman.
.sup.eAlcohol ethoxylate, nonionic surfactant from Union Carbide
.sup.fImidazoline amphoteric surfactant from Lonza .sup.gDimethyl
dehydrogenated tallow ammonium chloride, cationic surfactant from
Goldschmidt Chemical. .sup.hDimethyl amine oxide from Huntsman from
Lonza. .sup.iAntioxidant from UOP Inc.
[0177] The examples in Table 4 illustrate compositions of the
invention with alternative fluoropolymers and hydrophobic
agents.
4 TABLE 4 31 32 33 34 35 36 ZONYL 6700.sup.j 0.5 1.0 ZONYL
8300.sup.k 0.2 0.2 ZONYL NWG.sup.l 1.5 2.0 MICHEM EMULSION 1.0
723.sup.m MICHEM EMULSION 0.5 0.2 743.sup.n FREEPEL 1225.sup.o 2.0
Balance water and minors q.s. q.s. q.s. q.s. q.s. q.s.
.sup.jCationic fluoropolymer emulsion from DuPont Chemicals (20
weight % active) .sup.kFluoropolymer emulsion from DuPont Chemicals
.sup.lFluoropolymer emulsion from DuPont Chemicals
.sup.mNon-cationic microcrystalline wax emulsion from Michelman
.sup.nNon-cationic microcrystalline wax emulsion from Michelman
.sup.oCationic microcrystalline wax emulsion from Noveon
[0178] Contact Angle Measurements
[0179] Contact angles above 80 degrees that persist over relatively
significant contact times are good indicators of effective water or
oil repellency. Cotton weave swatches (also referred to as "flags")
were treated with different concentrations of ZONYL 6700 for 12 min
in 1500 grams of water at 25.degree. C. in the Terg-O-Tometer, then
squeezed and dried in the dryer for 40 min at 150.degree. F.
(65.5.degree. C.). The 5% treatment of fluoropolymer solution is 5%
as is based on the weight of cotton fabric in the treatment. This
corresponds to a rinse cycle concentration of 1.23 grams per liter
of rinse water. The contact angle was measured by putting a drop of
water on the flags and measuring after 30 sec and 2 min. The
results shown in Table 5 indicate that the fluoropolymer, used by
itself even at high levels, is not effective at either water or oil
repellency.
5 TABLE 5 Composition Contact Angle (water/oil) (weight %) 30 sec 2
min 0% ZONYL 6700 0/0 0/0 1% ZONYL 6700 0/0 0/0 2.5% ZONYL 6700 0/0
0/0 5% ZONYL 6700 0/0 0/0
[0180] Cotton weave swatches were then washed with different
concentrations of NALAN GN, an emulsified paraffin wax. The
swatches were treated for 12 min. at 25.degree. C. in a
Terg-O-Tometer, then squeezed to remove excess solution and dried
in the dryer for 40 min. at 150.degree. F. (65.5.degree. C.). The
5% treatment of hydrophobic agent solution is 5% as is based on the
weight of cotton fabric in the treatment. This corresponds to a
rinse cycle concentration of 1.23 grams per liter of rinse water.
The contact angle was measured by putting a drop of water on the
flags and measuring after 30 sec and 2 min. The results are shown
in Table 6 and indicate that the wax emulsion, by itself even at
high concentrations, is not effective at oil repellency.
6 TABLE 6 Composition Contact angle (water/oil) (weight %) 30 sec 2
min 0% NALAN GN 0/0 0/0 1.0% NALAN GN 0/0 0/0 2.5% NALAN GN 75/0
55/0 5% NALAN GN 100/0 76/0
[0181] Cotton weave swatches were treated at a low 1.0 weight %
concentration of ZONYL 6991 with different concentrations of
magnesium chloride for 12 min at 25.degree. C. in a Terg-O-Tometer,
then squeezed to remove excess solution and dried in the dryer for
40 min at 150.degree. F. (65.5.degree. C.). The 1.0 weight %
treatment of ZONYL 6991 is 1.0 weight % as is based on the weight
of cotton fabric in the treatment. This corresponds to a rinse
cycle concentration of 0.25 grams per liter of rinse water. The
contact angle was measured by putting a drop of water on the flags
and measuring after 30 sec and 2 min. The results shown in Table 7
indicate that the fluoropolymer with high electrolyte concentration
exhibits increased water repellency versus ZONYL 6991 used alone
for treatment.
