U.S. patent application number 13/934855 was filed with the patent office on 2013-11-07 for non-fluoropolymer surface protection composition.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to Richard BECKER, James Lee DANZIGER, Markus MERGET, Stephen Thomas MURPHY, David S. SALLOUM, Xiaoru Jenny WANG, Franz X. WIMMER.
Application Number | 20130296218 13/934855 |
Document ID | / |
Family ID | 44736068 |
Filed Date | 2013-11-07 |
United States Patent
Application |
20130296218 |
Kind Code |
A1 |
WANG; Xiaoru Jenny ; et
al. |
November 7, 2013 |
NON-FLUOROPOLYMER SURFACE PROTECTION COMPOSITION
Abstract
The present invention encompasses a surface treatment
composition which comprises a polyorganosiloxane fluid-silicone
resin mixture and a carrier. The polyorganosiloxane fluid-silicone
resin mixture comprises about 50% to about 99.99% by weight of one
or more polyorganosiloxane fluid compounds, at least 0.01% by
weight of one or more silicone resin, and a maximum of 5% by weight
of water.
Inventors: |
WANG; Xiaoru Jenny; (Mason,
OH) ; DANZIGER; James Lee; (Mason, OH) ;
SALLOUM; David S.; (West Chester, OH) ; MURPHY;
Stephen Thomas; (Harrison, OH) ; MERGET; Markus;
(Mehring, DE) ; WIMMER; Franz X.; (Burghausen,
DE) ; BECKER; Richard; (Burghausen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Family ID: |
44736068 |
Appl. No.: |
13/934855 |
Filed: |
July 3, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13237287 |
Sep 20, 2011 |
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13934855 |
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Current U.S.
Class: |
510/400 ;
510/528 |
Current CPC
Class: |
C08G 77/26 20130101;
D06M 15/285 20130101; D06M 2200/11 20130101; D06M 15/11 20130101;
D06M 15/643 20130101; D06M 15/3562 20130101; C08L 83/08 20130101;
C09K 3/18 20130101; C11D 3/3746 20130101; D06M 15/6436 20130101;
C11D 3/3742 20130101; C08L 83/00 20130101; D06M 15/03 20130101;
C08L 83/08 20130101; D06M 15/09 20130101; C09D 183/04 20130101;
C08G 77/04 20130101; D06M 2200/12 20130101 |
Class at
Publication: |
510/400 ;
510/528 |
International
Class: |
C09D 183/04 20060101
C09D183/04; C11D 3/37 20060101 C11D003/37; D06M 15/643 20060101
D06M015/643 |
Claims
1. A surface treatment composition which comprises: A.) a
polyorganosiloxane-silicone resin mixture comprising: i.) from
about 50% to about 99.99% by weight of one or more
polyorganosiloxane fluid compounds, wherein each polyorganosiloxane
fluid compound contains at least about 80 mol % of units selected
from the group consisting of units of the general formulae Ia, Ib,
II and III: R.sup.1.sub.2SiO.sub.(2/2) (Ia),
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(2/2) (Ib),
R.sup.3.sub.3SiO.sub.(1/2) (II), R.sup.3.sub.2R.sup.4SiO.sub.(1/2)
(III), in which: a has the value 0, 1 or 2, b has the value 1 or 2,
and the sum of a and b is equal to 2; R.sup.1 means monovalent
hydrocarbon residues with 1 to 40 carbon atoms, optionally
substituted with halogens; R.sup.2 means either: a) aminoalkyl
residues of the general formula IV: --R.sup.5--NR.sup.6R.sup.7
(IV), wherein: R.sup.5 means divalent hydrocarbon residues with 1
to 40 carbon atoms, R.sup.6 means monovalent hydrocarbon residues
with 1 to 40 carbon atoms, H, hydroxymethyl or alkanoyl residues,
and R.sup.7 means a residue of the general formula V
--(R.sup.8--NR.sup.6).sub.xR.sup.6 (V), wherein: x has the value 0
or an integer value from 1 to 40, and R.sup.8 means a divalent
residue of the general formula VI --(CR.sup.9.sub.2--).sub.y--
(VI), .degree.wherein: .degree.y has an integer value from 1 to 6,
and .degree.R.sup.9 means H or monovalent hydrocarbon residues with
1 to 40 carbon atoms, or b) aminoalkyl residues of the general
formula IV wherein R.sup.6 and R.sup.7 together with the N atom
forms a cyclic organic residue with 3 to 8 --CH.sub.2-- units, and
where nonadjacent --CH.sub.2-- units can be replaced by units that
are chosen from --C(.dbd.O)--, --NH--, --O--, and --S--, R.sup.3
means monovalent hydrocarbon residues with 1 to 40 carbon atoms
optionally substituted with halogens, R.sup.4 means the residues
--OR or --OH, wherein R means monovalent hydrocarbon residues with
1 to 40 carbon atoms, optionally substituted with halogens,
wherein: the average ratio of the sum of units of formulae Ia and
Ib to the sum of units of formulae II and III within the one or
more polyorganosiloxane fluid compounds ranges from about 0.5 to
about 500, the average ratio of units of formula II to the units of
formula III within the one or more polyorganosiloxane fluid
compounds ranges from about 1.86 to about 100, and the one or more
polyorganosiloxane fluid compound have an average amine number of
at least about 0.01 meq/g of polyorganosiloxane fluid compounds;
ii.) at least about 0.01% by weight of one or more silicone resins,
each of which contain at least about 80 mol % of units selected
from the group consisting of units of the general formulas VII,
VIII, IX and X R.sup.10.sub.3SiO.sub.1/2 (VII),
R.sup.10.sub.2SiO.sub.2/2 (VIII), R.sup.10SiO.sub.3/2 (IX),
SiO.sub.4/2 (X), in which: R.sup.10 means H, --OR, --OH residues,
or monovalent hydrocarbon residues with 1 to 40 carbon atoms,
optionally substituted with halogens, and at least about 20 mol %
of the units are selected from the group consisting of units of the
general formulas IX and X, and a maximum of about 10 wt % of the
R.sup.10 residues are --OR and --OH residues; and iii) a maximum of
about 5% by weight water; and B) a carrier.
2. A surface treatment composition according to claim 1, wherein
the surface treatment composition is selected from the group
consisting of laundry spray composition, laundry rinse additive
composition, liquid laundry detergent compositions, solid laundry
detergent compositions, hard surface cleaning compositions, liquid
hand dishwashing compositions, solid automatic dishwashing
compositions, liquid automatic dishwashing, tablet form automatic
dishwashing compositions and laundry detergent compositions and
unit dose form automatic dishwashing compositions and laundry
detergent compositions contained in a water-soluble pouch.
3. A surface treatment composition according to claim 1, wherein
the composition further comprises a perfume.
4. A surface treatment composition according to claim 1, wherein
the composition further comprises a dye transfer inhibitor.
5. A surface treatment composition according to claim 1, further
comprising a surfactant system.
6. A surface treatment composition according to claim 5 where the
surfactant system comprises C.sub.10-C.sub.16 alkyl benzene
sulfonates.
7. A surface treatment composition according to claim 5, wherein
the surfactant system comprises C.sub.8-C.sub.18 linear alkyl
sulfonate surfactant.
8. A surface treatment composition according to claim 6, wherein
the surfactant system further comprises one or more co-surfactants
selected from the group consisting of nonionic surfactants,
cationic surfactants, anionic surfactants and mixtures thereof.
9. A surface treatment composition according to claim 1, wherein
the composition further comprises one or more cleaning adjunct
additives.
10. A surface treatment implement comprising a nonwoven substrate
and the surface treatment composition according to claim 1.
11. A surface treatment composition according to claim 1, wherein
the composition comprises from about 0.001% to about 95% by weight
of the composition, of the polyorganosiloxane-silicone resin
mixture.
12. A surface treatment composition according to claim 1, wherein
the silicone resin of the polyorganosiloxane-silicone resin mixture
is an MQ resin which contain at least about 80 mol % of units
selected from the group consisting of unit of the formula VII and
X, and the average ratio of the units of formula VII to the units
of formula X ranges from about 0.25 to about 4.0.
13. A surface treatment composition according to claim 1, wherein
the polyorganosiloxane fluid compound of the
polyorganosiloxane-silicone resin mixture contains at least about
95% of units selected from the group consisting of general formulae
I, II, and III.
14. A surface treatment composition according to claim 13, wherein
the monovalent hydrocarbon residues R, R.sup.1, R.sup.3, R.sup.6,
R.sup.9 and R.sup.10 are alkyl residues with 1 to 6 carbon atoms or
phenyl residues.
15. A surface treatment composition according to claim 13, wherein
the residues R.sup.2 are chosen from the group consisting of
--CH.sub.2NR.sup.6R.sup.7, --(CH.sub.2).sub.3NR.sup.6R.sup.7, and
--(CH.sub.2).sub.3N(R.sup.6)(CH.sub.2).sub.2N(R.sup.6).sub.2.
16. A surface treatment composition according to claim 1, wherein
the viscosity of the one or more polyorganosiloxane fluid compound
is from about 10 mPas to about 10,000 mPas at 25.degree. C.
17. A surface treatment composition according to claim 1, wherein
the polyorganosiloxane-silicone resin mixture comprises from about
5 to about 50 parts by weight MQ silicone resins.
18. A surface treatment composition according to claim 1, wherein
the polyorganosiloxane-silicone resin mixture comprises a maximum
of about 2 parts by weight water.
19. A surface treatment composition according to claim 1, wherein
the polyorganosiloxane-silicone resin mixture further comprises a
solvent which is selected from the group consisting of
monoalcohols, polyalcohols, ethers of monoalcohols, ethers of
polyalcohols, and mixtures thereof.
20. A surface treatment composition according to claim 1, wherein
the polyorganosiloxane-silicone resin mixture has a viscosity of
from about 100 to about 10,000 mPas at 25.degree. C.20.
21. A surface treatment composition according to claim 1, wherein
the average ratio of units of formula II to the units of formulas
III within the one or more polyorganosiloxane fluid compounds
ranges from about 7 to about 99.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to compositions that may be
used to protect surfaces from being stained. In particular, the
compositions of the present invention are used to protect fabric
from being stained.
BACKGROUND OF THE INVENTION
[0002] Numerous attempts have been made to develop a treatment
composition that provides protection of surfaces by repelling water
and oil based soils from the surface. Fluoropolymers, such as those
used in Scotchguard.RTM. from 3M, have become well established as
stain repellant molecules. However, fluoropolymers are not
preferred due to environmental, and health and safety concerns,
such as potential and possibility of persistent bioaccumulation and
toxicity.
[0003] The combination of polyorganosiloxane fluids and silicone
resins in attempts to treat hard or soft surfaces are also known.
See WO 2007/065067, WO 2006/097207, WO 2006/097227, and EP 1057924
as examples. U.S. Patent Application Publication US 2006/0041026,
by Mahr et al. of Wacker-Chemie GmbH, Munich, Germany discloses
solvent based compositions comprising polydimethylsiloxane fluids
which deliver water-repellant benefits on a wide range of
substrates.
[0004] Unfortunately, to date, the attempts at non-fluoropolymer
continue to demonstrate problems related to low efficiency,
difficult to achieve the desired benefits at affordable cost and
preferred format; challenging to obtain stable products without
significant sacrifices on other desired characteristics of the
products. A continued need exists for a non-fluoropolymer
technology that delivers significant water and oily soil repellency
to obtain a stain prevention benefit with high efficiency in a
convenient form.
SUMMARY OF THE INVENTION
[0005] The present invention encompasses a surface treatment
composition which comprises a polyorganosiloxane fluid-silicone
resin mixture and a carrier. The polyorganosiloxane fluid-silicone
resin mixture comprises from about 50% to about 99.9%, by weight of
the mixture, of one or more polyorganosiloxane fluid compounds; at
least 0.01%, by weight of the mixture, of one or more silicone
resins; and a maximum of about 5%, by weight of the mixture, of
water.
[0006] Each of the one or more polyorganosiloxane fluid compounds
contains at least 80 mol % of units selected from the group
consisting of units of the general formulae Ia, Ib, II and III:
R.sup.1.sub.2SiO.sub.(2/2) (Ia),
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(2/2) (Ib),
R.sup.3.sub.3SiO.sub.(1/2) (II),
R.sup.3.sub.2R.sup.4SiO.sub.(1/2) (III),
in which a has the value 0, 1 or 2, b has the value 1 or 2, and the
sum of a and b is equal to 2. R.sup.1 means monovalent hydrocarbon
residues with 1 to 40 carbon atoms, optionally substituted with
halogens. R.sup.2 means either a) aminoalkyl residues of the
general formula IV:
--R.sup.5--NR.sup.6R.sup.7 (IV),
wherein R.sup.5 means divalent hydrocarbon residues with 1 to 40
carbon atoms, R.sup.6 means monovalent hydrocarbon residues with 1
to 40 carbon atoms, H, hydroxymethyl or alkanoyl residues, and
R.sup.7 means a residue of the general formula V
--(R.sup.8--NR.sup.6).sub.xR.sup.6 (V),
wherein x has the value 0 or an integer value from 1 to 40, and
R.sup.8 means a divalent residue of the general formula VI
--(CR.sup.9.sub.2--).sub.y-- (VI),
wherein y has an integer value from 1 to 6, and R.sup.9 means H or
monovalent hydrocarbon residues with 1 to 40 carbon atoms, or b)
aminoalkyl residues of the general formula IV wherein R.sup.6 and
R.sup.7 together with the N atom forms a cyclic organic residue
with 3 to 8 --CH.sub.2-- units, and where nonadjacent --CH.sub.2--
units can be replaced by units that are chosen from --C(.dbd.O)--,
--NH--, --O--, and --S--. R.sup.3 means monovalent hydrocarbon
residues with 1 to 40 carbon atoms optionally substituted with
halogens. R.sup.4 means the residues --OR or --OH, wherein R means
monovalent hydrocarbon residues with 1 to 40 carbon atoms,
optionally substituted with halogens. Additionally, the average
ratio of the sum of the units of formulae Ia and Ib to the sum of
units of formulae II and III within the one or more
polyorganosiloxane fluid compounds ranges from about 0.5 to about
500. The average ratio of units of formula II to the units of
formula III within the one or more polyorganosiloxane fluid
compounds ranges from about 1.86 to about 100. The one or more
polyorganosiloxane fluid compound have an average amine number of
at least about 0.01 meq/g of polyorganosiloxane fluid
compounds.