7 TABLE 7 Contact angle Composition (water) (weight %) 60 sec 1%
ZONYL 6991.sup.a 0 0% MgCl.sub.2 1% ZONYL 6991 50 5% MgCl.sub.2 1%
ZONYL 6991 100 20% MgCl.sub.2 .sup.aCationic fluoropolymer emulsion
from DuPont Chemicals
[0182] Cotton weave swatches were treated with different ratios of
ZONYL 6700 and NALAN GN for 12 min at 25.degree. C. in a
Terg-O-Tometer, then squeezed to remove excess solution, rinsed and
dried in the dryer for 40 min at 150.degree. F. (65.5.degree. C.).
The contact angles with both water and oil droplets were measured
after 30 seconds. The results shown in Table 8 indicate that
approximately a 4:1 to 1:4 ratio of fluoropolymer to hydrophobic
agent is desirable for both optimum oil and water repellency.
8 TABLE 8 37 38 39 40 41 42 ZONYL 6700 0.5% 2% 2.5% 3% 3.75% 4.5%
NALAN GN 4.5% 3% 2.5% 2% 1.25% 0.5% Contact Angle (water) 117 110
112 110 121 52 30 seconds Contact Angle (oil) 35 103 111 100 112 0
30 seconds
[0183] The examples in Table 9 show that using the inventive
composition in the rinse is surprisingly superior to pretreatment
with surface finishing treatments employing fluoropolymers that are
commercially available for consumer usage. The pretreatment product
locks in stains already on the fabric, while the inventive
composition, in contrast, does not hinder removal of existing
stains, but surprisingly, further acts to improve stain removal. A
variety of stains were applied to untreated fabrics and allowed to
age for at least 7 days to mimic the typical consumer delay before
washing soiled laundry. The garments were then treated per label
instructions using either a commercial consumer surface finishing
treatment (SCOTCHGARD) or rinsed in a 5% loading of ZONYL 6991
(Inventive treatment). In both cases, fabric treatment was
performed at solution temperatures of 25.degree. C. for 12 minutes,
followed by squeezing to remove excess solution and fabrics were
then dried in a dryer for 40 minutes at 150.degree. F.
(65.5.degree. C.). The stained/treated garments were then washed
and rinsed in a commercially available residential washer using a
label recommended level of LIQUID TIDE detergent (produced by the
Procter & Gamble Company) and dried in a dryer for 40 minutes.
Stain removal was judged visually using a 5 point scale where
comparing treated and not-treated stained and washed garments where
numeric scores were assigned based on the following descriptive
scale: 1--Much worse than untreated, 2--Worse than untreated,
3--Equal to untreated, 4--Better than untreated, 5--Much better
than untreated.
9 TABLE 9 Inventive Stain Type Untreated Treatment SCOTCHGARD Grass
Basis 4 1 Coffee Basis 4 1 Clay Basis 3 2 Salad Dressing Basis 3
3
[0184] An experiment was conducted to compare the breathability of
fabrics treated with commercially available anti-stain treatments
with that of the invention. The porosity of the fabric to liquid
water was used as a judge of breathability. The porosity was
determined by the ability of the fabric to support a measured
weight of a column of water. SCOTCHGARD Protector (3M Company) was
used as a representative of commercially available anti-stain
treatments, and the SCOTCHGARD treatment was used per the label
instructions. 100% cotton weave fabrics were prepared with a 5%
wash added loading of the ZONYL 6991 (Inventive treatment,
25.degree. C. wash, hand wrung, dried for 40 minutes in a dryer at
150.degree. F. (65.5.degree. C.)). The sample fabrics were
stretched over a 1 in. (2.54 cm) internal diameter plastic tube and
a piece of facial tissue was placed on top of the fabric (facing
away from the tube). The fabric and tissue were secured to the tube
in a watertight fashion by use of a plastic tie. The tube was
oriented so that the fabric faced downward. Water was then
gradually added to the tube until the tissue showed signs of
wetting. The measured quantity of water added before wetting of the
tissue was noted and was recorded as the corresponding porosity or
breathability value. The results are set forth in Table 10.