[0007] Each of the one or more silicone resins of the
polyorganosiloxane-silicone resin mixture contains at least about
80 mol % of units selected from the group consisting of units of
the general formulas VII, VIII, IX and X:
R.sup.10.sub.3SiO.sub.1/2 (VII),
R.sup.10.sub.2SiO.sub.2/2 (VIII),
R.sup.10SiO.sub.3/2 (IX),
SiO.sub.4/2 (X),
in which R.sup.10 means H, --OR or --OH residues or monovalent
hydrocarbon residues with 1 to 40 carbon atoms, optionally
substituted with halogens, at least 20 mol % of the units are
selected from the group consisting of units of the general formulas
IX and X, and a maximum of 10 wt % of the R.sup.10 residues are
--OR and --OH residues.
DETAILED DESCRIPTION OF THE INVENTION
Surface Treatment Composition
[0008] The present invention relates to compositions to be used for
the treatment of surfaces. Certain embodiments of the compositions
provide water and/or oil repellency to the treated surface thereby
reducing the propensity of the treated surface to become stained by
deposited water or oil based soils.
[0009] By "surfaces" it is meant any inanimate surface. These
surfaces may include porous or non-porous, absorptive or
non-absorptive substrates. Surfaces may include, but are not
limited to, celluloses, paper, natural and/or synthetic textiles
fibers and fabrics, imitation leather and leather. Selected
embodiments of the present invention are applied to natural and/or
synthetic textile fibers and fabrics.
[0010] By "treating a surface" it is meant the application of the
composition onto the surface. The application may be performed
directly, such as the spray or wiping the composition onto a hard
surface. The composition may or may not be rinsed off depending on
the desired benefit.
[0011] The present invention also encompasses the treatment of a
fabric as the surface. This can be done either in a "pretreatment
mode", where the composition is applied neat onto the fabric before
the fabrics are washed or rinsed, or a "post-treatment mode", where
the composition is applied neat onto the fabric after the fabric is
washed or rinsed. The treatment may be performed in a "soaking
mode", where the fabric is immersed and soaked in a bath of neat or
diluted composition. The treatment may also be performed in a
"through the wash" or "through the rinse" mode where the treatment
composition, as defined herein, is added to the wash cycle or the
rinse cycle of a typical laundry wash machine cycle. When used in
the wash or rinse cycle, the compositions are typically used in a
diluted form. By "diluted form" it is meant that the compositions
may be diluted in the use, preferably with water at a ratio of
water to composition up to 500:1, or from 5:1 to 200:1, or from
10:1 to 80:1.
Polyorganosiloxane-Silicone Resin Mixture
[0012] The present invention encompasses a surface treatment
composition which comprises a polyorganosiloxane-silicone resin
mixture and a carrier. The polyorganosiloxane-silicone resin
mixture comprises between about 50% to about 99.9% by weight of the
mixture, of one or more polyorganosiloxane fluid compounds, at
least about 0.01% by weight of the mixture, of one or more silicone
resins, and a maximum of about 5% by weight of the mixture, of
water. Certain embodiments of the polyorganosiloxane-silicone resin
mixture may comprise between about 75% to about 98% of the
polyorganosiloxane fluid compounds. Other embodiments may comprise
between about 80% to about 90%, or alternatively between about 80%
to about 87% of the polyorganosiloxane fluid compounds.
Additionally, certain embodiments of the
polyorganosiloxane-silicone resin mixture may comprise between
about 0.1% and 50%, or between about 2% and about 30% of the
silicone resins. Other embodiments of the mixture may comprise
between about 5% and about 20% of the silicone resins.
[0013] Each of the one or more polyorganosiloxane fluid compounds
contains at least 80 mol % of units selected from the group
consisting of units of the general formulae Ia, Ib, II and III:
R.sup.1.sub.2SiO.sub.(2/2) (Ia),
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(2/2) (Ib),
R.sup.3.sub.3SiO.sub.(1/2) (II),
R.sup.3.sub.2R.sup.4SiO.sub.(1/2) (III),
in which a has the value 0, 1 or 2, b has the value 1 or 2, and the
sum of a and b is equal to 2. R.sup.1 means monovalent hydrocarbon
residues with 1 to 40 carbon atoms, optionally substituted with
halogens. R.sup.2 means either a) aminoalkyl residues of the
general formula IV:
--R.sup.5--NR.sup.6R.sup.7 (IV),
wherein R.sup.5 means divalent hydrocarbon residues with 1 to 40
carbon atoms, R.sup.6 means monovalent hydrocarbon residues with 1
to 40 carbon atoms, H, hydroxymethyl or alkanoyl residues, and
R.sup.7 means a residue of the general formula V
--(R.sup.8--NR.sup.6).sub.xR.sup.6 (V),
wherein x has the value 0 or an integer value from 1 to 40, and
R.sup.8 means a divalent residue of the general formula VI
--(CR.sup.9.sub.2--).sub.y-- (VI),
wherein y has an integer value from 1 to 6, and R.sup.9 means H or
monovalent hydrocarbon residues with 1 to 40 carbon atoms, or b)
aminoalkyl residues of the general formula IV wherein R.sup.6 and
R.sup.7 together with the N atom forms a cyclic organic residue
with 3 to 8 --CH.sub.2-- units, and where nonadjacent --CH.sub.2--
units can be replaced by units that are chosen from --C(.dbd.O)--,
--NH--, --O--, and --S--. R.sup.3 means monovalent hydrocarbon
residues with 1 to 40 carbon atoms optionally substituted with
halogens. R.sup.4 means the residues --OR or --OH, wherein R means
monovalent hydrocarbon residues with 1 to 40 carbon atoms,
optionally substituted with halogens.
[0014] Additionally, the average ratio of the sum of units of
formulae Ia and Ib to the sum of units of formulae II and III
within the one or more polyorganosiloxane fluid compounds may range
from about 0.5 to about 500. The average ratio of units of formula
II to the units of formula III within the one or more
polyorganosiloxane fluid compounds may range from about 1.86 to
about 100. The one or more polyorganosiloxane fluid compounds have
an average amine number of at least about 0.01 meq/g of
polyorganosiloxane fluid compounds.
[0015] The monovalent hydrocarbon residues R, R.sup.1, R.sup.3,
R.sup.6, R.sup.9 and R.sup.10 can be halogen-substituted, linear,
cyclic, branched, aromatic, saturated or unsaturated. Some
embodiments of the monovalent hydrocarbon residues R, R.sup.1,
R.sup.3, R.sup.6, R.sup.9 and R.sup.10 have from 1 to 6 carbon
atoms, including alkyl residues and phenyl residues. Certain
embodiments have halogen substituents such as fluorine and/or
chlorine. Monovalent hydrocarbon residues R, R.sup.1, R.sup.3,
R.sup.6, R.sup.9 and R.sup.10 methyl, ethyl and phenyl are useful
in the present compositions.
[0016] The divalent hydrocarbon residues R.sup.5 can be halogen
substituted, linear, cyclic, branched, aromatic, saturated or
unsaturated. The residues R.sup.5 may have from 1 to 10 carbon
atoms. Alkylene residues with 1 to 6 carbon atoms, including
propylene, are especially useful embodiments. If R.sup.5 is
halogenated, the halogen substituents may be fluorine and
chlorine.
[0017] Residues R.sup.6 may be alkyl and/or alkanoyl residues.
Embodiments of R.sup.6 may contain halogen substituents such as
fluorine and chlorine. Embodiments of R.sup.6 which are alkanoyl
residues may have the general formula --C(.dbd.O)OR.sup.11, where
R.sup.11 has the meanings and preferred meanings of R.sup.1
described above. Especially preferred substituents R.sup.6 are
methyl, ethyl, cyclohexyl, acetyl and hydrogen.
[0018] Cyclic organic residues may be formed from the connection of
R.sup.6 and R.sup.7 in the general formula IV together with the
bonded N atom. These cyclic residues include pentacycles and
hexacycles, such as the residues of pyrrolidine, pyrrolidin-2-one,
pyrrolidin-2,4-dione, pyrrolidin-3-one, pyrazol-3-one, oxazolidine,
oxazolidin-2-one, thiazolidine, thiazolidin-2-one, piperidine,
piperazine, piperazin-2,5-dione and morpholine.
[0019] Embodiments of the residues R.sup.2 include
--CH.sub.2NR.sup.6R.sup.7, --(CH.sub.2).sub.3NR.sup.6R.sup.7,
--(CH.sub.2).sub.3N(R.sup.6), and
--(CH.sub.2).sub.2N(R.sup.6).sub.2. Examples include the
aminoethylaminopropyl and cyclohexylaminopropyl residues.
[0020] In certain embodiments of the polyorganosiloxane fluid b has
the value 1 or 2. Some embodiments have the sum of a+b having an
average value of from about 1.9 to about 2.2.
[0021] In some useful embodiments the ratio of a to b is chosen so
that the polyorganosiloxane fluid compounds have an amine number of
at least about 0.1, and some at least 0.3, meq/g polyorganosiloxane
fluid compound. The amine number designates the number of
milliliters of 1N hydrochloric acid which are required for
neutralizing 1 gram of polyorganosiloxane fluid. Some embodiments
have the amine number of the polyorganosiloxane fluid is being a
maximum of about 7. Others have a maximum of about 2.0, and yet
others have a maximum of 1.0 meq/g polyorganosiloxane fluid. x may
have the value of 0 or a value from 1 to 18. Certain embodiments
have x being from 1 to 6. Certain embodiments of the fluid have y
having a value of 1, 2 or 3. The polydimethylsiloxane fluids
contain at least 3, especially at least 10 units of the general
formula I.
[0022] The viscosity of the polyorganosiloxane fluid compounds is
at least about 1 mPas at 25.degree. C., especially at least about
10 mPas, and has a maximum of about 100,000, especially at least
about 10,000 mPas, Certain embodiments of the polyorganosiloxane
fluid compound have a viscosity of at least about 100 mPas and a
maximum of 5,000 mPas, at 25.degree. C.
[0023] The average ratio of the units of the general formula I to
the sum of units II and III may range from about 0.5 to about 500.
In certain embodiments the ratio may be at least about 10,
particularly at least about 50 and range to a maximum of about 250,
particularly a maximum of about 150.
[0024] The ratio of the units II to units III may range from about
1.86 to about 100. Useful embodiments may have this ratio being at
least about 3 and may range to a maximum of about 70. Other
embodiments may have this ration being at least about 6 or at least
about 10, and may range to a maximum of about 50.
[0025] Each of the one or more silicone resins of the
polyorganosiloxane-silicone resin mixture contains at least 80 mol
% of units selected from the group consisting of units of the
general formulas VII, VIII, IX and X
R.sup.10.sub.3SiO.sub.1/2 (VII),
R.sup.10.sub.2SiO.sub.2/2 (VIII),
R.sup.10SiO.sub.3/2 (IX),
SiO.sub.4/2 (X),
in which R.sup.10 means H, --OR or --OH residues or monovalent
hydrocarbon residues with 1 to 40 carbon atoms, optionally
substituted with halogens. Certain useful embodiments of the
polyorganosiloxane-silicone resin mixture may comprise silicone
resins comprising at least about 90%, at least about 95%, or at
least about 98% of units selected from the group consisting of
units of the general formulas VII, VIII, IX and X.
[0026] The silicone resins are preferably MQ silicone resins (MQ)
comprising at least 80 mol % of units, preferably at least 95 mol %
and particularly at least 97 mol % of units of the general formulae
VII and X. The average ratio of units of the general formulae VII
to X is preferably at least 0.25, particularly at least 0.5 and
preferably 4, more preferably at most 1.5.
[0027] The silicone resins (S) are also preferably DT silicone
resins (DT) comprising at least 80 mol % of units, preferably at
least 95 mol % and particularly at least 97 mol % of units of the
general formulae VIII and IX. The average ratio of units of the
general formulae VIII to IX is preferably at least 0.01,
particularly at least 0.02 and preferably at most 3.5, more
preferably at most particularly at most 0.5.
[0028] At least 20 mol % of the units of the silicone resins are
selected from the group consisting of units of the general formulas
IX and X. Other embodiments comprise silicone resins have at least
40% or even 50% of units selected from the group consisting of
units of the general formulas IX and X, A maximum of 10 wt % of the
R.sup.10 residues in the one or more silicone resins are --OR and
--OH residues. In other useful embodiments a maximum of 3% or even
1% may be desired.
[0029] The carrier of the surface treatment composition may be any
known material, generally, but not necessarily, a liquid useful in
delivering the polyorganosiloxane-silicone resin mixture to the
surface which is desired to be treated. The carrier may be as
simple as a single component delivery vehicle such as water or
alcohol which would allow the mixture to be sprayed onto a surface.
Alternatively, the carrier may be complex such as a cleaning
composition such as a laundry detergent where the mixture would be
applied in conjunction with the other beneficial uses of the
complex carrier.
Optional Adjunct Ingredients
[0030] To enhance the performance of the surface treatment
composition of the present invention, additional deposition aid
polymers may be added. As used herein, "deposition aid polymer"
refers to any polymer or combination of polymers that enhance the
deposition of fabric care agent(s) onto fabric during laundering.
Without wishing to be bound by theory, it is believed that in order
to drive the fabric care agent onto the fabric, the net charge of
the deposition polymer is positive in order to overcome the
repulsion between the fabric care agent and the fabric since most
fabrics are comprised of fabric fibers that have a slightly
negative charge in aqueous environments. Examples of fibers
exhibiting a slightly negative charge in water include but are not
limited to cotton, rayon, silk, wool, and the like.
[0031] The deposition aid of the present disclosure may be a
cationic or amphoteric oligomer or polymer or a combination or
blend of cationic and/or amphoteric oligomers and/or polymers that
enhance the deposition of the fabric care composition onto the
surface of the fabric or fiber during the treatment process.
Without wishing to be bound by any theory, it is believed that in
order to drive the fabric care agent onto the surface of the
fabric, the net charge of the deposition aid, such as a positive
net charge, may be used to overcome repulsive interactions between
the fabric care agent and the fabric surface. For example, many
fabrics (such as cotton, rayon, silk, wool, etc.) are comprised of
fibers that may have a slightly negative charge in aqueous
environment. In certain embodiments, an effective amphoteric or
cationic oligomeric/polymeric deposition aid may be characterized
by a strong binding capability with the present fabric care agents
and compositions via physical forces, such as, van der Waals
forces, and/or non-covalent chemical binds such as hydrogen bonding
and/or ionic bonding. In some embodiments, the deposition aids may
also have a strong affinity to natural fabric fibers, such as
cotton or wool fibers.