10 TABLE 10 Breathability (grams Treatment Detail of water in
column) SCOTCHGARD treated side facing 0.44 away from the water
column SCOTCHGARD treated side facing 16.04 toward the water column
Inventive Treatment 0.12
[0185] The examples in Table 11 demonstrate the preferred transient
durability of the inventive treatment, as measured by the slow loss
of protection benefit imparted to the treated fabrics, illustrated
by the slow loss of water repellency after multiple washes using a
commercial detergent, but without subsequent treatment using the
inventive compositions. Thus in actual use, fabrics treated using
the inventive compositions will resist the build up of the fabric
protective film that results from treatment which may otherwise
compromise the appearance due to excessive coating and
discoloration of the treated fabrics, or which may otherwise
compromise the softness and handfeel of the treated fabrics after
multiple treatments. Accordingly, fabrics treated using the
inventive compositions will eventually lose their fabric protective
benefits unless subsequent treatments with the inventive
composition are repeated at some regular frequency. Advantageously,
subsequent treatments may be employed using lower levels of the
inventive composition to maintain the full protective benefits
provided to treated fabrics without the undesirable build-up of the
treatment on said fabrics. The swatches were treated with a 5%
loading of the invention for 12 min at 25.degree. C. in the
Terg-O-Tometer, then squeezed to remove excess solution and dried
in the dryer for 40 min at 150.degree. F. (65.5.degree. C.). The
commercially available pants were purchased from Spiegel precoated
with TEFLON brand stain resistant coating. Both garments were
washed in a residential washing machine with label recommended
doses of LIQUID TIDE and subsequently dried in a residential
dryer.
11 TABLE 11 Contact angle using water after 30 sec Number of wash
cycles Inventive Treatment TEFLON treated pants 1 96 117 2 22 112 3
0 110
[0186] Table 12 compares the handfeel of 100% cotton fabrics
treated with the inventive treatment and those treated via a
commercial application of fluoropolymer (SCOTCHGARD). Thirty
respondents were asked to choose the garment with the best
handfeel. The table shows the number of times each garment was
chosen to have the better handfeel in a blind test.
12 TABLE 12 Inventive Commercially Treatment treated garment Chosen
better handfeel 30 0
[0187] In the following examples, the surprising dependence of
adding additional surfactants to the inventive treatment is
demonstrated. These surfactants can be added either directly via
the formulation, or via added detergent.
[0188] Table 13 shows the dependence of adding nonionic surfactants
in addition to the inventive system. The swatches were treated with
a 5% loading of the inventive treatment with various amount of
surfactant added and exhausted for 12 min at 25.degree. C. in the
Terg-O-Tometer, then squeezed to remove excess solution. The
swatches were then rinsed in water for 5 minutes at 25.degree. C.,
squeezed to remove excess solution and dried in the dryer for 40
min at 150.degree. F. (65.5.degree. C.). The table reveals the
contact angle for fabrics exhausted with a combination of the
inventive treatment along with surfactant. It is clearly seen that
at levels of nonionic surfactant equal to that supplied by use of a
commercial detergent, the repellency is negligible, but
surprisingly, there is a critical level at which a fabric
protective benefit is still realized. This indicates that in some
nonionic surfactant systems, such as those employed by commercial
laundry detergents, addition of at least some zeta potential
modifier may be further required in order to provide the optimum
fabric protective benefit. Conversely, this also demonstrates that
the level of use of primarily nonionic surfactant based detergents
may be effectively reduced when used for cleaning clothing
previously treated using the inventive treatment, as lower levels
of the nonionic detergent would be sufficient to effectively clean
treated clothing yet maintain, to some extent, the previously
existing protective benefit carried by the clothing.