[0032] In particular embodiments, the deposition aids described
herein are water soluble and may have flexible molecular structures
such that they may associate with the surface of a fabric care
agent particle or hold several of the particles together.
Therefore, the deposition enhancing agent may typically not be
cross-linked and typically does not have a network structure.
[0033] According to certain embodiments of the fabric care
compositions of the present disclosure, the amphoteric or cationic
oligomeric/polymeric deposition aid may be a cationic polymer
selected from the group consisting of a cationic polysaccharide, a
cationic guar, a cationic lignin, a cationic polymer, an amine
containing polymer, an amide containing polymer, and combinations
of any thereof. The term "cationic polymer" refers to a polymer
having a net cationic charge. Polymers containing amine groups or
other protonatable groups are included in the term "cationic
polymer," wherein the polymer is protonated at the pH of intended
use. In specific embodiments, the cationic polymer may be a
branched cationic polymer. For example, according to certain
embodiments, the cationic polymer may be a branched cationic
polysaccharide, wherein the polysaccharide has a fraction of
alpha-1,4-glycosidic linkages of at least about 0.01 up to about
1.0.
[0034] In another aspect, the fabric care composition and/or
treatment composition may comprise a deposition aid selected from
the group consisting of cationic or amphoteric polysaccharides.
Suitable cationic polysaccharides for the various embodiments of
the deposition aids described herein include, but are not limited
to, cationic cellulose derivatives, cationic and amphoteric
cellulose ethers, cationic or amphoteric galactomannan, cationic
guar gum derivatives, cationic or amphoteric starches and
derivatives, and cationic chitosan and derivatives. In specific
embodiments, the branched cationic polysaccharides may be a
branched cationic starch.
[0035] In some embodiments, the cationic polysaccharide deposition
aid may be a cationic guar derivative having a general formula
(A):
##STR00001##
where G is a galactomannan backbone; R.sup.13 is a group selected
from CH.sub.3, CH.sub.2CH.sub.3, phenyl, a C.sub.8-C.sub.24 alkyl
group (linear or branched) and combinations thereof; R.sup.14 and
R.sup.15 are groups independently selected from CH.sub.3,
CH.sub.2CH.sub.3, phenyl, and combinations thereof; and Z.sup.- is
a suitable anion. In certain embodiments, the guar derivatives
include guar hydroxypropyl trimethyl ammonium chloride. Examples of
cationic guar gums are Jaguar.TM. C13 and Jaguar.TM. Excel,
available from Rhodia, Inc. (Cranberry, N.J.).
[0036] In one aspect, the fabric care and/or treatment composition
may comprise from about 0.01% to about 10%, or from about 0.05 to
about 5%, or from about 0.1 to about 3% of the deposition aid.
Suitable deposition aids are disclosed in, for example, U.S.
application Ser. No. 12/080,358.
[0037] In one aspect, the one or more deposition aids may be a
cationic polymer. In one aspect, the deposition aid may comprise a
cationic polymer having a cationic charge density of from about 0.1
meq/g to about 23 meq/g from about 0.1 to about 12 meq/g, or from
about 0.3 to about 7 meq/g, at the pH of intended use of the
composition. For amine-containing polymers, wherein the charge
density depends on the pH of the composition, charge density is
measured at the pH of the intended use of the product. Such pH will
generally range from about 2 to about 11, more generally from about
2.5 to about 9.5. Charge density is calculated by dividing the
number of net charges per repeating unit by the molecular weight of
the repeating unit. The positive charges may be located on the
backbone of the polymers and/or the side chains of polymers. For
example, for the copolymer of acrylamide and
diallyldimethylammonium chloride with a monomer feed ratio of
70:30, the charge density of the feed monomers is about 3.05 meq/g.
However, if only 50% of diallyldimethylammonium is polymerized, the
polymer charge density is only about 1.6 meq/g. The polymer charge
density may be measured by dialyzing the polymer with a dialysis
membrane or by NMR. For polymers with amine monomers, the charge
density depends on the pH of the carrier. For these polymers,
charge density is measured at a pH of 7.
[0038] In one aspect, the cleaning and/or treatment composition may
comprise an amphoteric deposition aid polymer so long as the
polymer possesses a net positive charge. The polymer may have a
cationic charge density of from about 0.05 meq/g to about 12
meq/g.
[0039] Suitable polymers may be selected from the group consisting
of cationic or amphoteric polysaccharides, polyethylene imine and
its derivatives, and a synthetic polymer made by polymerizing one
or more cationic monomers selected from the group consisting of
N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl methacrylate,
N,N-dialkylamino alkyl acrylamide,
N,N-dialkylaminoalkylmethacrylamide, quaternized N,N dialkylamino
alkyl acrylate, quaternized N,N-dialkylaminoalkyl methacrylate,
quaternized N,N-dialkylaminoalkyl acrylamide, quaternized
N,N-dialkylaminoalkylmethacrylamide,
methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-ammonium
dichloride,
N,N,N,N',N',N'',N''-heptamethyl-N''-3-(1-oxo-2-methyl-2-propenyl)aminopro-
pyl-9-oxo-8-azo-decane-1,4,10-triammonium trichloride, vinylamine
and its derivatives, allylamine and its derivatives, vinyl
imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium
chloride and combinations thereof, and optionally a second monomer
selected from the group consisting of acrylamide, N,N-dialkyl
acrylamide, methacrylamide, N,N-dialkyl methacrylamide,
C.sub.1-C.sub.12 alkyl acrylate, C.sub.1-C.sub.12 hydroxyalkyl
acrylate, polyalkylene glyol acrylate, C.sub.1-C.sub.12 alkyl
methacrylate, C.sub.1-C.sub.12 hydroxyalkyl methacrylate,
polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol,
vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl
pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam,
and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl
sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane
sulfonic acid (AMPS) and their salts. The polymer may optionally be
branched or cross-linked by using branching and crosslinking
monomers. Branching and crosslinking monomers include ethylene
glycoldiacrylate divinylbenzene, and butadiene. A suitable
polyethyleneinine useful herein is that sold under the trade name
Lupasol.RTM. by BASF, AG, Lugwigshafen, Germany
[0040] In another aspect, the deposition aid may be selected from
the group consisting of cationic polysaccharides, cationic hydroxy
ethyl cellulose (such as Cat HEC polymer PK having a molecular
weight of about 400,000 Daltons and a charge density of 1.25 meq/g,
commercially available from Dow Chemical, Midland Mich.), cationic
starches (such as Akzo, EXP 5617-2301-28 (National Starch
126290-82), available from National Starch, Bridgewater, N.J.),
polyethylene imine and its derivatives,
poly(acrylamide-co-diallyldimethylammonium chloride),
poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride),
poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its
quaternized derivatives, poly(acrylamide-co-N,N-dimethyl aminoethyl
methacrylate) and its quaternized derivative,
poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate),
poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate),
poly(hydroxpropyl acrylate-co-methacrylamidopropyltrimethylammonium
chloride), poly(acrylamide-co-diallyldimethylammonium
chloride-co-acrylic acid), poly(acrylamide-methacrylamido
propyltrimethyl ammonium chloride-co-acrylic acid),
poly(diallyldimethyl ammonium chloride) (such as that sold under
trade names: Merquat.RTM. 100 and having a molecular weight of
150,000 Daltons, commercially available from Nalco Co., Naperville,
Ill.), poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate),
poly(ethyl methacrylate-co-quaternized dimethylaminoethyl
methacrylate), poly(ethyl methacrylate-co-oleyl
methacrylate-co-diethylaminoethyl methacrylate),
poly(diallyldimethylammonium chloride-co-acrylic acid), poly(vinyl
pyrrolidone-co-quaternized vinyl imidazole) and
poly(acrylamide-co-methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-a-
mmonium dichloride). In a specific embodiment, the deposition aid
may be a terpolymer with a mole ratio of 90% polyacrylamide:5%
acrylic acid:5% methylenebis-acrylamide-methacrylamido-propyl
trimethylammonium chloride ("MAPTAC", sold under the trade names
TX12528SQ, or Merquat.RTM. 5300, commercially available from Nalco
Co, Naperville, Ill.). Suitable deposition aids include
Polyquaternium-1, Polyquaternium-5, Polyquaternium-6,
Polyquaternium-7, Polyquaternium-8, Polyquaternium-11,
Polyquaternium-14, Polyquaternium-22, Polyquaternium-28,
Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33, as
named under the International Nomenclature for Cosmetic
Ingredients.
[0041] In one aspect, the deposition aid may comprise
polyethyleneimine or a polyethyleneimine derivative. In another
aspect, the deposition aid may comprise a cationic acrylic based
polymer. In another aspect, the deposition aid may comprise a
cationic polyacrylamide. In another aspect, the deposition aid may
comprise a polymer comprising polyacrylamide and
polymethacrylamidoproply trimethylammonium cation. In another
aspect, the deposition aid may comprise
poly(acrylamide-N,N-dimethylaminoethyl acrylate) and its
quaternized derivatives. In this aspect, the deposition aid may be
that sold under the trade name Sedipur.RTM., available from BTC
Specialty Chemicals, a BASF Group, Florham Park, N.J. In another
aspect, the deposition aid may comprise
poly(acrylamide-co-methacrylamidopropyltrimethyl ammonium
chloride). In another aspect, the deposition aid may be a
non-acrylamide based polymer, such as that sold under the trade
name Rheovis.RTM. CDE, available from Ciba Specialty Chemicals, a
BASF group, Florham Park, N.J., or as disclosed in U.S. Published
Application No. 2006/0252668.
[0042] Another group of suitable cationic polymers may include
alkylamine-epichlorohydrin polymers which are reaction products of
amines and oligoamines with epicholorohydrin, for example, those
polymers listed in, for example, U.S. Pat. Nos. 6,642,200 and
6,551,986. Examples include
dimethylamine-epichlorohydrin-ethylenediamine, available under the
trade name Cartafix.RTM. CB and Cartafix.RTM. TSF from Clariant,
Basel, Switzerland.
[0043] Another group of suitable synthetic cationic polymers may
include polyamidoamine-epichlorohydrin (PAE) resins of
polyalkylenepolyamine with polycarboxylic acid. The common PAE
resins may include the condensation products of diethylenetriamine
with adipic acid followed by a subsequent reaction with
epichlorohydrin. Suitable examples are available from Hercules Inc.
of Wilmington Del. under the trade name Kymene.TM. or from BASF AG
(Ludwigshafen, Germany) under the trade name Luresin.TM.. These
polymers are described in "Wet Strength Resins and their
Applications," edited by L. L. Chan, TAPPI Press (1994).
[0044] In various embodiments, the weight-average molecular weight
of the oligomeric/polymeric deposition aids may range from about
500 to about 10,000,000, from about 1,000 to about 5,000,000, or
from about 10,000 to about 5,000,000 Daltons, as determined by size
exclusion chromatography relative to polyethyleneoxide standards
with R.sup.1 detection. In one aspect, the MW of the cationic
polymer may be from about 50,000 to about 3,000,000 Daltons.
[0045] The cationic polymers may contain charge neutralizing anions
such that the overall polymer is neutral under ambient conditions.
Non-limiting examples of suitable counter ions (in addition to
anionic species generated during use) include chloride, bromide,
sulfate, methylsulfate, sulfonate, methylsulfonate, carbonate,
bicarbonate, formate, acetate, citrate, nitrate, and mixtures
thereof.
[0046] Useful cationic polysaccharides, such as the branched
cationic polysaccharides, such as the branched cationic starches,
described herein may have at least one of a viscosity of less than
about 1000 centipoise (cps), a charge density ranging from about
0.001 milliequivalents per gram (meq/g) of the polymer to about 5.0
meq/g of the polymer, and a weight average molecular weight ranging
from about 500 Daltons to about 10,000,000 Daltons. In one
embodiment, the deposition aid may be a cationic starch (such as
Akzo, EXP 5617-2301-28 (National Starch 126290-82), available from
National Starch, Bridgewater, N.J.) having a structure (XI):
##STR00002##
where R.sup.16 may be --OH or
--(O).sub.p--(CH.sub.2).sub.n(CH(OH)).sub.mCH.sub.2N.sup.+(CH.sub.3).sub.-
3 where p is 0 or 1, n is 1-10 and m is 0 or 1, provided that at
least one R.sup.16 group per substituted glucose unit is not --OH,
and having a suitable counteranion, charge density of from about
0.35 to about 0.6 meq/g, an amylose content of about 28%, a water
fluidity (WF) of from about 62 to about 70, and a molecular weight
of from about 1,200,000 Daltons to about 3,000,000 Daltons. In one
specific embodiment, the starch may be derived from maize, and
modified with R.sup.16 where
--O--CH.sub.2CH(OH).sub.mCH.sub.2N.sup.+(CH.sub.3).sub.3, and the
charge density may be about 0.42 meq/g, the molecular weight may be
about 1,500,000 Daltons, and the amylose content may be about
28%.
[0047] As used herein, the charge density of the cationic or
amphoteric polymers means the measurement of the charge of a
polymer (measured in meq) per gram of the polymer and may be
calculated, for example, by dividing the number of net charges per
repeating unit by the molecular weight of the repeating unit. As
recited above, in one embodiment, the charge density of the
deposition aid may range from about 0.001 meq/g to about 5.0 meq/g
of polymer. In another embodiment, the charge density of the
deposition aid may range from about 0.1 meq/g to about 3.0 meq/g of
polymer. According to the various embodiments, the charges, for
example, the positive charges may be located on the backbone of the
polymer and/or on a side chain of the polymer.
[0048] Other embodiments of the branched cationic polysaccharides
may have a weight average molecular weight ranging from about
50,000 Daltons to about 10,000,000 Daltons, or even from about
100,000 Daltons to about 5,000,000 Daltons. Certain embodiments of
branched cationic celluloses (including cationic hydroxyethyl
cellulose) may have a weight average molecular weight ranging from
about 200,000 Daltons to about 3,000,000 Daltons and certain
embodiments of the cationic guars may have a weight average
molecular weight ranging from about 500,000 Daltons to about
2,000,000 Daltons.
[0049] Other branched cationic polymers can include branched
cationic lignins and branched cationic synthetic polymers. Branched
cationic lignins include lignin structures, such as, but not
limited to lignin sulfonates, Kraft lignins, soda lignins,
organosolv lignins, softwood lignin, hardwood lignin, steam
explosion lignins, cellulosic grasses lignins, corn stover lignins,
and combinations of any thereof, that have been modified to have
cationic substituents, such as quaternary ammonium containing
substituents. Modifying the lignin polymer may include, for
example, substituting one or more of the hydroxyl groups on a
lignin polymer backbone with one or more R substituent groups
having a cationic charge, such as a quaternary ammonium charged
group. In other embodiments, modifying the lignin polymer may
include substituting at least one of the hydroxy, methoxy or
aromatic carbons on the lignin polymer backbone with at least one R
substituent group having a cationic charge.
[0050] The synthetic cationic or amphoteric oligomeric/polymeric
deposition aids may be random, block or grafted copolymers and may
be linear or branched. Certain embodiments of the synthetic
oligomeric/polymeric deposition aid may have a weight average
molecular weight ranging from about 2,000 Daltons to about
10,000,000 Daltons, or in specific embodiments from about 10,000,
Daltons to about 3,000,000 Daltons or even ranging from about
500,000 Daltons to about 2,000,000 Daltons.
[0051] Specific embodiments of the fabric care compositions
described herein may further comprise a surfactant quencher.
Without intending to be limited by any theory, it is believed that
certain surfactants may inhibit suitable and uniform deposition of
at least one of the hydrophobic fluid and/or the particulate
material onto the fabric or fiber surface. Therefore, excess or
unintended surfactant in the composition or wash/rinse solution may
be quenched or otherwise removed using the surfactant quencher.
According to certain embodiments, the surfactant quencher may be
present in from about 0.001% to about 5.0% by weight of the fabric
care composition, or in other embodiments from about 0.05% to about
3.0%. The surfactant quencher according to various embodiments may
have a solubility in the wash solution ranging from about 0.1% to
about 40%. In other embodiments, the surfactant quencher may be a
cationic surfactant quencher having a cationic charge ranging from
about 0.1 milliequivalents/gram (meq/g) to about 23 meq/g. In
further embodiments the surfactant quencher may have a molecular
weight ranging from about 50 g/mole to about 1000 g/mole. In
particular embodiments, the surfactant quencher may be coconut
trimethyl ammonium chloride, dimethyl hydroxymethyl lauryl ammonium
chloride, STEPANQUAT.RTM. 6585 (dipalmethyl hydroxyethylammonium
methosulfate, lauryl trimethyl ammonium chloride or ditallow
dimethyl ammonium chloride ("DTDMAC") and/or other cationic
surfactants, including blends of the various surfactant
quenchers.
[0052] Further embodiments of the fabric care compositions
described herein may further comprise a dispersant. As used herein,
a dispersant is a chemical compound or compounds that are used to
stabilize an emulsion, dispersion or suspension of particles in a
liquid. Suitable dispersants for use in the various embodiments
described herein include non-ionic surfactants, polymeric
surfactants, and silicone based dispersants. According to various
embodiments, the dispersant may comprise from about 0.001% to 5% by
weight of the composition; in certain embodiments from 0.05% to 2%
by weight of the composition and in specific embodiments from
0.05%-0.5% by weight of the composition.
[0053] For example, suitable non-ionic surfactant include, but are
not limited to, ethoxylated alcohols (aliphatic ethoxylate),
polyethylene oxide (PEO) caprilic acid, PEO stearic acid, PEO oleic
acid, PEO Lauric acid, nonionic hydroxylamines, ethoxylated
alkylphenols, fatty esters, proxylated & ethoxylated fatty
acids, alcohols, or alkyl phenols, fatty esters series, ethoxylated
fatty acids, Ethoxylated fatty esters and oils, alkanolamides
series, amine oxides series, ethoxylated amines and/or amides, POE
stearic acid series, glycerol esters, glycol esters, ethoxylated
oxazoline derivatives, monoglycerides and derivatives, lanolin
based derivatives, amides, alkanolamides, amine oxides,
hydrotropes, lecithin and Lecithin derivatives, phosphorous organic
derivatives, sorbitan derivatives, protein based surfactants, allyl
polyglycosides, thio and mercapto derivatives, imidazolines and
imidazoline derivatives, cetearyl alcohols, emulsifying wax, octyl
phenol ethoxylate, sucrose and glucose esters and derivatives,
dipropyleneglycol isocetech-20 acetate, phosphate esters,
organo-phosphate ester, propylene glycol mono- and diesters of fats
ad fatty acids, mono- and diglycerides, partially hydrogenated
vegetable oil with lecithin, BHT and citric acid, lauramine oxides,
refined soya sterol, emulsified trichlorobenzene, emulsified
aromatic and aliphatic solvents and esters, emulsified proprietary
aromatic, fatty esters, modified ethoxylate, phenoxy compound,
ethylene oxide condensate, polyglyceryl dimerate, lecithin and
lecithin derivatives, pentaerythrityl tetracaprylate/tetracaprate,
lauramide MEA, linoleamide DEA, coco imidazoline, imidazolines and
imidazoline derivatives, carboxylated alcohol or alkylphenol
ethoxylates, ethoxylated aryl phenols, and many others. Nonionic
surfactants, such as Abex.RTM. series from Rhodia Inc.,
Actrafos.RTM. series from Georgia Pacific, Acconon.RTM. series from
Abitec Corporation, Adsee.RTM. series from Witco Corp., Aldo.RTM.
series from Lonza Inc., Amidex.RTM. series from Chemron Corp.,
Amodox series from Stepan Company, heterocyclic type products, and
many other companies. Preferred nonionic surfactants are TAE 80
from BASF, Surforic L24-7 from BASF and some others.
[0054] Suitable polymeric dispersants include, but are not limited
to, polyethylene glycols, PEO polymers, PEO ether, PEO/PPO block
polymers, polyether, polyoxyalkylated alcohol, polyoxyethylene
styrenated phenyl ether, block copolymer of alkoxylated glycols,
polysaccharides, alkyl polyglycosides, PEG, PEG corn glycerides,
PEG palm kernel glycerides, polyacrylic acid copolymers,
polyacryamides, polymethyl acrylic acid, polyoxyalkylene ether,
polyamides, polyproxylated & ethoxylated fatty acids, alcohols,
or alkyl phenols, polycarboxylate polymers, any polymers comprising
a hydrophilic side chain substituted polyimide or polyamide
composition, any polymers having a hydrophilic groups, such as
--COOH, a derivative of --COOH, sulfonic acid, a derivative of
sulfonic acid, amine, and epoxy. Preferred polymeric surfactants
are polyvinyl alcohols (PVOH), Polyvinyl pyrrolidone (PVP), and
more.
[0055] Suitable silicone-based surfactants are dimethicone
copolyols, polysiloxane polyether copolymer, cetyl dimethicone
copolyol, polysiloxane polyalkyl polyether copolymers, silicone
ethylene oxide copolymers, silicone glycol, cocamide DEA, silicone
glycol copolymers, such as Abil B series, Abil EM series, Abil WE
series from Goldschmodt AG, Silwet series from Witco
Corporation.
Adjunct Materials
[0056] Any number of additional ingredients can also be included as
components in the various detergent and cleaning compositions
described herein. These include other detergency builders,
bleaches, bleach activators, suds boosters or suds suppressors,
anti-tarnish and anti-corrosion agents, soil suspending agents,
soil release agents, germicides, pH adjusting agents, non-builder
alkalinity sources, chelating agents, smectite clays, enzymes,
enzyme-stabilizing agents and perfumes. See U.S. Pat. No.
3,936,537.
[0057] Bleaching agents and activators are described in U.S. Pat.
Nos. 4,412,934 and 4,483,781. Chelating agents are also described
in U.S. Pat. No. 4,663,071 from column 17, line 54 through column
18, line 68. Suds modifiers are also optional ingredients and are
described in U.S. Pat. Nos. 3,933,672 and 4,136,045. Suitable
smectite clays for use herein are described in U.S. Pat. No.
4,762,645 column 6, line 3 through column 7, line 24. Suitable
additional detergency builders for use herein are enumerated in
U.S. Pat. No. 3,936,537 at column 13, line 54 through column 16,
line 16, and in U.S. Pat. No. 4,663,071.
[0058] In yet another aspect of the present disclosure, the fabric
care compositions disclosed herein, may take the form of rinse
added fabric conditioning compositions. Such compositions may
comprise a fabric softening active and the dispersant polymer of
the present disclosure, to provide a stain repellency benefit to
fabrics treated by the composition, typically from about 0.00001
wt. % (0.1 ppm) to about 1 wt. % (10,000 ppm), or even from about
0.0003 wt. % (3 ppm) to about 0.03 wt. % (300 ppm) based on total
rinse added fabric conditioning composition weight. In another
specific embodiment, the compositions are rinse added fabric
conditioning compositions. Examples of typical rinse added
conditioning composition can be found in U.S. Provisional Patent
Application Ser. No. 60/687,582 filed on Oct. 8, 2004.
[0059] While not essential for the purposes of the present
disclosure, the non-limiting list of adjuncts illustrated
hereinafter are suitable for use in various embodiments of the
cleaning compositions and may be desirably incorporated in certain
embodiments of the disclosure, for example to assist or enhance
performance, for treatment of the substrate to be cleaned, or to
modify the aesthetics of the composition as is the case with
perfumes, colorants, dyes or the like. It is understood that such
adjuncts are in addition to the components that were previously
listed for any particular embodiment. The total amount of such
adjuncts may range from about 0.1% to about 50%, or even from about
1% to about 30%, by weight of the cleaning composition.
[0060] The precise nature of these additional components, and
levels of incorporation thereof, will depend on the physical form
of the composition and the nature of the operation for which it is
to be used. Suitable adjunct materials include, but are not limited
to, polymers, for example cationic polymers, surfactants, builders,
chelating agents, dye transfer inhibiting agents, dispersants,
enzymes, and enzyme stabilizers, catalytic materials, bleach
activators, polymeric dispersing agents, clay soil
removal/anti-redeposition agents, brighteners, suds suppressors,
dyes, additional perfume and perfume delivery systems, structure
elasticizing agents, fabric softeners, carriers, hydrotropes,
processing aids and/or pigments. In addition to the disclosure
below, suitable examples of such other adjuncts and levels of use
are found in U.S. Pat. Nos. 5,576,282; 6,306,812; and
6,326,348.
[0061] As stated, the adjunct ingredients are not essential to the
cleaning compositions. Thus, certain embodiments of the
compositions do not contain one or more of the following adjuncts
materials: bleach activators, surfactants, builders, chelating
agents, dye transfer inhibiting agents, dispersants, enzymes, and
enzyme stabilizers, catalytic metal complexes, polymeric dispersing
agents, clay and soil removal/anti-redeposition agents,
brighteners, suds suppressors, dyes, additional perfumes and
perfume delivery systems, structure elasticizing agents, fabric
softeners, carriers, hydrotropes, processing aids and/or pigments.
However, when one or more adjuncts are present, such one or more
adjuncts may be present as detailed below:
[0062] Surfactants--The compositions according to the present
disclosure can comprise a surfactant or surfactant system wherein
the surfactant can be selected from nonionic and/or anionic and/or
cationic surfactants and/or ampholytic and/or zwitterionic and/or
semi-polar nonionic surfactants. The surfactant is typically
present at a level of from about 0.1%, from about 1%, or even from
about 5% by weight of the cleaning compositions to about 99.9%, to
about 80%, to about 35%, or even to about 30% by weight of the
cleaning compositions.
[0063] Builders--The compositions of the present disclosure can
comprise one or more detergent builders or builder systems. When
present, the compositions will typically comprise at least about 1%
builder, or from about 5% or 10% to about 80%, 50%, or even 30% by
weight, of said builder. Builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of
polyphosphates, alkali metal silicates, alkaline earth and alkali
metal carbonates, aluminosilicate builders polycarboxylate
compounds, ether hydroxypolycarboxylates, copolymers of maleic
anhydride with ethylene or vinyl methyl ether,
1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and
carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium
and substituted ammonium salts of polyacetic acids such as
ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well
as polycarboxylates such as mellitic acid, succinic acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic
acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
[0064] Chelating Agents--The compositions herein may also
optionally contain one or more copper, iron and/or manganese
chelating agents. If utilized, chelating agents will generally
comprise from about 0.1% by weight of the compositions herein to
about 15%, or even from about 3.0% to about 15% by weight of the
compositions herein.
[0065] Dye Transfer Inhibiting Agents--The compositions of the
present disclosure may also include one or more dye transfer
inhibiting agents. Suitable polymeric dye transfer inhibiting
agents include, but are not limited to, polyvinylpyrrolidone
polymers, polyamine N-oxide polymers, copolymers of
N-vinylpyrrolidone and N-vinylimidazole (PVPVI),
polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
When present in the compositions herein, the dye transfer
inhibiting agents are present at levels from about 0.0001%, from
about 0.01%, from about 0.05% by weight of the cleaning
compositions to about 10%, about 2%, or even about 1% by weight of
the cleaning compositions.
[0066] Dispersants--The compositions of the present disclosure can
also contain dispersants. Suitable water-soluble organic materials
are the homo- or co-polymeric acids or their salts, in which the
polycarboxylic acid may comprise at least two carboxyl radicals
separated from each other by not more than two carbon atoms.
[0067] Enzymes--The compositions can comprise one or more detergent
enzymes which provide cleaning performance and/or fabric care
benefits. Examples of suitable enzymes include, but are not limited
to, hemicellulases, peroxidases, proteases, cellulases, xylanases,
lipases, phospholipases, esterases, cutinases, pectinases,
keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,
.beta.-glucanases, arabinosidases, hyaluronidase, chondroitinase,
laccase, and amylases, or mixtures thereof. A typical combination
is a cocktail of conventional applicable enzymes like protease,
lipase, cutinase and/or cellulase in conjunction with amylase.
[0068] Enzyme Stabilizers--Enzymes for use in compositions, for
example, detergents can be stabilized by various techniques. The
enzymes employed herein can be stabilized by the presence of
water-soluble sources of calcium and/or magnesium ions in the
finished compositions that provide such ions to the enzymes.