13 TABLE 13 43 44 45 ZONYL 6991 0.98 0.98 1.23 (g/l) Non-ionic 0.11
0.22 0.43 surfactant (g/l) Contact angle 100 72 0 water
(initial)
[0189] In another example, it was demonstrated that the inventive
treatment can also tolerate low levels of anionic surfactants. In
Table 14, the swatches were treated with a 5% loading of the
inventive treatment with various amount of surfactant added and
exhausted for 12 min at 25.degree. C. in the Terg-O-Tometer, then
squeezed to remove excess solution and dried in the dryer for 40
min at 150.degree. F. (65.5.degree. C.). The table reveals the
resultant contact angles, demonstrating a surprising critical level
in which the anionic surfactants can be incorporated. Furthermore,
a commercially available laundry detergent was used at 10% and 100%
of the recommended dosage. At full usage levels, no repellency is
observed, however repellency was observed at the reduced level.
14 TABLE 14 46 47 48 49 50 51 52 ZONYL 6991 1.23 1.23 1.23 1.23
1.23 1.23 1.23 (g/l) Anionic 0.026.sup.a 0.065.sup.a 0.16.sup.a
0.65.sup.a surfactant(g/l) FRESH 0.043.sup.b 0.22.sup.b 0.43.sup.b
START Contact angle 82 70 0 0 83 0 0 water (initial) .sup.aMixture
of 77% AEOS and 23% LAS, both anionic surfactants. .sup.bCommercial
laundry detergent from Colgate-Palmolive, containing LAS and
alcohol ethoxylate, 10% recommended level .sup.csee footnote b, 50%
recommended level .sup.dsee footnote b, 100% recommended level
[0190] Surprisingly, the reduction of surfactant levels in the
above examples, though key to the ultimate repellency imparted to
the fabric, does not materially affect the final appearance of the
washed samples relative to fabrics that were washed at full doses
of detergent without the inventive system. Very good cleaning
systems can thus be realized at significantly reduced surfactant
levels, thereby reducing the overall biological challenge to the
environment.
[0191] In the following three sets of experiments, fabric treatment
compositions containing fluoropolymers, hydrophobic agents, and
zeta potential modifiers were tested for their effectiveness in
enhancing water and oil repellency. Although fragrance and colorant
were not added in the compositions tested, these optional
components typically would be included in commercial products at
amounts of about 0.4% and 0.004%, respectively.
[0192] In the first experiments, six compositions each having the
same amounts of fluoropolymers and hydrophobic agents but different
amounts of zeta potential modifier (e.g., cationic surfactant in
the form of a quaternary ammonium compound) were prepared. The
compositions were diluted using water to effective use levels
equivalent to 5% by weight of the undiluted compositions. The zeta
potential of each composition was measured using two instruments,
i.e., from Beckman and Particle Sizing. The compositions were also
applied onto cotton fabrics with a U.S. Testing TERG-O-TOMETER
water bath that was maintained at 70.degree. F. (21.degree. C.) to
which cotton fabric and sufficient amounts of composition to
produce a 5% load by fabric weight was attained. The fabric was
exposed for 3.5 minutes and then dried in a commercial dryer at
150.degree. F. (65.6.degree. C.) for 50 minutes. The contact angles
of water and oil droplets on the dried fabric were initially
measured and measured again 2 minutes later. The results are set
forth in Table 15.
15 TABLE 15 Composition (wt. %) Composition Contact Angle ZONYL
MICHEM ACCOSOFT Parameters Zeta Pot. Zeta Pot. (t = 0-t = 2 min.)
No. 8300(a) 473(b) 550(c) water* pH (mV)** (mV)*** Water Oil 1 34
51 0 balance 3.60 .+-. 0.05 -21.2 -9.1 0--0 0--0 2 34 51 2 balance
3.60 .+-. 0.05 36.5 21.2 116-112 116--116 3 34 51 4 balance 3.60
.+-. 0.05 45.1 27.9 111-103 115--115 4 34 51 6 balance 3.60 .+-.