[0069] If desired, the compositions herein can be catalyzed by
means of a manganese compound. Such compounds and levels of use are
well known in the art and include, for example, the manganese-based
catalysts disclosed in U.S. Pat. No. 5,576,282.
[0070] Cobalt bleach catalysts useful herein are known, and are
described, for example, in U.S. Pat. Nos. 5,597,936 and 5,595,967.
Such cobalt catalysts are readily prepared by known procedures,
such as taught for example in U.S. Pat. Nos. 5,597,936, and
5,595,967.
[0071] Compositions herein may also suitably include a transition
metal complex of a macropolycyclic rigid ligand ("MRL"). As a
practical matter, and not by way of limitation, the compositions
and cleaning processes herein can be adjusted to provide on the
order of at least one part per hundred million of the benefit agent
MRL species in the aqueous washing medium, and may provide from
about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10
ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the
wash liquor.
[0072] Preferred transition-metals in the instant transition-metal
bleach catalyst include manganese, iron and chromium. Preferred
MRLs herein are a special type of ultra-rigid ligand that is
cross-bridged such as
5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane. Suitable
transition metal MRLs are readily prepared by known procedures,
such as taught, for example, in WO 00/32601, and U.S. Pat. No.
6,225,464.
EXAMPLES
Surface Treatment Compositions
Example 1
Preparation of Polyorganosiloxane-Silicone Resin Mixtures
1-A. Preparation of a Stable Oil Mixture
[0073] 13.2 g MQ silicone resin
([Me.sub.3SiO.sub.1/2].sub.0.373[SiO.sub.2].sub.0.627, Mn=2700
g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether
(obtainable from Sigma-Aldrich Chemicals GmbH) by stiffing and then
mixed with 76.3 g amine oil (viscosity of approximately 1000
mm.sup.2/sec at 25.degree. C., functional residues
--(CH.sub.2).sub.3NH(CH.sub.2)NH.sub.2, amine number 0.6 mmol/g,
90% SiMe.sub.3 end groups, 10% SiMe.sub.2OH end groups) at
25.degree. C. A clear, colorless solution with a viscosity of
approximately 3000 mPas is obtained.
1-B. Preparation of a Stable Oil Mixture
[0074] 13.2 g MQ silicone resin
([Me.sub.3SiO.sub.1/2].sub.0.373[SiO.sub.2].sub.0.627, Mn=2700
g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether
(Sigma-Aldrich Chemicals GmbH) by stirring and then mixed with 76.3
g amine oil (viscosity of approximately 500 mm.sup.2/sec at
25.degree. C., functional residues
--(CH.sub.2).sub.3NH(CH.sub.2)NH.sub.2, amine number 0.6 mmol/g,
68% SiMe.sub.3 end groups, 25% SiMe.sub.2OH end groups, 7%
SiMe.sub.2OMe end groups) at 25.degree. C. A clear, colorless
solution with a viscosity of approximately 3000 mPas is
obtained.
1-C. Preparation of a Stable Oil Mixture
[0075] 13.2 g MQ silicone resin
([Me.sub.3SiO.sub.1/2].sub.0.373[SiO.sub.2].sub.0.627, Mn=2700
g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether
(Sigma-Aldrich Chemicals GmbH) by stirring and then mixed with 76.3
g amine oil (viscosity of approximately 1300 mm.sup.2/sec at
25.degree. C., functional residues
--(CH.sub.2).sub.3NH(CH.sub.2)NH.sub.2, amine number 0.8 mmol/g,
60% SiMe.sub.3 end groups, 33% SiMe.sub.2OH end groups, 7%
SiMe.sub.2OMe end groups) at 25.degree. C. A clear, colorless
solution with a viscosity of approximately 3000 mPas is
obtained.
1-D. Preparation of a Stable/Low Performance Oil Mixture
[0076] 13.2 g MQ silicone resin
([Me.sub.3SiO.sub.1/2].sub.0.373[SiO.sub.2].sub.0.627, Mn=2700
g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether
(Sigma-Aldrich Chemicals GmbH) by stirring and then mixed with 76.3
g amine oil (viscosity of approximately 2500 mm.sup.2/sec at
25.degree. C., functional residues
--(CH.sub.2).sub.3NH(CH.sub.2)NH.sub.2, amine number 0.3 mmol/g,
72% SiMe.sub.3 end groups, 26% SiMe.sub.2OH end groups, 2%
SiMe.sub.2OMe end groups) at 25.degree. C. A clear, colorless
solution with a viscosity of approximately 3000 mPas is
obtained.
1-E. Preparation of an Unstable Oil Mixture, not in Accordance with
the Invention
[0077] 13.2 g MQ silicone resin
([Me.sub.3SiO.sub.1/2].sub.0.373[SiO.sub.2].sub.0.627, Mn=2700
g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether
(Sigma-Aldrich Chemicals GmbH) by stirring and then mixed with 76.3
g amine oil (viscosity of approximately 2800 mm.sup.2/sec at
25.degree. C., functional residues
--(CH.sub.2).sub.3NH(CH.sub.2)NH.sub.2, amine number 0.6 mmol/g,
47% SiMe.sub.3 end groups, 45% SiMe.sub.2OH end groups, 8%
SiMe.sub.2OMe end groups) at 25.degree. C. A clear, colorless
solution with a viscosity of approximately 3000 mPas is obtained.
This mixture formed a gel after 3 days and was no longer
usable.
Example 2
Application Examples
[0078] 2-A. The mixtures prepared above were for applications
testing. The said oil mixture was diluted with isopropyl alcohol to
a solids content of 2%. The solutions were sprayed onto cotton
fabrics and the fabrics were line dried. After drying, time to wick
was measured on all fabrics according to the Time to Wick (T2W)
testing method protocol described below.
TABLE-US-00001 Water T2W Untreated 0 second Example A >20 minute
Example B >20 minute Example C >20 minute Example D >20
minute Example E Not applicable (unstable)
[0079] 2-B. The above mixture was mixed with emulsifiers (fatty
alcohol ethoxylate with 6 EO) and acetic acid and then water to
make 35% emulsions. The emulsions were diluted into 2% solution
with water. Cotton fabric was dipped in the solution and then line
dried. The time to wick was measured on the fabrics according to
the T2W testing method.
TABLE-US-00002 Water T2W Untreated 0 second Example A >20 minute
Example B >20 minute Example C >20 minute Example D >20
minute Example E Not applicable (unstable)
[0080] According to certain embodiments, the
polyorganosiloxane-silicone resin mixture of the present disclosure
may also be incorporated into any surface treatment or cleaning
composition, such as, but not limited to, a fabric care
composition, a dish cleaning composition, a home surface care
composition or a personal care composition. Examples of treatment
and cleaning compositions include, but are not limited to, liquid
laundry detergents, solid laundry detergents, laundry soap
products, laundry spray treatment products, laundry pre-treatment
products, hand dish washing detergents, automatic dishwashing
detergents, a beauty care detergent, hard surface cleaning
detergents, carpet cleaning detergents, a shampoo, and a household
cleaning detergent. Examples of fabric care compositions suitable
for the present disclosure include, but are not limited to, liquid
laundry detergents, heavy duty liquid laundry detergents, solid
laundry detergents, laundry soap products, laundry spray treatment
products, laundry pre-treatment products, laundry soak products,
heavy duty liquid detergents, and rinse additives. Examples of
suitable dish cleaning compositions include, but are not limited
to, automatic dishwasher detergents, detergents for hand washing of
dishes, liquid dish soap, and solid granular dish soap. Examples of
suitable home care compositions include, but are not limited to,
rug or carpet cleaning compositions, hard surface cleaning
detergents, floor cleaning compositions, window cleaning
compositions, toilet and bathroom cleaning compositions, household
cleaning detergents, and car washing detergents. Examples of
suitable personal care compositions include, but are not limited
to, beauty care detergents, beauty bars, bar soap, bath beads, bath
soaps, hand washing compositions, body washes and soaps, shampoo,
conditioners, cosmetics, hair removal compositions, and oral care
compositions.
Example 3
Liquid Laundry Additive Compositions
[0081] The above mixtures were mixed with emulsifiers (fatty
alcohol ethoxylate with 6 EO) and acetic acid and then water to
make 35% emulsions. The emulsions were then made into products with
the following formulation. The formulated products were used in the
rinse cycle in the washing machine with loaded cotton garments.
Normal wash conditions were used and Tide detergent was used in the
wash cycle.
TABLE-US-00003 Formula (w/w active %) Si Fluid-Resin Mixtures from
Example 1 10.67 Cationic Starch (Maize, MW 1,500,000 Daltons, 0.72
charge density 0.42 meq/g, amylase 28%) DTDMAC 1.33 Perfume: 0.20
Preservant: Proxel 0.015
[0082] Cotton fabric was dipped in the solution and then line
dried. The time to wick was measured on the fabrics according to
the T2W testing method.
TABLE-US-00004 Water T2W Untreated 0 second Product/Example A 977
second Product/Example B 1200 second Product/Example C >20
minute Product/Example D 7 second Product/Example E Not applicable
(unstable)
[0083] Liquid laundry additive compositions 1-9 detailed below have
detailed percentages based on 100% active basis.
TABLE-US-00005 Ingredient 1 2 3 4 5 6 7 8 9 Dosage 30 g 30 g 30 g
30 g 30 g 30 g 30 g 30 g 30 g Wacker HC306 6.00% 6.00% 6.00% 6.00%
6.00% 12.00% 12.00% 12.00% 12.00% Akzo Nobel 1.20% 1.20% 1.20%
1.20% 1.20% 1.20% 1.20% 1.20% 1.20% EXP5617 TAE80 0.25% 0.25% 0.25%
0.25% 0.25% 0.25% 0.25% 0.25% 0.25% Proxel GXL 0.02% 0.02% 0.02%
0.02% 0.02% 0.02% 0.02% 0.02% 0.02% Best B perfume 0.40% 0.40%
0.40% 0.40% 0.40% 0.40% 0.40% 0.40% 0.40% Butyl Carbitol 3.00%
3.00% 3.00% 3.00% 3.00% 2.00% 2.00% 2.00% 2.00% Polyamine N- 0.00%
0.83% 1.67% 3.34% 5.00% 0.00% 1.67% 3.34% 5.00% oxide T2W (sec.) 7
14 37 73 78 15 75 149 282
Example 4
Liquid Detergent Compositions
[0084] The treatment or cleaning compositions herein, such as, but
not limited to liquid detergent compositions, may take the form of
an aqueous solution or uniform dispersion or suspension of
surfactant and water, polyorganosiloxane-silicone resin mixture,
and certain optional adjunct ingredients, some of which may
normally be in solid form, that have been combined with the
normally liquid components of the composition. Suitable surfactants
may be anionic, nonionic, cationic, zwitterionic and/or amphoteric
surfactants. In one embodiment, the cleaning composition comprises
anionic surfactant, nonionic surfactant, or mixtures thereof.
[0085] Suitable anionic surfactants may be any of the conventional
anionic surfactant types typically used in cleaning compositions,
such as liquid or solid detergent products. Such surfactants
include the alkyl benzene sulfonic acids and their salts as well as
alkoxylated or non-alkoxylated alkyl sulfate materials. Exemplary
anionic surfactants are the alkali metal salts of C.sub.10-C.sub.16
alkyl benzene sulfonic acids, preferably C.sub.11-C.sub.14 alkyl
benzene sulfonic acids. In one aspect, the alkyl group is linear.
Such linear alkyl benzene sulfonates are known as "LAS". Such
surfactants and their preparation are described for example in U.S.
Pat. Nos. 2,220,099 and 2,477,383. Especially preferred are the
sodium and potassium linear straight chain alkylbenzene sulfonates
in which the average number of carbon atoms in the alkyl group is
from about 11 to 14. Sodium C.sub.11-C.sub.14, e.g., C.sub.12 LAS
is a specific example of such surfactants.
[0086] Another exemplary type of anionic surfactant comprises
ethoxylated alkyl sulfate surfactants. Such materials, also known
as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those
which correspond to the formula:
R'--O--(C.sub.2H.sub.4O).sub.n--SO.sub.3M wherein R' is a
C.sub.8-C.sub.20 alkyl group, n is from about 1 to 20, and M is a
salt-forming cation. In a specific embodiment, R' is
C.sub.10-C.sub.18 alkyl, n is from about 1 to 15, and M is sodium,
potassium, ammonium, alkylammonium, or alkanolammonium. In more
specific embodiments, R' is a C.sub.12-C.sub.16, n is from about 1
to 6, and M is sodium.
[0087] The alkyl ether sulfates will generally be used in the form
of mixtures comprising varying R' chain lengths and varying degrees
of ethoxylation. Frequently such mixtures will inevitably also
contain some non-ethoxylated alkyl sulfate materials, i.e.,
surfactants of the above ethoxylated alkyl sulfate formula wherein
n=0. Non-ethoxylated alkyl sulfates may also be added separately to
the cleaning compositions of this disclosure and used as or in any
anionic surfactant component which may be present. Specific
examples of non-alkoxylated, e.g., non-ethoxylated, alkyl ether
sulfate surfactants are those produced by the sulfation of higher
C.sub.8-C.sub.20 fatty alcohols. Conventional primary alkyl sulfate
surfactants have the general formula: R''OSO.sub.3.sup.-M.sup.+
wherein R'' is typically a linear C.sub.8-C.sub.20 hydrocarbyl
group, which may be straight chain or branched chain, and M is a
water-solubilizing cation. In specific embodiments, R'' is a
C.sub.10-C.sub.15 alkyl, and M is alkali metal, more specifically
R'' is C.sub.12-C.sub.14 and M is sodium.
[0088] Specific, nonlimiting examples of anionic surfactants useful
herein include: a) C.sub.11-C.sub.18 alkyl benzene sulfonates
(LAS); b) C.sub.10-C.sub.20 primary, branched-chain and random
alkyl sulfates (AS); c) C.sub.10-C.sub.18 secondary (2,3)-alkyl
sulfates having Formulae (XII) and (XIII):
##STR00003##
wherein M in Formulae (XII) and (XIII) is hydrogen or a cation
which provides charge neutrality, and all M units, whether
associated with a surfactant or adjunct ingredient, can either be a
hydrogen atom or a cation depending upon the form isolated by the
artisan or the relative pH of the system wherein the compound is
used, with non-limiting examples of preferred cations including
sodium, potassium, ammonium, and mixtures thereof, and x in Formula
XII is an integer of at least about 7, preferably at least about 9,
and y in Formula XIII is an integer of at least 8, preferably at
least about 9; d) C.sub.10-C.sub.18 alkyl alkoxy sulfates
(AE.sub.xS) wherein preferably x in Formula XII is from 1-30; e)
C.sub.10-C.sub.18 alkyl alkoxy carboxylates preferably comprising
1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed
in U.S. Pat. Nos. 6,020,303 and 6,060,443; g) mid-chain branched
alkyl alkoxy sulfates as discussed in U.S. Pat. Nos. 6,008,181 and
6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed
in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084,
WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; i) methyl
ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).
[0089] Suitable nonionic surfactants useful herein can comprise any
of the conventional nonionic surfactant types typically used in
liquid detergent products. These include alkoxylated fatty alcohols
and amine oxide surfactants. Preferred for use in the liquid
detergent products herein are those nonionic surfactants which are
normally liquid. Suitable nonionic surfactants for use herein
include the alcohol alkoxylate nonionic surfactants. Alcohol
alkoxylates are materials which correspond to the general formula:
R.sup.7(C.sub.mH.sub.2mO).sub.nOH wherein R.sup.7 is a
C.sub.8-C.sub.16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12. Preferably R.sup.7 is an alkyl group, which may be
primary or secondary, that contains from about 9 to 15 carbon
atoms, more preferably from about 10 to 14 carbon atoms. In one
embodiment, the alkoxylated fatty alcohols will also be ethoxylated
materials that contain from about 2 to 12 ethylene oxide moieties
per molecule, more preferably from about 3 to 10 ethylene oxide
moieties per molecule.
[0090] The alkoxylated fatty alcohol materials useful in the liquid
detergent compositions herein will frequently have a
hydrophilic-lipophilic balance (HLB) which ranges from about 3 to
17. More preferably, the HLB of this material will range from about
6 to 15, most preferably from about 8 to 15. Alkoxylated fatty
alcohol nonionic surfactants have been marketed under the tradename
NEODOL.RTM. by the Shell Chemical Company.
[0091] Another suitable type of nonionic surfactant useful herein
comprises the amine oxide surfactants. Amine oxides are materials
which are often referred to in the art as "semi-polar" nonionics.
Amine oxides have the formula:
R'''(EO).sub.x(PO).sub.y(BO).sub.zN(O)(CH.sub.2R').sub.2.qH.sub.2O.
In this formula, R''' is a relatively long-chain hydrocarbyl moiety
which can be saturated or unsaturated, linear or branched, and can
contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is
more preferably C.sub.12-C.sub.16 primary alkyl. R' is a
short-chain moiety, preferably selected from hydrogen, methyl and
--CH.sub.2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO
is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants
are illustrated by C.sub.12-C.sub.14 alkyldimethyl amine oxide.
[0092] Non-limiting examples of nonionic surfactants include: a)
C.sub.12-C.sub.18 alkyl ethoxylates, such as, NEODOL.RTM. nonionic
surfactants; b) C.sub.6-C.sub.12 alkyl phenol alkoxylates wherein
the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy
units; c) C.sub.12-C.sub.18 alcohol and C.sub.6-C.sub.12 alkyl
phenol condensates with ethylene oxide/propylene oxide block
polymers such as PLURONIC.RTM. from BASF; d) C.sub.14-C.sub.22
mid-chain branched alcohols, BA, as discussed in U.S. Pat. No.
6,150,322; e) C.sub.14-C.sub.22 mid-chain branched alkyl
alkoxylates, BAE.sub.x, wherein x is 1-30, as discussed in U.S.
Pat. Nos. 6,153,577; 6,020,303; and 6,093,856; f)
alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647;
specifically alkylpolyglycosides as discussed in U.S. Pat. Nos.
4,483,780 and 4,483,779; g) polyhydroxy fatty acid amides as
discussed in U.S. Pat. No. 5,332,528; WO 92/06162; WO 93/19146; WO
93/19038; and WO 94/09099; and h) ether capped poly(oxyalkylated)
alcohol surfactants as discussed in U.S. Pat. No. 6,482,994 and WO
01/42408.
[0093] In the laundry detergent compositions and other cleaning
compositions herein, the detersive surfactant component may
comprise combinations of anionic and nonionic surfactant materials.
When this is the case, the weight ratio of anionic to nonionic will
typically range from 10:90 to 90:10, more typically from 30:70 to
70:30.
[0094] Cationic surfactants are well known in the art and
non-limiting examples of these include quaternary ammonium
surfactants, which can have up to 26 carbon atoms. Additional
examples include a) alkoxylate quaternary ammonium (AQA)
surfactants as discussed in U.S. Pat. No. 6,136,769; b) dimethyl
hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.
6,004,922; c) polyamine cationic surfactants as discussed in WO
98/35002; WO 98/35003; WO 98/35004; WO 98/35005; and WO 98/35006;
d) cationic ester surfactants as discussed in U.S. Pat. Nos.
4,228,042; 4,239,660; 4,260,529; and 6,022,844; and e) amino
surfactants as discussed in U.S. Pat. No. 6,221,825 and WO
00/47708, specifically amido propyldimethyl amine (APA).
[0095] Non-limiting examples of zwitterionic surfactants include:
derivatives of secondary and tertiary amines, derivatives of
heterocyclic secondary and tertiary amines, or derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium
compounds. See U.S. Pat. No. 3,929,678 at column 19, line 38
through column 22, line 48, for examples of zwitterionic
surfactants; betaine, including alkyl dimethyl betaine and
cocodimethyl amidopropyl betaine, C.sub.8-C.sub.18 (preferably
C.sub.12-C.sub.18) amine oxides and sulfo and hydroxy betaines,
such as N-alkyl-N,N-dimethylammino-1-propane sulfonate where the
alkyl group can be C.sub.8-C.sub.18, preferably
C.sub.m--C.sub.14.
[0096] Non-limiting examples of ampholytic surfactants include:
aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines in which
the aliphatic radical can be straight- or branched-chain. One of
the aliphatic substituents contains at least about 8 carbon atoms,
typically from about 8 to about 18 carbon atoms, and at least one
contains an anionic water-solubilizing group, e.g. carboxy,
sulfonate, sulfate. See U.S. Pat. No. 3,929,678 at column 19, lines
18-35, for examples of ampholytic surfactants.
[0097] The cleaning compositions disclosed herein may be prepared
by combining the components thereof in any convenient order and by
mixing, e.g., agitating, the resulting component combination to
form a phase stable cleaning composition. In one aspect, a liquid
matrix is formed containing at least a major proportion, or even
substantially all, of the liquid components, e.g., nonionic
surfactant, the non-surface active liquid carriers and other
optional liquid components, with the liquid components being
thoroughly admixed by imparting shear agitation to this liquid
combination. For example, rapid stirring with a mechanical stirrer
may usefully be employed. While shear agitation is maintained,
substantially all of any anionic surfactant and the solid
ingredients can be added. Agitation of the mixture is continued,
and if necessary, can be increased at this point to form a solution
or a uniform dispersion of insoluble solid phase particulates
within the liquid phase. After some or all of the solid-form
materials have been added to this agitated mixture, particles of
any enzyme material to be included, e.g., enzyme prills are
incorporated. As a variation of the composition preparation
procedure described above, one or more of the solid components may
be added to the agitated mixture as a solution or slurry of
particles premixed with a minor portion of one or more of the
liquid components. After addition of all of the composition
components, agitation of the mixture is continued for a period of
time sufficient to form compositions having the requisite viscosity
and phase stability characteristics. Frequently this will involve
agitation for a period of from about 30 to 60 minutes.
[0098] In another aspect of producing liquid cleaning compositions,
the polyorganosiloxane-silicone resin mixture may first be combined
with one or more liquid components to form a
polyorganosiloxane-silicone resin mixture premix, and this
polyorganosiloxane-silicone resin mixture premix is added to a
composition formulation containing a substantial portion, for
example more than 50% by weight, more than 70% by weight, or even
more than 90% by weight, of the balance of components of the
cleaning composition. For example, in the methodology described
above, both the polyorganosiloxane-silicone resin mixture
polyorganosiloxane-silicone resin mixture premix and the enzyme
component are added at a final stage of component additions. In
another aspect, the polyorganosiloxane-silicone resin mixture is
encapsulated prior to addition to the detergent composition, the
encapsulated polyorganosiloxane-silicone resin mixture is suspended
in a structured liquid, and the suspension is added to a
composition formulation containing a substantial portion of the
balance of components of the cleaning composition.
Heavy Duty Liquid Laundry Detergent Formulations
[0099] In this Example, three sample formulations for a heavy duty
liquid (HDL) laundry detergent are prepared using the
polyorganosiloxane-silicone resin mixture according to embodiments
of the present disclosure. The polyorganosiloxane-silicone resin
mixture is added to the formulations in an amount ranging from 0.5%
to 10.0% by weight.
TABLE-US-00006 A B C D E Ingredient Wt % Wt % Wt % Wt % Wt % Sodium
alkyl 20.5 20.5 20.5 ether sulfate C12-15 Alkyl 9.0 Polyethoxylate
(1.1) Sulfonic Acid Branched alcohol 5.8 5.8 5.8 sulfate Linear
alkylbenzene 2.5 2.5 2.5 1.0 8.0 sulfonic acid Alkyl ethoxylate 0.8
0.8 0.8 1.5 6.0 Amine oxide 0 0.5 2 1.0 Citric acid 3.5 3.5 3.5 2.0
2.5 Fatty acid 2.0 2.0 2.0 5.5 Protease 0.7 0.7 0.7 0.4 0.4 Amylase
0.37 0.37 0.37 0.08 0.08 Mannanase 0.03 0.03 Borax (38%) 3.0 3.0
3.0 1.0 MEA Borate 1.5 Calcium and sodium 0.22 0.22 0.22 0.7
formate Amine ethoxylate 1.2 0.5 1.0 1.0 1.5 polymers Zwitterionic
amine 1.0 2.0 1.0 ethoxylate polymer Polyorganosiloxane 0.5 1.0 2.0
1.0 1.0 Fluid - Silicone Resin Mixture.sup.1 DTPA.sup.2 0.25 0.25
0.25 0.3 0.3 Fluorescent 0.2 0.2 0.2 whitening agent Ethanol 2.9
2.9 2.9 1.5 1.5 Propylene Glycol 3.0 5.0 Propanediol 5.0 5.0 5.0
Diethylene glycol 2.56 2.56 2.56 Polyethylene glycol 0.11 0.11 0.11
4000 Monoethanolamine 2.7 2.7 2.7 1.0 0.5 Sodium hydroxide 3.67
3.67 3.67 1.4 1.4 (50%) Sodium cumene 0 0.5 1 0.7 sulfonate
Silicone suds 0.01 0.01 0.01 0.02 suppressor Perfume 0.5 0.5 0.5
0.30 0.3 Dye 0.01 0.01 0.01 0.016 0.016 Opacifier.sup.3 0.01 0.01
0.01 Water balance balance balance balance balance 100.0% 100.0%
100.0% 100.0% 100.0% .sup.1Polyorganosiloxane Fluid-Silicone Resin
Mixture of Example 1 .sup.2Diethylenetriaminepentaacetic acid,
sodium salt .sup.3Acusol OP 301
Example 5
Granular Laundry Detergent Compositions
[0100] In another aspect of the present disclosure, the fabric care
compositions disclosed herein, may take the form of granular
laundry detergent compositions. Such compositions comprise the
dispersant polymer of the present disclosure to provide soil and
stain removal and anti-redeposition, suds boosting, and/or soil
release benefits to fabric washed in a solution containing the
detergent. Typically, the granular laundry detergent compositions
are used in washing solutions at a level of from about 0.0001% to
about 0.05%, or even from about 0.001% to about 0.01% by weight of
the washing solution.
[0101] Detergent compositions may be in the form of a granule.
Typical components of granular detergent compositions include but
are not limited to surfactants, builders, bleaches, bleach
activators and/or other bleach catalysts and/or boosters, enzymes,
enzyme stabilizing agents, soil suspending agents, soil release
agents, pH adjusting agents and/or other electrolytes, suds
boosters or suds suppressers, anti-tarnish and anticorrosion
agents, non-builder alkalinity sources, chelating agents, organic
and inorganic fillers, solvents, hydrotropes, clays, silicones,
flocculant, dye transfer inhibitors, photobleaches, fabric
integrity agents, effervesence-generating agents, processing aids
(non-limiting examples of which include binders and hydrotropes),
germicides, brighteners, dyes, and perfumes. Granular detergent
compositions typically comprise from about 1% to 95% by weight of a
surfactant. Detersive surfactants utilized can be of the anionic,
nonionic, cationic, zwitterionic, ampholytic, amphoteric, or
catanionic type or can comprise compatible mixtures of these
types.
[0102] Granular detergents can be made by a wide variety of
processes, non-limiting examples of which include spray drying,
agglomeration, fluid bed granulation, marumarisation, extrusion, or
a combination thereof. Bulk densities of granular detergents
generally range from about 300 g/1-1000 g/l. The average particle
size distribution of granular detergents generally ranges from
about 250 microns-1400 microns.
[0103] Granular detergent compositions of the present disclosure
may include any number of conventional detergent ingredients. For
example, the surfactant system of the detergent composition may
include anionic, nonionic, zwitterionic, ampholytic and cationic
classes and compatible mixtures thereof. Detergent surfactants for
granular compositions are described in U.S. Pat. Nos. 3,664,961 and
3,919,678. Cationic surfactants include those described in U.S.
Pat. Nos. 4,222,905 and 4,239,659.