0.05 51.7 33.6 114-107 118--118 5 34 51 8 balance 3.60 .+-. 0.05
55.5 36.2 95-89 116--116 6 34 51 10 balance 3.60 .+-. 0.05 57.9
36.6 70-63 105--105 (a)fluoropolymer 18% active (b)paraffin 32%
active (c)cationic surfactant 75% active; Methyl bis(tallowamido
ethyl)-2-hydroxyethyl ammonium methyl sulfate *includes acid
addition to adjust composition pH **5% (by wt. of fabric)
equivalent dilution measured by Beckman instrument ***5% (by wt. of
fabric) equivalent dilution measured by Particle Sizing
instrument.
[0193] As is apparent, the formulation containing no zeta potential
modifier provided no repellency enhancement. Optimum repellency
occurred where the level of this particular zeta potential modifier
was between 2-6%; the water repellency decreased when the zeta
potential level reached 8% or higher which suggests that too much
of the zeta potential modifier may have an adverse effect as
well.
[0194] In the second set of experiments, eight identical fabric
treatment compositions containing fluoropolymers, hydrophobic
agents, and zeta potential modifiers were tested for their
effectiveness in enhancing water and oil repellency. They were used
with different types of detergents with and without a softener in a
commercial washing machine. Specifically, cotton fabric was washed
in a commercial washer (69 liter capacity, 6 lb (2.2 kg) ballast,
12 min. wash cycle at 93.degree. F., or 34.degree. C., and 3 min.
rinse cycle at 68.degree. F., or 20.degree. C.) and 140.6 grams of
one of the eight formations were added in the wash water. The
fabric was dried in a drying machine for 50 minutes at 150.degree.
F. (66.degree. C.). A primarily anionic surfactant containing
detergent (LIQUID TIDE from Procter & Gamble Co.), a nonionic
detergent (FRESH START from Colgate-Palmolive Co.), and/or a fabric
softener that contained a cationic surfactant (DOWNY from Procter
& Gamble) were also added as described herein. The contact
angles of water and oil droplets were also measured after the
fabric was dried. The procedures employed and the results are set
forth in Table 16.
16 TABLE 16 Additional Commercial Products Composition (wt %)
Composition Added to Washing Machine Contact Angle-Cotton ZONYL
MICHEM ACCOSOFT parameters Added to Added to (t = 0-t = 2 min.) No.
8300(a) 743(b) 550(c) water* pH Wash Rinse Water Oil 1 37.6 56.4 6
balance 3.60 .+-. 0.05 none Downy** 113-93 113-110 2 37.6 56.4 6
balance 3.60 .+-. 0.05 Downy** none 81-64 110--110 3 37.6 56.4 6
balance 3.60 .+-. 0.05 Fresh Start Downy** 88-44 0--0 4 37.6 56.4 6
balance 3.60 .+-. 0.05 Fresh Start and none 104--104 108-106
Downy** 5 37.6 56.4 6 balance 3.60 .+-. 0.05 Fresh Start none 0--0
0--0 6 37.6 56.4 6 balance 3.60 .+-. 0.05 Liquid Tide Downy** 0--0
0--0 7 37.6 56.4 6 balance 3.60 .+-. 0.05 Liquid Tide and none 36-0
15-0 Downy** 8 37.6 56.4 6 balance 3.60 .+-. 0.05 Liquid Tide none
0--0 0--0 (a)fluoropolymer 18% active (b)paraffin 32% active
(c)cationic surfactant 75% active; methyl bis(tallowamido
ethyl)-2-hydroxyethyl ammonium methyl sulfate *includes acid
addition to adjust composition pH **Downy usage = 30 g/69 L
[0195] As is apparent, detergent free systems (treatments 1 and 2)
yield effective repellency when the fabric softener was added to
either the wash or the rinse cycle. The presence of nonionic
detergent yielded effective repellency when it is added to the
washing cycle along with the softener as shown in treatment 4.
Finally, the presence of predominately anionic detergent appears to
disrupt the efficacy of treatment, with the softener added to
either the wash (treatment 7) or rinse (treatment 6).
[0196] Finally, in the third set of experiments, three different
treatment compositions were formulated and their effectiveness in
enhancing water and oil repellency was tested in conjunction with
either a liquid or dry anionic detergent (LIQUID TIDE or TIDE,
respectively, from Procter & Gamble). Each composition had
different amounts of zeta potential modifier. The fabrics tested in
each case included a combination comprising 70% cotton material and
30% of a cotton/synthetic blend, which is designated p/c. The
detergent, when employed, was added in the wash cycle. The
treatment composition was added in the rinse cycle and, in one
case, fabric softener, which included cationic surfactants, was
also added in the rinse cycle.
[0197] It was expected that a small amount of detergent would
adhere to the damp fabric following the wash cycle so that the
residual detergent would re-dissolve into the water at the
beginning of the rinse cycle. The results are presented in Table
17.
17 TABLE 17 Commercial Products Water Contact Composition (wt. %)
Composition Added to Wash (Inventive Angle Oil Contact Angle ZONYL
MICHEM ACCOSOFT parameters Treatment weight) (t = 0-t = 2 min.) (t
= 0-t = 2 min.) No. 18300(a) 743(b) 550(c) water* PH wash Rinse
cotton p/c cotton p/c 1 34 51 6 balance 3.60 .+-. 0.05 none none
(219 g) 88-78 97-85 100-96 100-94 Liquid Tide none (219 g) 69-45
0--0 0--0 0--0 Liquid Tide Downy (219 g) 99-78 102-90 112--112
110--110 2 34 51 10.6 balance 3.60 .+-. 0.05 none none (219 g)
109-89 114-106 113-110 115-110 Liquid Tide none (219 g) 108-87
100-93 106--106 117-113 Dry Tide none (219 g) 103-87 118-106
118-114 114-113 Liquid Tide none (219 g) 118-98 112-98 111-104
112-108 Liquid Tide none (177 g) 109-84 112-86 102-98 107-106
Liquid Tide none (118 g) 0--0 0--0 0--0 0--0 3 34 51 13.1 balance
3.60 .+-. 0.05 Liquid Tide none (219 g) 104-94 110-98 108-102
121-118 Liquid Tide none (177 g) 100-85 113--103 110-108 111-108
Liquid Tide none (118 g) 72-0 102-0 85-55 87-73 (a)fluoropolymer
18% active (b)paraffin 32% active (c)cationic surfactant 75%
active; methyl bis(tallowamido ethyl)-2-hydroxyethyl ammonium
methyl sulfate *includes acid addition to adjust composition pH
[0198] As is apparent, the 6% zeta potential modifier formulation
(no. 1) exhibited good repellency performance in the absence of
wash added detergent but it exhibited poor repellency performance
when detergent was added in the wash. However, the same formulation
exhibited good repellency performance when a fabric softener was
added to the rinse cycle to increase the amount of cationic
surfactant, i.e., zeta potential modifier. In addition, increasing
the level of the zeta potential modifier (i.e., ACCOSOFT 550) to
10.6% in formulation no. 2 improved repellency performance when
detergent was present in the wash cycle but, even with the increase
in zeta potential modifier, repellency performance actually
decreased at the lower dose (i.e., 118 g) of treatment composition
2 when detergent was present in the wash. This suggests that the
amount of zeta potential modifier was not enough to counteract the
adverse effects of the anionic surfactants in the detergent.
However, when the amount of zeta potential modifier was increased
to 13.1%, there was an improvement in repellency performance even
at the lower dose (i.e., 118 g) of treatment composition 3 when
detergent was present.
[0199] Although only preferred embodiments of the invention are
specifically disclosed and described above, it will be appreciated
that many modifications and variations of the present invention are
possible in light of the above teachings and within the purview of
the appended claims without departing from the spirit and intended
scope of the invention.
* * * * *