[0104] Non-limiting examples of surfactant systems include the
conventional C.sub.11-C.sub.18 alkyl benzene sulfonates ("LAS") and
primary, branched-chain and random C.sub.10-C.sub.20 alkyl sulfates
("AS"), the C.sub.10-C.sub.18 secondary (2,3) alkyl sulfates of the
formula CH.sub.3(CH.sub.2).sub.x(CHOSO.sub.3.sup.-M.sup.+)CH.sub.3
and
CH.sub.3(CH.sub.2).sub.y(CHOSO.sub.3.sup.-M.sup.+)CH.sub.2CH.sub.3
where x and (y+1) are integers of at least about 7, preferably at
least about 9, and M is a water-solubilizing cation, especially
sodium, unsaturated sulfates such as oleyl sulfate, the
C.sub.10-C.sub.18 alkyl alkoxy sulfates ("AE.sub.xS"; especially EO
1-7 ethoxy sulfates), C.sub.10-C.sub.18 alkyl alkoxy carboxylates
(especially the EO 1-5 ethoxycarboxylates), the C.sub.10-C.sub.18
glycerol ethers, the C.sub.10-C.sub.18 alkyl polyglycosides and
their corresponding sulfated polyglycosides, and C.sub.12-C.sub.18
alpha-sulfonated fatty acid esters. If desired, the conventional
nonionic and amphoteric surfactants such as the C.sub.12-C.sub.18
alkyl ethoxylates ("AE") including the so-called narrow peaked
alkyl ethoxylates and C.sub.6-C.sub.12 alkyl phenol alkoxylates
(especially ethoxylates and mixed ethoxy/propoxy),
C.sub.12-C.sub.18 betaines and sulfobetaines ("sultaines"),
C.sub.10-C.sub.18 amine oxides, and the like, can also be included
in the surfactant system. The C.sub.10-C.sub.18 N-alkyl polyhydroxy
fatty acid amides can also be used. See WO 92/06154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty
acid amides, such as C.sub.10-C.sub.18 N-(3-methoxypropyl)
glucamide. The N-propyl through N-hexyl C.sub.12-C.sub.18
glucamides can be used for low sudsing. C.sub.10-C.sub.20
conventional soaps may also be used. If high sudsing is desired,
the branched-chain C.sub.10-C.sub.16 soaps may be used. Mixtures of
anionic and nonionic surfactants are especially useful. Other
conventional useful surfactants are listed in standard texts.
[0105] The cleaning composition can, and in certain embodiments
preferably does, include a detergent builder. Builders are
generally selected from the various water-soluble, alkali metal,
ammonium or substituted ammonium phosphates, polyphosphates,
phosphonates, polyphosphonates, carbonates, silicates, borates,
polyhydroxy sulfonates, polyacetates, carboxylates, and
polycarboxylates. Preferred are the alkali metals, especially
sodium, salts of the above. Preferred for use herein are the
phosphates, carbonates, silicates, C.sub.10-C.sub.18 fatty acids,
polycarboxylates, and mixtures thereof. More preferred are sodium
tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate
mono- and di-succinates, sodium silicate, and mixtures thereof.
[0106] Specific examples of inorganic phosphate builders are sodium
and potassium tripolyphosphate, pyrophosphate, polymeric
metaphosphate having a degree of polymerization of from about 6 to
21, and orthophosphates. Examples of polyphosphonate builders are
the sodium and potassium salts of ethylene diphosphonic acid, the
sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic
acid and the sodium and potassium salts of
ethane-1,1,2-triphosphonic acid. Other phosphorus builder compounds
are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021;
3,422,137; 3,400,176; and 3,400,148. Examples of non-phosphorus,
inorganic builders are sodium and potassium carbonate, bicarbonate,
sesquicarbonate, tetraborate decahydrate, and silicates having a
weight ratio of SiO.sub.2 to alkali metal oxide of from about 0.5
to about 4.0, preferably from about 1.0 to about 2.4.
Water-soluble, non-phosphorus organic builders useful herein
include the various alkali metal, ammonium and substituted ammonium
polyacetates, carboxylates, polycarboxylates and polyhydroxy
sulfonates. Examples of polyacetate and polycarboxylate builders
are the sodium, potassium, lithium, ammonium and substituted
ammonium salts of ethylene diamine tetraacetic acid,
nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, and citric acid.
[0107] Polymeric polycarboxylate builders are set forth in U.S.
Pat. No. 3,308,067. Such materials include the water-soluble salts
of homo- and copolymers of aliphatic carboxylic acids such as
maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic
acid, citraconic acid and methylenemalonic acid. Some of these
materials are useful as the water-soluble anionic polymer as
hereinafter described, but only if in intimate admixture with the
non-soap anionic surfactant. Other suitable polycarboxylates for
use herein are the polyacetal carboxylates described in U.S. Pat.
Nos. 4,144,226 and 4,246,495.
[0108] Water-soluble silicate solids represented by the formula
SiO.sub.2.M.sub.2O, M being an alkali metal, and having a
SiO.sub.2:M.sub.2O weight ratio of from about 0.5 to about 4.0, are
useful salts in the detergent granules of this disclosure at levels
of from about 2% to about 15% on an anhydrous weight basis.
Anhydrous or hydrated particulate silicate can be utilized, as
well.
[0109] Various techniques for forming cleaning compositions in such
solid forms are well known in the art and may be used herein. In
one aspect, when the cleaning composition, such as a fabric care
composition, is in the form of a granular particle, the
polyorganosiloxane-silicone resin mixture is provided in
particulate form, optionally including additional but not all
components of the cleaning composition. The
polyorganosiloxane-silicone resin mixture particulate is combined
with one or more additional particulates containing a balance of
components of the cleaning composition. Further, the
polyorganosiloxane-silicone resin mixture, optionally including
additional but not all components of the cleaning composition may
be provided in an encapsulated form, and the
polyorganosiloxane-silicone resin mixture encapsulate is combined
with particulates containing a substantial balance of components of
the cleaning composition.
Powder Laundry Detergent Formulations
[0110] In this Example, four sample formulations for a powder
laundry detergent are prepared using the polysiloxane-silicone
resin mixture according to embodiments of the present disclosure.
The polyorganosiloxane-silicone resin mixture is added to the
formulations in an amount ranging from 1.0% to 10.0% by weight.
TABLE-US-00007 A B C D Ingredients Wt. % Wt. % Wt. % Wt. % Sodium
16.0000 14.0000 12.0000 7.9 alkylbenzenesulfonate Sodium alkyl
alcohol -- -- -- 4.73 ethoxylate (3) sulfate Sodium mid-cut alkyl
1.5000 1.5000 -- sulfate Alkyl dimethyl -- -- -- 0.5 hydroxyethyl
quaternary amine (chloride) Alkyl ethoxylate 1.3000 1.3000 1.3000
-- Polyamine.sup.1 -- -- -- 0.79 Nonionic Polymer.sup.2 1.0000
1.0000 1.0000 1.0 Carboxymethylcellulose 0.2000 0.2000 0.2000 1.0
Sodium polyacrylate -- -- -- -- Sodium polyacrylate/ 0.7000 0.7000
0.7000 3.5 maleate polymer Polyorganosiloxane 1.0000 1.0000 1.0000
3.0000 Fluid - Silicone Resin Mixture.sup.3 Sodium tripolyphosphate
10.0000 5.0000 -- -- Zeolite 16.0000 16.0000 16.0000 -- Citric Acid
-- -- -- 5.0 Sodium Carbonate 12.5000 12.5000 12.5000 25.0 Sodium
Silicate 4.0 4.0 4.0 -- Enzymes.sup.4 0.30 0.30 0.30 0.5 Minors
including moisture.sup.5 balance balance balance balance
.sup.1Hexamethylenediamine ethoxylated to 24 units for each
hydrogen atom bonded to a nitrogen, quaternized. .sup.2Comb polymer
of polyethylene glycol and polyvinylacetate
.sup.3Polyorganosiloxane Fluid - Silicone Resin Mixture of Example
1 .sup.4Enzyme cocktail selected from known detergent enzymes
including amylase, cellulase, protease, and lipase. .sup.5Balance
to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, soil release polymer,
chelating agents, bleach additives and boosters, dye transfer
inhibiting agents, aesthetic enhancers (example: Speckles),
additional water, and fillers, including sulfate, CaCO.sub.3, talc,
silicates, etc.
Example 6
Automatic Dishwasher Detergent Formulation
[0111] In this Example, five sample formulations for an automatic
dishwasher detergent are prepared using the
polyorganosiloxane-silicone resin mixture according to embodiments
of the present disclosure. The polyorganosiloxane-silicone resin
mixture is added to the formulations in an amount ranging from
0.05% to 15% by weight.
TABLE-US-00008 A B C D E Ingredients Wt. % Wt. % Wt. % Wt. % Wt. %
Polymer dispersant.sup.1 0.5 5 6 5 5 Carbonate 35 40 40 35-40 35-40
Sodium tripolyphosphate 0 6 10 0-10 0-10 Silicate solids 6 6 6 6 6
Bleach and Bleach activators 4 4 4 4 4 Enzymes 0.3-0.6 0.3-0.6
0.3-0.6 0.3-0.6 0.3-0.6 Disodium citrate dihydrate 0 0 0 2-20 0
Nonionic surfactant.sup.2 0 0 0 0 0.8-5.sup. Polyorganosiloxane
Fluid- 0.05-15.sup. 0.05-15.sup. 0.05-15.sup. 0.05-15.sup.
0.05-15.sup. Silicone Resin Mixture.sup.3 Water, sulfate, perfume,
Balance Balance Balance Balance Balance dyes and other adjuncts to
100% to 100% to 100% to 100% to 100% .sup.1Anionic polymers such as
Acusol, Alcosperse and other modified polyacrylic acid polymers.
.sup.2Such as SLF-18 polytergent from Olin Corporation
.sup.3Polyorganosiloxane Fluid - Silicone Resin Mixture of Example
1
Example 7
Liquid Dishwashing Liquid
Liquid Dish Handwashing Detergents
TABLE-US-00009 [0112] Composition A B C.sub.12-13 Natural AE0.6S
270 240 C.sub.10-14 mid-branched Amine Oxide -- 6.0 C.sub.12-14
Linear Amine Oxide 6.0 -- SAFOL .RTM. 23 Amine Oxide 1.0 1.0
C.sub.11E.sub.9 Nonionic .sup.1 2.0 2.0 Ethanol 4.5 4.5 Sodium
cumene sulfonate 1.6 1.6 Polypropylene glycol 2000 0.8 0.8 NaCl 0.8
0.8 1,3 BAC Diamine.sup.2 0.5 0.5 Polyorganosiloxane Fluid -
Silicone 0.05-15 0.05-15 Resin Mixture.sup.3 Water Balance Balance
.sup.1 Nonionic may be either C.sub.11 Alkyl ethoxylated surfactant
containing 9 ethoxy groups. .sup.21,3, BAC is 1,3
bis(methylamine)-cyclohexane. .sup.3Polyorganosiloxane Fluid -
Silicone Resin Mixture of Example 1
Example 8
Unit Dose
[0113] The detergent product of the present invention may comprise
a water-soluble pouch, more preferably a multi-compartment
water-soluble pouch. Such a pouch comprises a water-soluble film
and at least a first, and optionally a second compartment. The
first compartment comprises a first composition, comprising an
opacifier and an antioxidant. The second compartment comprises a
second compartment. Preferably the pouch comprises a third
compartment and a third composition. The optionally second and
third compositions are preferably visibly distinct from each other
and the first composition.
[0114] Optionally, a difference in aesthetic appearance may be
achieved in a number of ways. However the first compartment of the
pouch may comprise an opaque liquid composition. The compartments
of the pouch may be the same size or volume. Alternatively, the
compartments of the pouch may have different sizes, with different
internal volumes.
[0115] The compartments may also be different from one another in
terms of texture. Hence one compartment may be glossy, while the
other is matt. This can be readily achieved as one side of a
water-soluble film is often glossy, while the other has a matt
finish. Alternatively the film used to make a compartment may be
treated in a way so as to emboss, engrave or print the film.
Embossing may be achieved by adhering material to the film using
any suitable means described in the art. Engraving may be achieved
by applying pressure onto the film using any suitable technique
available in the art. Printing may be achieved using any suitable
printer and process available in the art. Alternatively, the film
itself may be colored, allowing the manufacturer to select
different colored films for each compartment. Alternatively the
films may be transparent or translucent and the composition
contained within may be colored.
[0116] Unit dose compositions may have compartments which can be
separate, but are preferably conjoined in any suitable manner. Most
preferably the second and optionally third or subsequent
compartments are superimposed on the first compartment. In one
embodiment, the third compartment may be superimposed on the second
compartment, which is in turn superimposed on the first compartment
in a sandwich configuration. Alternatively the second and third
compartments are superimposed on the first compartment. However it
is also equally envisaged that the first, second and optionally
third and subsequent compartments may be attached to one another in
a side by side relationship. The compartments may be packed in a
string, each compartment being individually separable by a
perforation line. Hence each compartment may be individually
torn-off from the remainder of the string by the end-user, for
example, so as to pre-treat or post-treat a fabric with a
composition from a compartment.
[0117] In a preferred embodiment the pouch may comprise three
compartments consisting of a large first compartment and two
smaller compartments. The second and third smaller compartments are
superimposed on the first larger compartment. The size and geometry
of the compartments are chosen such that this arrangement is
achievable.
[0118] The geometry of the compartments may be the same or
different. In a preferred embodiment the second and optionally
third compartment have a different geometry and shape to the first
compartment. In this embodiment the second and optionally third
compartments are arranged in a design on the first compartment.
Said design may be decorative, educative, illustrative for example
to illustrate a concept or instruction, or used to indicate origin
of the product. In a preferred embodiment the first compartment is
the largest compartment having two large faces sealed around the
perimeter. The second compartment is smaller covering less than
75%, more preferably less than 50% of the surface area of one face
of the first compartment. In the embodiment wherein there is a
third compartment, the above structure is the same but the second
and third compartments cover less than 60%, more preferably less
than 50%, even more preferably less than 45% of the surface area of
one face of the first compartment.
[0119] The pouch is preferably made of a film material which is
soluble or dispersible in water, and has a water-solubility of at
least 50%, preferably at least 75% or even at least 95%, as
measured by the method set out here after using a glass-filter with
a maximum pore size of 20 microns:
[0120] 50 grams.+-.0.1 gram of pouch material is added in a
pre-weighed 400 ml beaker and 245 ml.+-.1 ml of distilled water is
added. This is stirred vigorously on a magnetic stirrer set at 600
rpm, for 30 minutes. Then, the mixture is filtered through a folded
qualitative sintered-glass filter with a pore size as defined above
(max. 20 micron). The water is dried off from the collected
filtrate by any conventional method, and the weight of the
remaining material is determined (which is the dissolved or
dispersed fraction). Then, the percentage solubility or
dispersability can be calculated.
Preferred pouch materials are polymeric materials, preferably
polymers which are formed into a film or sheet. The pouch material
can, for example, be obtained by casting, blow-moulding, extrusion
or blown extrusion of the polymeric material, as known in the
art.
[0121] Preferred polymers, copolymers or derivatives thereof
suitable for use as pouch material are selected from polyvinyl
alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide,
acrylic acid, cellulose, cellulose ethers, cellulose esters,
cellulose amides, polyvinyl acetates, polycarboxylic acids and
salts, polyaminoacids or peptides, polyamides, polyacrylamide,
copolymers of maleic/acrylic acids, polysaccharides including
starch and gelatine, natural gums such as xanthum and carragum.
More preferred polymers are selected from polyacrylates and
water-soluble acrylate copolymers, methylcellulose,
carboxymethylcellulose sodium, dextrin, ethylcellulose,
hydroxyethyl cellulose, hydroxypropyl methylcellulose,
maltodextrin, polymethacrylates, and most preferably selected from
polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl
methyl cellulose (HPMC), and combinations thereof. Preferably, the
level of polymer in the pouch material, for example a PVA polymer,
is at least 60%. The polymer can have any weight average molecular
weight, preferably from about 1000 to 1,000,000, more preferably
from about 10,000 to 300,000 yet more preferably from about 20,000
to 150,000.
[0122] Mixtures of polymers can also be used as the pouch material.
This can be beneficial to control the mechanical and/or dissolution
properties of the compartments or pouch, depending on the
application thereof and the required needs. Suitable mixtures
include for example mixtures wherein one polymer has a higher
water-solubility than another polymer, and/or one polymer has a
higher mechanical strength than another polymer. Also suitable are
mixtures of polymers having different weight average molecular
weights, for example a mixture of PVA or a copolymer thereof of a
weight average molecular weight of about 10,000-40,000, preferably
around 20,000, and of PVA or copolymer thereof, with a weight
average molecular weight of about 100,000 to 300,000, preferably
around 150,000. Also suitable herein are polymer blend
compositions, for example comprising hydrolytically degradable and
water-soluble polymer blends such as polylactide and polyvinyl
alcohol, obtained by mixing polylactide and polyvinyl alcohol,
typically comprising about 1-35% by weight polylactide and about
65% to 99% by weight polyvinyl alcohol. Preferred for use herein
are polymers which are from about 60% to about 98% hydrolysed,
preferably about 80% to about 90% hydrolysed, to improve the
dissolution characteristics of the material.
[0123] Naturally, different film material and/or films of different
thickness may be employed in making the compartments of the present
invention. A benefit in selecting different films is that the
resulting compartments may exhibit different solubility or release
characteristics.
[0124] Most preferred pouch materials are PVA films known under the
trade reference Monosol M8630, as sold by Chris-Craft Industrial
Products of Gary, Ind., US, and PVA films of corresponding
solubility and deformability characteristics. Other films suitable
for use herein include films known under the trade reference PT
film or the K-series of films supplied by Aicello, or VF-HP film
supplied by Kuraray.
[0125] The pouch material herein can also comprise one or more
additive ingredients. For example, it can be beneficial to add
plasticizers, for example glycerol, ethylene glycol,
diethyleneglycol, propylene glycol, sorbitol and mixtures thereof.
Other additives include functional detergent additives to be
delivered to the wash water, for example organic polymeric
dispersants, etc.
[0126] For reasons of deformability pouches or pouch compartments
containing a component which is liquid will preferably contain an
air bubble having a volume of up to about 50%, preferably up to
about 40%, more preferably up to about 30%, more preferably up to
about 20%, more preferably up to about 10% of the volume space of
said compartment.
[0127] The water soluble pouch may be made using any suitable
equipment and method. Single compartment pouches are made using
vertical, but preferably horizontal form filling techniques
commonly known in the art. The film is preferably dampened, more
preferably heated to increase the malleability thereof. Even more
preferably, the method also involves the use of a vacuum to draw
the film into a suitable mould. The vacuum drawing the film into
the mould can be applied for 0.2 to 5 seconds, preferably 0.3 to 3
or even more preferably 0.5 to 1.5 seconds, once the film is on the
horizontal portion of the surface. This vacuum may preferably be
such that it provides an under-pressure of between -100 mbar to
-1000 mbar, or even from -200 mbar to -600 mbar.
[0128] The moulds, in which the pouches are made, can have any
shape, length, width and depth, depending on the required
dimensions of the pouches. The moulds can also vary in size and
shape from one to another, if desirable. For example, it may be
preferred that the volume of the final pouches is between 5 and 300
ml, or even 10 and 150 ml or even 20 and 100 ml and that the mould
sizes are adjusted accordingly.
[0129] Heat can be applied to the film, in the process commonly
known as thermoforming, by any means. For example the film may be
heated directly by passing it under a heating element or through
hot air, prior to feeding it onto the surface or once on the
surface. Alternatively it may be heated indirectly, for example by
heating the surface or applying a hot item onto the film. Most
preferably the film is heated using an infra red light. The film is
preferably heated to a temperature of 50 to 120.degree. C., or even
60 to 90.degree. C. Alternatively, the film can be wetted by any
mean, for example directly by spraying a wetting agent (including
water, solutions of the film material or plasticizers for the film
material) onto the film, prior to feeding it onto the surface or
once on the surface, or indirectly by wetting the surface or by
applying a wet item onto the film.
[0130] Once a film has been heated/wetted, it is drawn into an
appropriate mould, preferably using a vacuum. The filling of the
molded film can be done by any known method for filling (preferably
moving) items. The most preferred method will depend on the product
form and speed of filling required. Preferably the molded film is
filled by in-line filling techniques. The filled, open pouches are
then closed, using a second film, by any suitable method.
Preferably, this is also done while in horizontal position and in
continuous, constant motion. Preferably the closing is done by
continuously feeding a second film, preferably water-soluble film,
over and onto the open pouches and then preferably sealing the
first and second film together, typically in the area between the
moulds and thus between the pouches.
[0131] Preferred methods of sealing include heat sealing, solvent
welding, and solvent or wet sealing. It is preferred that only the
area which is to form the seal, is treated with heat or solvent.
The heat or solvent can be applied by any method, preferably on the
closing material, preferably only on the areas which are to form
the seal. If solvent or wet sealing or welding is used, it may be
preferred that heat is also applied. Preferred wet or solvent
sealing/welding methods include applying selectively solvent onto
the area between the moulds, or on the closing material, by for
example, spraying or printing this onto these areas, and then
applying pressure onto these areas, to form the seal. Sealing rolls
and belts as described above (optionally also providing heat) can
be used, for example.
[0132] The formed pouches can then be cut by a cutting device.
Cutting can be done using any known method. It may be preferred
that the cutting is also done in continuous manner, and preferably
with constant speed and preferably while in horizontal position.
The cutting device can, for example, be a sharp item or a hot item,
whereby in the latter case, the hot item `burns` through the
film/sealing area.
[0133] The different compartments of a multi-compartment pouch may
be made together in a side-by-side style and consecutive pouches
are not cut. Alternatively, the compartments can be made
separately.
[0134] According to this process and preferred arrangement, the
pouches are made according to the process comprising the steps of:
a) forming an first compartment (as described above); b) forming a
recess within some or all of the closed compartment formed in step
a), to generate a second moulded compartment superposed above the
first compartment; c) filling and closing the second compartments
by means of a third film; d) sealing said first, second and third
films; and e) cutting the films to produce a multi-compartment
pouch.
[0135] Said recess formed in step b) is preferably achieved by
applying a vacuum to the compartment prepared in step a).
Alternatively the second, and optionally third, compartment(s) can
be made in a separate step and then combined with the first
compartment as described in our co-pending application EP
08101442.5 which is incorporated herein by reference. A
particularly preferred process comprises the steps of: a) forming a
first compartment, optionally using heat and/or vacuum, using a
first film on a first forming machine; b) filling said first
compartment with a first composition; c) on a second forming
machine, deforming a second film, optionally using heat and vacuum,
to make a second and optionally third moulded compartment; d)
filling the second and optionally third compartments; e) sealing
the second and optionally third compartment using a third film; f)
placing the sealed second and optionally third compartments onto
the first compartment; g) sealing the first, second and optionally
third compartments; and h) cutting the films to produce a
multi-compartment pouch
[0136] The first and second forming machines are selected based on
their suitability to perform the above process. The first forming
machine is preferably a horizontal forming machine. The second
forming machine is preferably a rotary drum forming machine,
preferably located above the first forming machine.
[0137] It will be understood moreover that by the use of
appropriate feed stations, it is possible to manufacture
multi-compartment pouches incorporating a number of different or
distinctive compositions and/or different or distinctive liquid,
gel or paste compositions.
Detergent Composition of the Unit Dose Product
[0138] At least one of the compartments of the unit dose product
comprises the main wash detergent composition. One embodiment of
the Unit Dose Product Detergent is shown below.
Unit Dose Composition
TABLE-US-00010 [0139] Wt % Glycerol (min 99) 5.3 1,2-propanediol
10.0 Citric Acid 0.5 Monoethanolamine 10.0 Caustic soda -- Dequest
2010 1.1 Potassium sulfite 0.2 Nonionic Marlipal C24EO7 20.1 HLAS
24.6 Optical brightener FWA49 0.2 Polyorganosiloxane Fluid -
Silicone Resin Mixture.sup.1 0.05-15 C12-15 Fatty acid 16.4 Polymer
Lutensit Z96 2.9 Polyethyleneimine ethoxylate PEI600 E20 1.1 MgCl2
0.2 Enzymes ppm .sup.1Polyorganosiloxane Fluid - Silicone Resin
Mixture of Example 1
Processes of Making Cleaning Compositions
[0140] The cleaning compositions, such as, but not limited to, the
fabric care compositions of the present disclosure can be
formulated into any suitable form and prepared by any process
chosen by the formulator, non-limiting examples of which are
described in U.S. Pat. Nos. 5,879,584; 5,691,297; 5,574,005;
5,569,645; 5,565,422; 5,516,448; 5,489,392; and 5,486,303.
Methods of Using Fabric Care Compositions
[0141] The fabric care compositions disclosed in the present
specification may be used to clean or treat a fabric, such as those
described herein. Typically at least a portion of the fabric is
contacted with an embodiment of the aforementioned fabric care
compositions, in neat form or diluted in a liquor, for example, a
wash liquor and then the fabric may be optionally washed and/or
rinsed. In one aspect, a fabric is optionally washed and/or rinsed,
contacted with an embodiment of the aforementioned fabric care
compositions and then optionally washed and/or rinsed. For purposes
of the present disclosure, washing includes but is not limited to,
scrubbing, and mechanical agitation. The fabric may comprise most
any fabric capable of being laundered or treated.
[0142] The fabric care compositions disclosed in the present
specification can be used to form aqueous washing solutions for use
in the laundering of fabrics. Generally, an effective amount of
such compositions is added to water, preferably in a conventional
fabric laundering automatic washing machine, to form such aqueous
laundering solutions. The aqueous washing solution so formed is
then contacted, preferably under agitation, with the fabrics to be
laundered therewith. An effective amount of the fabric care
composition, such as the liquid detergent compositions disclosed in
the present specification, may be added to water to form aqueous
laundering solutions that may comprise from about 500 to about
7,000 ppm or even from about 1,000 to about 3,000 pm of fabric care
composition.
[0143] In one aspect, the fabric care compositions may be employed
as a laundry additive, a pre-treatment composition and/or a
post-treatment composition.
[0144] While various specific embodiments have been described in
detail herein, the present disclosure is intended to cover various
different combinations of the disclosed embodiments and is not
limited to those specific embodiments described herein. The various
embodiments of the present disclosure may be better understood when
read in conjunction with the following representative examples. The
following representative examples are included for purposes of
illustration and not limitation.
Test Methods
Time-to Wick (T2W) Measurement Protocol
[0145] The fabric Time to Wick property is measured as follows: The
test is conducted in a room or chamber with air temperature of
20-25.degree. C. and Relative Humidity of 50-60%. All fabrics and
paper products used in the test are equilibrated in the temperature
and humidity condition of the test location for 24 hrs prior to
collecting measurements. On a flat, horizontal and level,
impermeable surface, place 1 piece of test fabric 8 cm.times.10 cm
in size, on top of a single sheet of kitchen paper towel (eg
Bounty). The fabric surface facing upwards, which is not in contact
with the paper towel, can be either side of the fabric. Visually
confirm that the fabric is lying flat and in uniform contact with
the paper towel before proceeding. Distilled Water is used as the
testing liquid. Automated single or multi-channel pipettes (eg
Rainin, Gilson, Eppendorf), are used to deliver a liquid droplet
size of 300 .mu.L of the testing liquid onto the fabric surface. A
stop-watch or timer is used to count time in seconds, from the
moment when the liquid droplet contacts the fabric surface. The
timer is stopped when the whole droplet of the test liquid wets
into the fabric. The point when the liquid droplet wets into the
fabric is determined by visual observation that the liquid droplet
has moved from sitting above the fabric surface to having
completely penetrated into the fabric. The time period shown
elapsed on the timer is the Time to Wick Measurement. The test is
stopped after 20 minutes if wetting of the liquid droplet has not
been seen yet. The Time to Wick measurement is recorded as >20
mins in this case. If wetting of the liquid is seen immediately
upon contact of the droplet with the fabric surface, then the Time
to Wick property is recorded as 0 for that fabric. Multiple repeats
are performed for each test fabric. These replicates are comprised
of 10 pieces of each test fabric, and 3 droplets of test liquid per
piece of fabric, resulting in a total of 30 droplets being measured
per test fabric. In addition to the average of the 30 Time to Wick
measurements, the Standard Deviation and the 95% confidence
interval should also be reported.
[0146] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm"
[0147] Every document cited herein, including any cross referenced
or related patent or application, is hereby incorporated herein by
reference in its entirety unless expressly excluded or otherwise
limited. The citation of any document is not an admission that it
is prior art with respect to any invention disclosed or claimed
herein or that it alone, or in any combination with any other
reference or references, teaches, suggests or discloses any such
invention. Further, to the extent that any meaning or definition of
a term in this document conflicts with any meaning or definition of
the same term in a document incorporated by reference, the meaning
or definition assigned to that term in this document shall
govern.
[0148] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *