Note: Descriptions are shown in the official language in which they were submitted.
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Liquid Laundry Detergent Compositions with Silicone Fabric Care Agents
Field of the Invention
This invention relates to liquid laundry detergent compositions containing
functionalized
silicone materials as fabric care agents.
Background of the Invention
When consumers launder fabrics, they desire not only excellence in cleaning,
they also
seek to impart superior fabric care benefits via the laundering process. Such
fabric care benefits
to be imparted can be exemplified by one or more of reduction, prevention or
removal of
wrinkles; the improvement of fabric softness, fabric feel or garment, shape
retention or recovery;
improved elasticity; ease of ironing benefits; color care; anti-abrasion; anti-
pilling; or any
combination of such benefits. Detergent compositions which provide both fabric
cleaning
performance and additional fabric care effects, e.g., fabric softening
benefits, are known as "2-in-
1"-detergent compositions and/or as "softening-through-the-wash"-compositions.
Due to the incompatibility of anionic detersive surfactants and many cationic
fabric care
agents, e.g.~ quaternary ammonium fabric softening agents, in liquid detergent
compositions, the
detergent industry has formulated alternative compositions which utilize
fabric care agents which
are not necessarily cationic in nature. One such type of alternative fabric
care agents comprises
silicone, i.e., polysiloxane-based, materials. Silicone materials include
nonfunctional types such
as polydimethylsiloxane (PDMS) and functionalized silicones, and can be
deposited onto fabrics
during the wash cycle of the laundering process. Such deposited silicone
materials can provide a
variety of benefits to the fabrics onto which they deposit. Such benefits
include those listed
hereinbefore.
Non-functionalized silicones, however good in their compatibility with
detergents, have
shortcomings. Such non-functionalized silicones can produce excellent fabric
care benefits when
directly applied to textiles, yet are found to work ineffectively in liquid
laundry detergents. The
problem is a complex one and includes inadequate deposition in the presence of
surfactants,
unsatisfactory spreading, inadequate emulsion stability and other factors.
When such non-
functional materials do not deposit effectively, a major proportion of the
silicone is lost to the
drain at the end of the wash, rather than being deposited evenly and uniformly
on the fabrics, e:g.,
clothing, being washed.
One specific type of silicones which can provide especially desirable
deposition and
fabric substantivity improvements comprises the functionalized, nitrogen-
containing silicones.
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These are materials wherein the organic substituents of the silicon atoms in
the polysiloxane chain
contain one or more amino and/or quaternary ammonium moieties. The terms
"amino" and
"ammonium" in this context most generally means that there is at least one
substituted or
unsubstituted amino or ammonium moiety covalently bonded to, or covalently
bonded in, a
polysiloxane chain and the covalent bond is other than an Si-N bond, e.g., as
in the moieties -
[Si]-O-CR'2-NR3 , -[Si]-O-CR'Z-NR3 -[Si]-OCR'Z-N~ , -[Si]-OCR'2-N~'HRZ -[Si]-O-
CR'Z-
N+HRZ -[Si]-CR'2-NR3 etc. where -[Si]- represents one silicon atom of a
polysiloxane chain.
Amino and ammonium functionalized silicones as fabric care and fabric
treatment agents are
described, for example, in EP-A-150,872; EP-A-577,039; EP-A-1,023,429; EP-A-
1,076,129; and
WO 02/018528.
Functionalized, nitrogen-containing silicones such as these can be used in and
of
themselves to impart a certain amount and degree of fabric care benefit.
However such
functionalized silicones also have shortcomings. For example it is known that
they can react
chemically with components of detergents. Mechanisms of reaction have not been
well
documented but can in principle include reactions of aminofunctional groups
themselves, as well
as reactions of curable groups present within such functionalized polymers.
The art is ambivalent
on the possibility of successfully including reactive or curable silicones in
detergents without
stability problems. On one hand there are references teaching desirablity of
having curable or
reactive moieties, and on the other hand there are references teaching
desirability of avoiding all
reactive moieties (in this context including ammonium or aminofunctional
moieties) in various
cleaning compositions.
Functionalized, nitrogen-containing silicone materials useful as fabric care
agents can be
prepared from nitrogen-substituted alkoxysilanes or alkoxysiloxanes as
starting materials. (See
for example, the processes disclosed in EP-A-269,886 and US-A-6,093,841.) Such
preparation
can involve hydrolysis of the starting materials followed by catalytic
equilibration and
condensation with non-functionalized siloxanes. Depending on the process
involved and
conditions used, the resulting amino or ammonium functionalized silicones will
contain reactive
groups on the silicon atoms, and especially the terminal silicon atoms, of the
siloxane chains in
such reaction product material. Such reactive groups can comprise -H, -OH, and
-OR moieties
originally present in the silane and siloxane starting materials. In view of
the state of the art it is
not currently possible to predict what overall structures, and what levels of
reactive groups in
particular, can be accommodated in a stable and effective fabric-care-benefit-
providing liquid
laundry detergent composition. Yet, it would be highly desirable to solve this
problem in order
that synthesis routes such as the above, found desirable for manufacturing
reasons, can be applied
to the provision of improved fabric care detergents.
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Processes which remove reactive groups from the functionalized silicone end
product
serve to render those end products "nonreactive." However, it is desirable to
conduct such
additional processes only to the minimum extent required for good liquid
detergent fabric care
benefit performance and stability, or the processes are wasteful and costly.
The problem of
determining the correct composition of miscible blends of silicones in terms
of structure and in
terms of parameters such as nitrogen content and reactive group content so as
to select preferred
fabric care liquid laundry detergents has now been solved.
It has now been determined what concentrations of residual reactive groups can
cause
problems when the resulting functionalized silicone materials are used as, or
as part of, fabric care
agents in liquid detergent compositions. The use of silicones containing these
reactive group
concentrations leads to deactivation of the functionalized silicones
themselves and/or to
deactivation of other components of the liquid detergent compositions. Use in
liquid detergents
of functionalized silicones with significant levels of reactive groups can
also lead to formation of
higher molecular weight, higher viscosity, or unspreadable polymeric materials
upon storage of
the liquid detergent products and this in turn leads to severe reduction or
even loss of fabric care
benefits either immediately or on storage and with passage of time.
It has now been discovered that such problems can be negated or minimized by
using in
liquid laundry detergent products droplets of a silicone blend of preferably
miscible silicones
comprising certain amino and ammonium functionalized silicone material in
combination with
certain kinds of non-functionalized polysiloxanes. The amino and ammonium
functionalized
silicones used are those which have been prepared in a manner to minimize the
presence therein
of certain types of reactive moieties. These selected amino and ammonium
functionalized
silicones are also those which have a specific balance of amine and/or
ammonium functionality,
as quantified by nitrogen content, and silicone viscosity and preferably
molecular weight. Without
being limited by theory, the nitrogen content is fundamentally linked to the
ability to obtain
miscibility of the functionalized and non-functionalized silicones, and the
blend combination of
the two acts synergistically. Moreover, while the levels of reactive group
content needed are low,
they do not need to be zero. This is believed to be due, at least in part, to
the ability of the non-
functionalized silicone to protect the functionalized silicone from
interaction with other
components of the detergent composition. Furthrmore, use of combinations of
functionalized and
non-functionalized silicones also permits formulation of liquid detergent
products which do not
need to contain a cationic deposition aid or a coacervate phase-forming
polymer in order to
promote deposition of the silicone materials onto fabrics.
The present invention therefore offers numerous advantages. First, an improved
aqueous
liquid laundry detergent having excellent fabric care benefits, especially
softness and handle, is
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obtained. Second, use of wasteful levels of silicones is avoided. Third, the
more expensive and
complex functionalized silicones can be used at reasonable levels. Fourth, the
compositions are
stable and effective for their intended industrial purposes. Other advantages
include that the
compositions are non-yellowing on white textiles and moreover, that they do
not give uneven
deposition or lead to unacceptable visual results on clothing.
Summary of the Invention
The present invention is directed to aqueous (e.g., containing upwards of from
4% by weight
water) liquid laundry detergent compositions which are suitable for cleaning
and imparting fabric
care benefits to fabrics laundered using such a composition. Such compositions
comprise:
(A) at least one detersive surfactant selected from anionic surfactants,
nonionic surfactants,
zwitterionic surfactants, amphoteric surfactants, and combinations thereof;
(B) droplets of a blend of silicone materials wherein the blend comprises both
amino- and/or
ammonium- functionalized polysiloxanes and nitrogen-free, non-functionalized
polysiloxanes; and,
(C) at least one additional non-silicone laundry adjunct selected from
detersive enzymes; dye
transfer inhibiting agents, optical brighteners, suds suppressors, and
combinations thereof.
The specific amino and/or ammonium functionalized polysiloxane materials used
are those
which have been prepared by a process which intrinsically leaves
reactive/curable groups in the
functionalized polysiloxane material which is produced. Preferably such a
process comprises
hydrolysis of nitrogen-containing alkoxysilane and/or allcoxysiloxane starting
materials and
catalytic equilibration and condensation of these hydrolyzed starting
materials. Notwithstanding
the tendency of the process used to leave reactive/curable groups within the
resulting
functionalized polysiloxane materials, such materials must be further
processed in a manner
which reduces and minimizes the amount of such reactivelcurable groups which
remain. In fact,
the amino and/or ammonium functionalized polysiloxane materials used must have
a molar ratio
of curable/reactive group-containing , silicon atoms to terminal silicon atoms
containing no
reactive/curable groups which is less than 30%. Syntheses of the
functionalized silicones are
adapted herein to secure appropriate curable/reactive group contents, which
can theoretically be
zero or, more economically, can be non-zero while remaining at low and
compatible levels. Such
amino and/or ammonium functionalized polysiloxane materials also have a
nitrogen content
ranging from 0.05% to 0.5% by weight and a viscosity at 20 °C ranging
from 0.00002 mz/s to 2.0
ma/s.
The nitrogen-free, non-functionalized polysiloxane material which forms part
of the
silicone blend has a viscosity which ranges from O.Olmz/s to 2~Om2/s. It is
present in an amount
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such that the weight iatio of functionalized to non-functionalized siloxanes
within the silicone
blend ranges from 100:1 to 1:100. The functionalized silicone and nitrogen-
free, non-
functionalized polysiloxane materials are preferably fully miscible at the
specified nitrogen
content of the functionalized silicone. This leads to droplets of the
resulting blend which are
more effective for providing fabric care benefits, e.g., softness or feel of
textiles on the skin, than
either of the materials alone.
These compositions are essentially free of any coacervate phase-forming
polymers. Likewise such compositions are essentially free of any cationic
deposition aids.
Detailed Description of the Invention
The essential and optional components of the liquid laundry detergent
compositions herein, as well as composition form, preparation and use, are
described in greater
detail as follows: In this description, all concentrations and ratios are on a
weight basis of the
liquid laundry detergent unless otherwise specified. Percentages of certain
compositions herein,
such as silicone emulsions prepared independently of the liquid laundry
detergent, are likewise
percentages by weight of the total of the ingredients that are combined to
form these
compositions. Elemental compositions such as percentage nitrogen (%I~ are
percentages by
weight of the silicone referred to.
Molecular weights of polymers are number average molecular weights unless
otherwise
specifically indicated. Particle size ranges are ranges of median particle
size. For example a
particle size range of from 0.1 micron to 200 micron refers to the median
particle size having a
lower bound of 0.1 micron and an upper bound of 200 microns. Particle size may
be measured by
means of a laser scattering technique, using a Coulter LS 230 Laser
Diffraction Particle Size
Analyser from Coulter Corporation, Miami, Florida, 33196, USA.
Viscosity is measured with a Carrimed CSL2 Rheometer at a shear rate of 21 sec
1.
Viscosity expressed in m2lsec can be multiplied by 1,000,000 to obtain
equivalent values in
Centistokes (Cst). Viscosity expressed in Cst can be divided by 1,000,000 to
obtain equivalent
values in m2/sec. Additionally, Kinematic viscosity can be converted to
Absolute viscosity using
the following conversion: multiply kinematic viscosity given in centistokes by
density
(grams/cm3) to get absolute viscosity in centipoise (cp or cps).
All documents cited herein are, in relevant part, incorporated herein by
reference. The
citation of any document is not to be considered as an admission that it is
prior art with respect to
the present invention.
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A) Surfactants - The present compositions comprise as one essential component
at least
one surfactant selected from the group consisting anionic surfactants,
nonionic surfactants,
zwitterionic surfactants, amphoteric surfactants, and combinations thereof.
The surfactant
component can be employed in any concentration which is conventionally used to
effectuate
cleaning of fabrics during conventional laundering processes such as those
carned out in
automatic washing machines in the home. Suitable surfactant component
concentrations include
those within the range from 5% to 80%, preferably from 7% to 65%, and more
preferably from
10% to 45%, by weight of the composition.
Any detersive surfactant known for use in conventional laundry detergent
compositions
may be utilized in the compositions of this invention. Such surfactants, for
example include those
disclosed in "Surfactant Science Series", Vol. 7, edited by W. M. Linfield,
Marcel Dekker. Non-
limiting examples of anionic, nonionic, zwitterionic, amphoteric or mixed
surfactants suitable for
use in the compositions herein are described in McCutcheon's, Emulsifiers and
Detergents, 1989
Annual, published by M. C. Publishing Co., and in U.S. Patent Nos. 5,104,646;
5,106,609;
3,929,678; 2,658,072; 2,438,091; and 2,528,378.
Preferred anionic surfactants useful herein include the alkyl benzene sulfonic
acids and their
salts as well as alkoxylated or un-alkoxylated alkyl sulfate materials. Such
materials will
generally contain form 10 to 18 carbon atoms in the alkyl group. Preferred
nonionic surfactants
for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol
alkoxylates are
materials which correspond to the general formula:
Rl(CmH2mC)nCH
wherein Rl is a Cg - C16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12.
Preferably Rl 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.
Preferably also the
alkoxylated fatty alcohols will 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.
B) Silicone Component - The present compositions essentially contain droplets
of a
blend of certain types of silicone materials. This blend of silicone materials
comprises both
amino and/or ammonium group-containing functionalized polysiloxane materials
and nitrogen-
free, non-functionalized polysiloxane materials. (For purposes of describing
this invention, the
terms "polysiloxane" and "silicone" can be and are herein used
interchangeably.)
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Both the functionalized and non-functionalized polysiloxanes used in the
silicone blend are
built up from siloxy units which are chosen from the following groups:
O ~i,
Ri Ri Ri
-O i; Si-O -O i; Si-O i= -O i; Si-O ~i~ -O y; Si-
i2 Rl
O ~i~ O ~i= R' Ri
CT) CD)
wherein the R' substituents represent organic radicals, which can be identical
or different from
one another. In the amino or ammonium group-containing functionalized
polysiloxanes used
herein, at least one of the R' groups essentially comprises nitrogen in the
form of an amino or
quaternary moiety, and optionally and additionally may comprise nitrogen in
the form of an
amide moiety so as to form an amino-amide. In the non-functionalized
polysiloxanes used herein,
none of the R' groups are substituted with nitrogen in the form of an amino or
quaternary
ammonium moiety.
The R' groups for each type of polysiloxanes correspond 'to those defined more
particularly in one or more of the additional general formulas set forth
hereinafter for these
respective types of polysiloxane materials. However, these Q, T, D and M
designations for these
several siloxy unit types will be used in describing the preparation of the
functionalized
polysiloxanes in a manner which minimizes the content of reactive groups in
these functionalized
materials. These Q, T, D and M designations are also used in describing the
NMR monitoring of
the preparation of these materials and the use of NMR techniques to determine
and confirm
reactive group concentrations.
(b1) Functionalized Polysiloxanes:
For purpose of the present invention, the functionalized silicone is a
polymeric mixture of
molecules each having a straight, comb - like or branched structure containing
repeating Si0
groups. The molecules comprise functional substituents which comprise at least
one nitrogen
atom which is not directly bonded to a silicon atom. The functionalized
silicones selected for use
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in the compositions of the present inventions include amino-functionalized
silicones, i.e., there are
silicone molecules present that contain at least one primary amine, secondary
amine, or tertiary
amine. Quaternized amino-functionalized silicones, i.e. quaternary ammonium
silicones, are also
encompassed by the definition of functionalized silicones for the purpose of
the present invention.
The amino groups can be modified, hindered or blocked in any known manner
which prevents or
reduces the known phenomenon of aminosilicone fabric care agents to cause
yellowing of fabrics
treated therewith if, for example, materials too high in nitrogen content are
employed.
The functionalized silicone component of the silicone blend will generally be
straight-
chain, or branched polysiloxane compounds which contain amino or ammonium
groups in the
side groups (i.e., the amino or ammonium groups are present in groups having
general structures
designated D or T) or at the chain ends (i.e., the amino or ammonium groups
are present in groups
having general structures designated M). Furthermore, in such functionalized
silicones the molar
ratio of curable/reactive group-containing silicon atoms to non-
curable/reactive group-containing
terminal silicon atoms, e.g., the molar ratio of hydroxyl- and alkoxy-
containing silicon atoms to
non-hydroxyl- or alkoxy-containing terminal silicon atoms, is from 0% to no
more than 30%, i.e.,
0.3 mole fraction. This includes, in preferred embodiments, low but non-zero
levels that are
preferably less than 20%, more preferably less than 10%, more preferably less
than 5%, more
preferably still, less than 1% Suitably this low level of reactive groups, as
determined on the neat
(undiluted, not yet formulated) functionalized silicone dissolved at a
concentration of, for
example, 20% by weight in a solvent such as deuterated chloroform is from
about the practical
analytical detection threshold (nuclear magnetic resonance) to no more than
30%.
"Hydroxyl- and alkoxy-containing silicon atoms" in this context means all M,
D, T and Q
groups which contain an Si-OH or Si-OR grouping. (It should be noted that D
groups which
contain -OH or -OR substituents on the silicon atom will generally comprise
the terminal Si atoms
of the polysiloxane chain.) The "non-hydroxyl- or alkoxy-containing terminal
silicon atoms"
means all M groups which contain neither a Si-OH nor a Si-OR group. This molar
ratio of
hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-
containing terminal
silicon atoms is expediently determined according to the present invention by
nuclear magnetic
resonance (NMR) spectroscopy methods, preferably by 1 H-NMR and a9 Si-NMR,
particularly
preferably by 29 Si-NMR. According to this invention, this molar ratio of
hydroxyl- and alkoxy-
containing silicon atoms to non-hydroxyl- or alkoxy-containing terminal
silicon atoms is
expediently the ratio of the integrals of the corresponding signals in a9 Si-
NMR.
The molar ratio used herein can be determined, for example in the case of the
functionalized silicone having Formula B hereinafter and where Rl = methyl,
aminopropyl and
methoxy, from the ratio of the signal integrals (I) at shifts represented by:
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-11 ppm (D-OH = (CH3)2(HO)Si0-),
-13 ppm (D-OMe = (CH3)z(CH30)Si0-) and
7 ppm (M = (CH3)3Si0-).
Thus the Ratio = (I_llppm "f" I_l3ppm)~7ppm x 100%. (For purposes of this
invention, this molar ratio is
expressed as a percentage which is referred to as the percent content of
curable/reactive groups in
the functionalized silicone.)
For other alkoxy groupings, such as, for example, ethoxy, signals in the a9Si-
NMRcan be
assigned accordingly. The NMR practitioner is readily able to assign the
corresponding chemical
shifts for differently substituted siloxy units. It is also possible to use
the 1H-NMR method in
addition to the a9Si-NMR method. A suitable set of NMR conditions, procedures
and parameters
is set forth in the Examples hereinafter. Infra-red spectroscopy can also be
used.
According to the invention, it is furthermore preferable that not only is the
molar ratio of
hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-
containing terminal
silicon atoms less than 20%, but also the molar ratio. of all the silicon
atoms carrying reactive
groups to the non-reactive M groups is less than 20%. The limit value of 0% in
the context of the
invention means that preferably silicon atoms containing reactive groups can
no longer be
detected by suitable analytical methods, such as NMR spectroscopy or infra-red
spectroscopy. It
should be noted that, in view of the preparative methods for the
functionalized silicone materials,
having no reactive groups or having them at very limited levels does not
follow automatically
from mere presentation of chemical structures not having such reactive groups.
Rather, reactive
group content must be practically secured at the specified levels by adapting
the synthesis
procedure for these materials, as is provided for herein.
In the context of this invention, non-reactive chain-terminating M groups
represent
structures which, in the environment of the detergent formulations herein, are
not capable of
forming covalent bonds with a resulting increase in the molecular weight of
materials formed. In
such non-reactive structures, the substituents Rl include, for example, Si-C-
linked alkyl, alkenyl,
alkynyl and aryl radicals, which optionally can be substituted by N, O, S and
halogen. The
substituents are preferably Cl to C,2 alkyl radicals, such as methyl, ethyl,
vinyl, propyl, isopropyl,
butyl, hexyl, cyclohexyl and ethylcyclohexyl.
In the context of the invention, M, D, T and Q structures with
curable/reactive groups
mean and represent, in particular, structures which do not contain the amino
or quaternary
nitrogen moieties and which, in the environment of the detergent formulations
herein, are capable
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of forming covalent bonds, thereby creating material of increased molecular
weight. In such
structures, the predominant curable/reactive units are the Si-OH and SiOR
units as mentioned,
and can furthermore also include epoxy andlor ---SiHand/or acyloxysilyl
groups, and/or Si-N-C-
linked silylamines and/or Si-N-Si-linked silazanes. Examples of alkoxy-
containing silicon units
are the radicals ---SiOCH3, ---SiOCH2CH3, ---SiOCH(CH3)2, =SiOCH2CH2CH2CH3 and
---SiOC6H5.
An example of an acyloxysilyl radical is ---SiOC(O)CH3. For silylamine groups,
---SiN(H)CH2CH=CHa may be mentioned by way of example, and for silazane units
---SiN(H)Si(CH3)3.
The primary reaction of the abovementioned curable/reactive groups present,
for example
in detergent formulations, which reaction leads to the undesirable increase in
molecular weight of
the functionalized silicone, is condensation and elimination with subsequent
formation of new
SiOSi bonds not originally present in the functionalized silicone.
Alternatively, it is conceivable
that in detergent formulations, for example, strong interactions occur with
non-volatile
polyhydroxy compounds, polycarboxy compounds or salts thereof, sulfonic acids
or salts thereof,
monoalkyl sulphates, monoalkyl ether-sulphates, carboxylic acids or salts
thereof and carbonates,
leading to an uncontrolled reaction or coordination of the aminosiloxane with
reaction of the
reactive groups mentioned, such as, in particular, the Si-OH and SiOR groups,
with formation of
material of increased molecular weight. It is not the precise nature of the
chemical reaction or
interaction which is essential in the context of the invention. Rather, it is
the fact that these
transformations occur which leads to a decrease in the fabric benefit effects
provided by the
amino- and/or ammoniumpolysiloxane if the molar ratio of reactive/curable
group-containing
silicon atoms to non-reactive/curable group-containing silicon atoms i.e., the
molar ratio of
hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-
containing terminal
silicon atoms, is more than the specified limited levels, for example in a
detergent matrix over a
relatively long period of time.
The functionalized silicones used herein and having the requisite levels of
reactive groups
can be prepared by a process which involves:
i) hydrolysis of alkoxysilanes or alkoxysiloxanes;
ii) catalytic equilibration and condensation; and
iii) removal of the condensation products from the reaction system, for
example with
anentraining agent such as an inert gas flow.
Using this combined hydrolysis/equilibration process, the functionalized
silicones herein
can be prepared for example, on the one hand from organofunctional
alkoxysilanes or
alkoxysiloxanes, and on the other hand with non-functional alkoxysilanes or
alkoxysiloxaries.
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Instead of the organofunctional alkoxysilanes or the non-functional
alkoxysilanes, other silanes
containing hydrolysable groups on the silicon, such as, for example,
alkylaminosilanes,
alkylsilazanes, alkylcarboxysilanes, chlorosilanes etc. can be subjected to
the combined
hydrolysis/equilibration process.
In accordance with this preparation procedure, amino-functional alkoxysilanes,
water,
corresponding siloxanes containing M, D, T and Q units and basic equilibration
catalysts initially
can be mixed with one another in appropriate ratios and amounts. Heating to 60
°C to 230 °C can
then be carried out, with constant thorough mixing. The alcohols split off
from the alkoxysilanes
and subsequently water can be removed stepwise. The removal of these volatile
components and
the substantial condensation of undesirable reactive groups can be promoted by
using a reaction
procedure at elevated temperatures and/or by applying a vacuum.
In order to achieve enhanced removal of the reactive groups, in particular the
hydroxyl
and alkoxy groups on the silicon atoms, which is as substantial as needed, it
has been found that
this is rendered possible by a further process step which comprises the
removal of the vaporizable
condensation products, such as, in particular, water and alcohols, from the
reaction mixture by
means of an entraining agent. Entraining agents which can be employed to
prepare functionalized
polysiloxanes to be used according to this invention are: carrier gases, such
as nitrogen, low-
boiling solvents or oligomeric silanes or siloxanes. The removal of the
vaporizable condensation
products is preferably carried out by azeotropic distillation out of the
equilibrium. Suitable
entraining agents for these azeotropic distillations include, for example,
entraining agents with a
boiling range from about 40 to 200 °C. under (normal pressure (1 bar)).
Higher alcohols, such as
butanol, pentanol and hexanol, halogenated hydrocarbons, such as, for example,
methylene
chloride and chloroform, aromatics, such as benzene, toluene and xylene, or
siloxanes, such as
hexamethyldisiloxane and octamethylcyclotetrasiloxane, are preferred. The
preparation of the
desired aminosiloxanes can be monitored by suitable methods, such as NMR
spectroscopy or
FTIR spectroscopy, and is concluded when a content of reactive groups which
lies within the
scope according to the invention is determined.
In one embodiment of this hydrolysis/equilibration process, the desired
aminoalkylalkoxysilanes can be prepared in a prior reaction from halogenoalkyl-
, epoxyalkyl- and
isocyanatoalkyl-functionalized alkoxysilanes. This procedure can be employed
successfully if the
aminoalkylalkoxysilanes required are not commercially available. Examples of
suitable
halogenoalkylalkoxysilanes are chloromethylmethyldimethoxysilane and
chloropropylmethyldimethoxysilane, an example of epoxyalkylalkoxysilanes is
glycidylpropylmethyldmethoxysilane and examples of isocyanate-functionalized
silanes are
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12
isocyanatopropylmethyl-diethoxysilane and isocyanatopropyltriethoxysilane. It
is also possible to
carry out the functionalization to amino-functional compounds at the stage of
the silanes or the
equilibrated siloxanes.
Ammonia or structures containing primary, secondary and tertiary amino groups
can be
used in the preparation of the amino-functionalized silanes and siloxanes.
Diprimary amines are
of particular interest, and here in particular diprimary alkylamines, such as
1,6-diaminohexane
and 1,12-diaminododecane, and diprimary amines based on polyethylene oxide-
polypropylene
oxide copolymers, such as Jeffamine~ of the D and ED series (Huntsman Corp.)
can be used.
Primary-secondary diamines, such as aminoethylethanolamine, are furthermore
preferred.
Primary-tertiary diamines, such as N,N-dimethylpropylenediamine, are also
preferred. Secondary-
tertiary diamines, such as N-methylpiperazine and bis-(N,N-
dimethylpropyl)amine, represent a
further group of preferred amines. Tertiaryamines, uch as trimethylamine, N-
methylmorpholine
and N,N-dimethylethanolamine, are also preferred. Aromatic amines, such as
imidazole, N-
methylimidazole, aminopropylimidazole, aniline and N-methylaniline, can also
advantageously
be employed. After the synthesis has been carried out, these
aminoalkylalkoxysilanes are used in
the combined hydrolysis/equilibration process hereinbefore described.
Alternatively to the combined hydrolysis/equilibration process, a two-stage
process
procedure can also be followed. A siloxane precursor high in amino groups is
prepared in a
separate first step. It is essential that this siloxane precursor is
substantially free from reactive
groups, for example silanol and alkoxysilane groups. The synthesis of this
siloxane precursor
high in amino groups is carned out using the
hydrolysis/condensation/equilibration concept
already described. A relatively large amount of the amino-functional
alkoxysilane, water and
relatively small amounts of siloxanes containing M, D, T and Q units as well
as basic
equilibration catalysts are first mixed with one another in appropriate ratios
and amounts. Heating
to 60 °C to 230 °C is then carried out with constant thorough
mixing, and the alcohols split off
from the alkoxysilanes and subsequently water are removed stepwise as
hereinbefore described.
The composition of this siloxane precursor high in amino groups, including the
content of reactive
groups, can be determined by suitable methods, such as titration, NMR
spectroscopy or FTIR
spectroscopy.
In a second, separate equilibration step, the actual target product can be
prepared from
this siloxane precursor high in amino groups and siloxanes containing M, D, T
and Q units under
base or acid catalysis. According to requirements for minimization of the end
contents of reactive
groups, this can again be carried out, as already described, at elevated
temperature and/or with
vacuum and with azeotropic distillation. The essential advantage of this two-
stage method is that
the final equilibration proceeds with substantial exclusion of e.g. water and
alcohols and the
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13
contents of reactive groups in the starting substances are small and known. It
is possible to carry
out the aminoalkylalkoxysilane synthesis described above in series with the
two-stage synthesis.
In addition to having the requisite relatively low content of reactivelcurable
groups, the
functionalized silicones used herein must also have a % amine/ammonium
functionality, i.e.,
nitrogen content or %N by weight, in the range of from 0.05% to 0.50%. More
preferably,
nitrogen content ranges from 0.10% to 0.45% by weight. Most preferably,
ntrogencontent ranges
from 0.3% to 0.4%. Nitrogen content can be determined by conventional
analytical techniques
such as by direct elemental analysis or by NMR.
In addition to having the specified curable/reactive group and nitrogen
content
characteristics, the functionalized silicone materials used herein must also
have certain viscosity
characteristics. In particular, the functionalized polysiloxane materials used
herein will have a
viscosity from 0.00002 ma/s (20 centistokes at 20 °C) to 0.2 ma/s
(200,000 centistokes at 20 °C),
preferably from 0.0015 m2/s (1500 centistokes at 20 °C) to 0.1 mals
(100,000 centistokes at 20
°C), and more preferably from 0.002 m2/s (2000 centistokes at 20
°C) to 0.01 ma/s (10,000
centistokes at 20 °C).
The preferred functionalized silicones will also have a molecular weight in
the range of
from 2,000 Da to 100,000 Da, preferably from 15,000 Da to 50,000 Da, most
preferably from
20,000 Da to 40,000 Da, most preferably. from 25,000 Da to 35,000 Da.
Examples of preferred functionalized silicones for use in the compositions of
the present
invention include but are not limited to, those which conform to the general
formula (A):
(Rl)aG3_a-Si-(-OSiG2)n-(-OSiGb(Rl)2_b)m'O'SiG3_a(Rl)a (A)
wherein G is phenyl, or C1-Cg alkyl, preferably methyl; a is 0 or an integer
having a value from
1 to 3, preferably 0; b is 0, 1 or 2, preferably 1; n is a number from 49 to
1299, preferably from
100 to 1000, more preferably from 150 to 600; m is an integer from 1 to S0,
preferably from 1 to
5; most preferably from 1 to 3 the sum of n and m is a number from 50 to 1300,
preferably from
150 to 600; Rl is a monovalent radical conforming to the general formula
CqH2qL, wherein q is
an integer having a value from 2 to 8 and L is selected from the following
groups:
-N(R2)CH2-CH2-N(R2)2; -N(R2)2; wherein R2 is hydrogen, phenyl, benzyl,
hydroxyalkyl or a
saturated hydrocarbon radical, preferably an alkyl radical of from C1 to C20.
A preferred aminosilicone corresponding to formula (A) is the shown below in
formula
(B):
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14
~H3 Hs ~H3 ~
H3
- I - -R
R i O- i O i O i
~ ~ ~ ~
CH3 CH3 ~ ~ C'H3
~
H2)3
NH
~ ~
Hz)z
NH2 m
wherein R is independently selected from Cl to C4 alkyl, hydroxyalkyl and
combinations thereof,
preferably from methyl and wherein n and m are hereinbefore defined. When both
R groups are
methyl, the above polymer is known as "trimethylsilylamodimethicone".
b1) Non-functionalized Silicones:
For purposes of this invention, a non-functionalized silicone is a polymer
containing
repeating Si0 groups and substitutents which comprise of carbon, hydrogen and
oxygen. Thus,
the non-functionalized silicones selected for use in the compositions of the
present invention
include any nonionic, non-cross linked, nitrogen-free, non-cyclic silicone
polymer.
Preferably, the non-functionalized silicone is selected from nonionic nitrogen-
free
silicone polymers having the Formula (I):
R~ R~ R~
R~ - ~ i-O--~ ~ -O -jw ~ i-R1
R~ R1 R~ (I)
wherein each Rl is independently selected from the group consisting of linear,
branched or cyclic
alkyl groups having from 1 to 20 carbon atoms; linear, branched or cyclic
alkenyl groups having
from 2 to 20 carbon atoms; aryl groups having from 6 to 20 carbon atoms;
alkylaryl groups
having from 7 to 20 carbon atoms; arylalkyl and arylalkenyl groups having from
7 to 20 carbon
atoms and combinations thereof. selected from the group consisting of linear,
branched or cyclic
alkyl groups having from 1 to 20 carbon atoms; linear, branched or cyclic
alkenyl groups having
from 2 to 20 carbon atoms; aryl groups having from 6 to 20 carbon atoms;
alkylaryl groups
having from 7 to 20 carbon atoms; arylalkyl; arylalkenyl groups having from 7
to 20 carbon
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atoms and wherein the index w has a value such that the viscosity of the
nitrogen-free silicone
polymer is between 0.01 mz/s (10,000 centistokes at 20 °C) to 2.0 m2/s
(2,000,000 centistokes at
°C), more preferably from 0.05 mils (50,000 centistokes at 20
°C) to 1.0 m2/s (1,000,000
centistokes at 20 °C).
More preferably, the non-functionalized silicone is selected from linear
nonionic silicones
having the Formulae (I), wherein Rl is selected from the group consisting of
methyl, phenyl, and
phenylalkyl, most preferably methyl.
Non-limiting examples of nitrogen-free silicone polymers of Formula (I)
include the
Silicone 200 fluid series from Dow Corning and Baysilone Fluids M 600,000 and
100,000 from
Bayer AG.
b3) Silicone Blend
The blend of functionalized and non-functionalized silicones can be formed by
simply
admixing these two types of silicones together in the appropriate desired
ratios. Silicone
materials of these two essential types are preferably miscible liquids when
their compositions are
as specified herein. The silicone blend then can then be added as is to the
detergent compositions
herein under agitation to form droplets of the silicone blend within the
detergent composition.
Generally the weight ratio of functionalized polysiloxane material to non-
functionalized
polysiloxane material in the silicone blend will range from 100:1 to 1:100.
More preferably the
blend will contain functionalized and non-functionalized silicones in a weight
ratio of from 1:25
to 5:1, even more preferably from 1:20 to 1:1, and most preferably from 1:15
to 1:2.
The blends of functionalized and non-functionalized polysiloxanes used in the
detergent
compositions herein are preferably also "miscible." For purposes of this
invention, such silicone
blends are "miscible" if they mix freely and exhibit no phase separation at 20
°C when admixed
within the broad weight ratio range of from 100:1 to 1:100.
The silicone blends present as droplets in the liquid detergent can get into
the liquid
detergent composition formulation in a number of different ways provided that
the two essential
silicones are mixed before adding them to the balance of the liquid detergent
composition. They
can be mixed "neat" to form the blend, or, more preferably, the silicone
blends can be introduced
into the liquid detergent being added as "silicone emulsions". "Silicone
emulsions" herein, unless
otherwise made clear, refers to combinations of the blended essential
silicones with water plus
other adjuncts such as emulsifiers, biocides, thickeners, solvents and the
like. The silicone
emulsions can be stable, in which case they are useful articles of commerce,
practically
convenient to handle in the detergent plant, and can be transported
conveniently. The silicone
emulsions can also be unstable. For example, a temporary silicone emulsion of
the blended
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16
silicones can be made from the neat silicones in a detergent plant, and this
temporary silicone
emulsion can then be mixed with the balance of the liquid detergent provided
that a dispersion of
the droplets having the particle sizes specified herein is the substantially
uniform result. (When
referring to percentages of ingredients in the liquid detergents, the
convention will be used herein
of accounting only the essential silicones in the "silicone blend" part of the
composition, with all
minor ingredients e.g., emulsifiers, biocides, solvents and the like, being
accounted for in
conjunction with recital of the non-silicone component levels of the
formulation.)
In a preferred embodiment of the present invention, the silicone blend is
emulsified with
water and an emulsifier to form an emulsion which can be used as a separate
component of the
detergent composition. Such a preformed oil-in-water emulsion can then be
added to the other
ingredients to form the final liquid laundry detergent composition of the
present invention.
The weight ratio of the silicone blend to the emulsifier is generally between
500:1 and
1:50, more preferably between 200:1 and 1:1, and most preferably greater than
2:1. The
concentration of the silicone blend in the oil-in-water emulsion will
generally range from 5% to
60% by weight of the emulsion, more preferably from 35% to SO% by weight of
the emulsion.
Preferred silicone blend emulsions for convenient transportation from a
silicone manufacturing
facility to a liquid detergent manufacturing facility will typically contain
these amounts of
silicone, with the balance of suitable transportation blends being water,
emulsifiers and minor
components such as bacteriostats. In such compositions the weight ratio of the
silicone blend to
water will generally lie in the range from 1:50 to 10:1, more preferably from
1:10 to 1:1.
Any emulsifier which is chemically and physically compatible with all other
ingredients
of the compositions of the present invention is suitable for use therein and
in general the
emulsifier can have widely ranging HLB, for example an HLB from 1 to 100.
Typically the HLB
of the emulsifier will lie in the range from 2 to 20. Cationic emulsifiers,
nonionic emulsifiers and
mixtures thereof are useful herein. Emulsifiers may also be silicone
emulsifiers or non-silicone
emulsifiers. Useful emulsifiers also include two- and three-component
emulsifier mixtures. The
invention includes embodiments wherein two emulsifiers or three emulsifiers
are added in
forming the silicone blends.
Nonionic emulsifiers:
One type of nonionic emulsifier suitable for use herein comprises the "common"
polyether alkyl nonionics. These include alcohol ethoxylates such as Neodol 23-
5 ex Shell and
Slovasol 458 ex Sasol. Other suitable nonionic emulsifiers include alkyl poly
glucoside-based
emulsifiers such as those disclosed in U.S. Patent 4,565,647, Llenado, issued
January 21, 1986,
having a hydrophobic group containing from 6 to 30 carbon atoms, preferably
from 8 to 16
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17
carbon atoms, more preferably from 10 to 12 carbon atoms, and a
polysaccharide, e.g. a
polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from
1.3 to 3, most .
preferably from 1.3 to 2.7 saccharide units. Any reducing saccharide
containing 5 or 6 carbon
atoms can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the
glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-,
4-, etc. positions
thus giving a glucose or galactose as opposed to a glucoside or galactoside).
The intersaccharide
bonds can be, e.g., between the one position of the additional saccharide
units and the 2-, 3-, 4-,
and/or 6- positions on the preceding saccharide units.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and combinations thereof in which the alkyl groups contain
from 6to 30,
preferably from 8 to 16, more preferably from 10 to 12 carbon atoms; n is 2 or
3, preferably 2; t is
from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3,
most preferably from
1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these
compounds, the
alcohol or alkylpolyethoxy alcohol is formed first and then reacted with
glucose, or a source of
glucose, to form the glucoside (attachment at the 1-position). The additional
glycosyl units can
then be attached between their 1-position and the preceding glycosyl units 2-,
3-, 4- and/or 6-
position, preferably predominately the 2-position. Compounds of this type and
their use in
',
detergents are disclosed in EP-B 0 070 077, 0 075 996, 0 094 118, and in WO
98/00498.
Still other types of useful nonionic emulsifiers for making silicone blend
emulsions include other polyol surfactants such as sorbitan esters (e.g. Span
80 ex
Uniqema, Crill 4 ex Croda) and ethoxylated sorbitan esters. Polyoxyethylene
fatty acid
esters (e.g. Myrj 59 ex Uniqema) and ethoxylated glycerol esters may also be
used as can
fatty amideslamines and ethoxylated fatty amides/amines.
Cationic emulsifiers:
Cationic emulsifiers suitable for use in the silicone blends of the present
invention have at
least one quaternized nitrogen and one long-chain hydrocarbyl group. Compounds
comprising
two, three or even four long-chain hydrocarbyl groups are also included.
Examples of such
cationic emulsifiers include alkyltrimethylammonium salts or their
hydroxyalkyl substituted
analogs, preferably compounds having the formula R1R2R3R4N'~X-. R1, R2, R3 and
R4 are
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18
independently selected from C1-C26 alkyl, alkenyl, hydroxyalkyl, benzyl,
alkylbenzyl,
alkenylbenzyl, benzylalkyl, benzylalkenyl and X is an anion. The hydrocarbyl
groups Rl, R2, R3
and R4 can independently be alkoxylated, preferably ethoxylated or
propoxylated, more
preferably ethoxylated with groups of the general formula (C2H40)xH where x
has a value from
1 to 15, preferably from 2 to 5. Not more than one of R2, R3 or R4 should be
benzyl. The
hydrocarbyl groups Rl, R2, R3 and R4 can independently comprise one or more,
preferably two,
ester- ([-O-C(O)-]; [-C(O)-O-]) and/or an amido-groups ([O-N(R)-]; [-N(R)-O-])
wherein R is
defined as Rl above. The anion X may be selected from halide, methysulfate,
acetate and
phosphate, preferably from halide and methylsulfate, more preferably from
chloride and bromide.
The Rl, R2, R3 and R4 hydrocarbyl chains can be fully saturated or unsaturated
with varying
Iodine value, preferably with an Iodine value of from 0 to 140. At least 50%
of each long chain
alkyl or alkenyl group is predominantly linear, but also branched and/or
cyclic groups are
included.
For cationic emulsifiers comprising only one long hydrocarbyl chain, the
preferred alkyl
chain length for Rl is Cla-C15 and preferred groups for R2,~ R3 and R4 are
methyl and
hydroxyethyl.
For cationic emulsifiers comprising two or three or even four long hydrocarbyl
chains, the
preferred overall chain length is Clg, though combinations of chain lengths
having non-zero
proportions of lower, e.g., Cla, C14, C16 and some higher, e.g., C20 chains
can be quite
desirable.
Preferred ester-containing emulsifiers have the general formula
{(RS)2N((CH2)nER6)2}~_
wherein each RS group is independently selected from C1_4 alkyl, hydroxyalkyl
or C2_4
alkenyl; and wherein each R6 is independently selected from Cg_2g alkyl or
alkenyl groups; E is
an ester moiety i.e., -OC(O)- or -C(O)O-, n is an integer from 0 to 5, and X'
is a suitable anion,
for example chloride, methosulfate and combinations thereof.
A second type of preferred ester-containing cationic emulsifiers can be
represented by the
formula: {(RS)3N(CH2)nCH(O(O)CR6)CH20(O)CR6}~'~X- wherein R5, R6, X, and n are
defined
as above. This latter class can be exemplified by 1,~ bis[hardened
tallowoyloxy]-3-
trimethylammonium propane chloride.
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19
The cationic emulsifiers, suitable for use in the blends of the present
invention can be
either water-soluble, water-dispersible or water-insoluble.
Silicone Emulsifiers:
Silicone emulsifiers useful herein are nonionic, do not include any nitrogen,
and do not
include any of the non-functionalized silicones described hereinbefore.
Silicone emulsifiers are
described for example in "Silicone Surfactants" in the Surfactant Science
Series, Volume 86
(Editor Randal M. Hill), Marcel Dekker, NY, 1999. See especially Chapter 2,
"Silicone Polyether
Copolymers: Synthetic Methods and Chemical Compositions and Chapter 1,
"Siloxane
Surfactants".
Especially suitable silicone emulsifiers are polyalkoxylated silicones
corresponding to
those of the structural Formula I set forth hereinbefore wherein Rt is
selected from the definitions
set forth hereinbefore and from poly(ethyleneoxide/propyleneoxide) copolymer
groups having the
general formula (II):
-(CH2)n ~(C2 H4 ~)c (C3 H6 ~)d R3
(II)
with at least one R' being such a poly(ethyleneoxy/propyleneoxy) copolymer
group, and each R3
is independently selected from the group consisting of hydrogen, an alkyl
having 1 to 4 carbon
atoms, and an acetyl group; and wherein the index w has a value such that the
viscosity of the
resulting silicone emulsifier ranges from 0.00002 m2/sec to 0.2 m2/sec.
Emulsifier Diluents:
The emulsifier may also optionally be diluted with a solvent or solvent system
before
emulsification of the silicone blend. Typically, the diluted emulsifier is
added to the pre-formed
silicone blend. Suitable solvents can be aqueous or non-aqueous; and can
include water alone or
organic solvents alone and/or combinations thereof. Preferred organic solvents
include
monohydric alcohols, dihydric alcohols, polyhydric alcohols, ethers,
alkoxylated ethers, low-
viscosity silicone-containing solvents such as cyclic dimethyl siloxanes and
combinations thereof.
Preferred are glycerol, glycols, polyalkylene glycols such as polyalkylene
glycols, dialkylene .
glycol mono Cl-Cg ethers and combinations thereof. Even more preferred are
diethylene glycol
mono ethyl ether, diethylene glycol mono propyl ether, diethylene glycol mono
butyl ether, and
combinations thereof. Highly preferred are combinations of solvents,
especially combinations of
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lower aliphatic alcohols such as ethanol, propanol, butanol, isopropanol,
and/or diols such as 1,2-
propanediol or 1,3-propanediol; or combinations thereof with dialkylene glycol
mono C1-Cg
ethers and/or glycols and/or water. Suitable monohydric alcohols especially
include C1-C4
alcohols.
b4) Silicone Blend in Detergent Composition
The silicone blend as hereinbefore described will generally comprise from
0.05% to 10%
by weight of the liquid detergent composition. More preferably, the silicone
blend will comprise
from 0.1% to 5.0%, even more preferably from 0.25% to 3.0%, and most
preferably from 0.5% to
2.0%, by weight of the liquid detergent composition. The silicone blend will
generally be added
to some or all of the other liquid detergent composition components under
agitation to disperse
the blend therein.
Within the liquid detergent compositions herein, the silicone blend, either
having added
emulsifiers present or absent, will be present in the form of droplets. Within
the detergent
composition, and within emulsions formed from the silicone blend, such
droplets will generally
have a median silicone particle size of from 0.5 ~,m to 300 ~,m, more
preferably from 0.5 ~m to
100 pm and even more preferably from 0.6 wm to 50 pm. As indicated, particle
size may be
measured by means of a laser scattering technique, using a Coulter LS 230
Laser Diffraction
Particle Size Analyser from Coulter Corporation, Miami, Florida, 33196, USA).
Particle sizes are
measured in volume weighted % mode, calculating the median particle size.
Another method
which can be used for measuring the particle size is by means of a microscope,
using a
microscope manufactured by Nikon~ Corporation, Tokyo, Japan; type Nikon~ E-
1000
(enlargement 700X).
C) Aqueous Base and Non-Silicone Laundry Adjunct
The liquid detergent compositions of the present invention must contain water
as well as
an additional non-silicone laundry adjunct selected from detersive enzymes,
dye transfer
inhibiting agents, optical brighteners, suds suppressors, and combinations
thereof.
c1) Water
The liquid detergent compositions herein are aqueous in nature. Accordingly,
the
detergent compositions herein will contain at least 4% by weight of water.
More preferably such
compositions will contain at least 20% by weight of water, even more
preferably at least ~0% by
weight of water.
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21
c2) Enzymes - The laundry adjuncts may also comprise one or more detersive
enzymes. Suitable detersive enzymes for use herein include: Proteases like
subtilisins from
Bacillus [e.g. subtilis, lentus, lichenifornZis, amyloliquefaciens (BPN, BPN),
alcalophilus,] e.g.
Esperase~~ Alcalase~, Everlase~ and Savinase~ (Novozymes), BLAP and variants
[Henkel].
Further proteases are described in EP130756, W091/06637, W095/10591 and
W099/20726.
Amylases (oc and/or (3) are described in WO 94/02597 and WO 96/23873:
Commercial examples
are Purafect Ox Am~ [Genencor] and Termamyl~, Natalase~, Ban~, Fungamyl~ and
Duramyl~
[all ex Novozymes]. Cellulases include bacterial or fungal cellulases, e.g.
produced by Humicola
articularl DSM 1800 e. . SOKda and "43kD Care e~]. Also suitable cellulases
insolens, p y ~ g [
are the EGIII cellulases from Trichoderma longibrachiatum. Suitable lipases
include those
produced by Pseudomonas and Chromobacter groups. Preferred are e.g. LipolaseR,
Lipolase
UltraR, LipoprimeR and LipexR from Novozymes. Also suitable are cutinases [EC
3.1.1.50] and
esterases. Carbohydrases e.g. mannanase (US6060299), pectate lyase
(W099/27083)
cyclomaltodextringlucanotransferase (W096133267) xyloglucanase (W099/02663).
Bleaching
enzymes eventually with enhancers include e.g. peroxidases, laccases,
oxygenases, (e.g. catechol
1,2 dioxygenase, lipoxygenase (WO 95/26393), (non-heme) haloperoxidases .
It is common practice to modify wild-type enzymes via protein / genetic
engineering
techniques in order to optimize their performance in the detergent
compositions. If used, these
enzymes are typically present at concentrations from 0.0001% to 2.0%,
preferably from 0.0001%
to 0.5%, and more preferably from 0.005% to 0.1%, by weight of pure enzyme
(weight % of
composition).
Enzymes can be stabilized using any known stabilizer system like calcium
and/or
magnesium compounds, boron compounds and substituted boric acids, aromatic
borate esters,
peptides and peptide derivatives, polyols, low molecular weight carboxylates,
relatively
hydrophobic organic compounds [e.g. certain esters, dialkyl glycol ethers,
alcohols or alcohol
alkoxylates], alkyl ether carboxylate in addition to a calcium ion source,
benzamidine
hypochlorite, lower aliphatic alcohols and carboxylic acids, N,N-
bis(carboxymethyl) serine salts;
(meth)acrylic acid-(meth)acrylic acid ester copolymer and PEG; lignin
compound, polyamide
oligomer, glycolic acid or its salts; poly hexamethylene bi guanide or N,N-bis-
3-amino-propyl-
dodecyl amine or salt; and combinations thereof.
In liquid matrix of the compositions of the present invention, the degradation
by the
proteolytic enzyme of second enzymes can be avoided by protease reversible
inhibitors [e.g.
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22
peptide or protein type, in particular the modified subtilisin inhibitor of
family VI and the
plasminostrepin; leupeptin, peptide trifluoromethyl ketones, peptide
aldehydes.
c3) Dye transfer inhibiting agents - The laundry adjuncts may also comprise
one or
more materials effective for inhibiting the transfer of dyes from one fabric
to another. Generally,
such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers,
polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine,
peroxidases, and combinations thereof. If used, these agents typically are
present at
concentrations from 0.01% to 10%, preferably from 0.01% to 5%, and more
preferably from
0.05% to 2%, by weight of the composition.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units
having the following structural formula: R-Ax-Z; wherein Z is a polymerizable
unit to which an
N-O group can be attached or the N-O group can form part of the polymerizable
unit or the N-O
group can be attached to both units; A is one of the following structures: -
NC(O)-, -C(O)O-, -S-,
O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics,
heterocyclic or alicyclic
groups or any combination thereof to.which the nitrogen of the N-O group can
be attached or the
N-O group is part of these groups. Preferred polyamine N-oxides are those
wherein R is~ a
heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,
piperidine and derivatives
thereof.
The N-O group can be represented by the following general structures:
O O
(Rt)X ~ -CR2)y~ =N-CRt)x
(R3)z
wherein Rl, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or combinations
thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be
attached or form part of
any of the aforementioned groups. The amine oxide unit of the polyamine N-
oxides has a pKa
<10, preferably pKa <~, more preferred pICa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-
soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are
polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and
combinations thereof. These polymers include random or block copolymers where
one monomer
type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-
oxide
polymers typically have a ratio of amine to the amine N-oxide of 10:1 to
1:1,000,000. However,
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23
the number of amine oxide groups present in the polyamine oxide polymer can be
varied by
appropriate copolymerization or by an appropriate degree of N-oxidation. The
polyamine oxides
can be obtained in almost any degree of polymerization. Typically, the average
molecular weight
is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most
preferred 5,000 to
100,000. This preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the present compositions and
processes
for carrying out domestic laundry herein is poly(4-vinylpyridine-N-oxide)
which as an average
molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class
as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an
average molecular
weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most
preferably from 10,000 to 20,000. (The average molecular weight range is
determined by light
scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern
Methods of
Polymer Characterization", the disclosures of which are incorporated herein by
reference.) .The
PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from
1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1
to 0.4:1. These
copolymers can be either linear or branched.
The present compositions also may employ a polyvinylpyrrolidone ("PVP") having
an
average molecular weight of from 5,000 to 400,000, preferably from 5,000 to
200,000, and more
preferably from 5,000 to 50,000. PVP's are known to persons skilled in the
detergent field; see,
for example, EP-A-262,897 and EP-A-256,696. Compositions containing PVP can
also contain
polyethylene glycol ("PEG") having an average molecular weight from 500 to
100,000, preferably
from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis
delivered in wash
solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
c4) Optical Brighteners
The compositions herein may comprise from 0.01% to 2.0% by weight of an
optical
brightener. Suitable optical brighteners include stilbene brighteners.
Stilbene brighteners are
aromatic compounds with two aryl groups separated by an alkylene chain.
Optical brighteners are
described in greater detail in U.S. Patents 4,309,316; 4,298,490; 5,035,825
and 5,776,878.
c5) Suds Suppressors
The compositions may comprise a suds suppressing system present at a level of
from
0.01% to 15%, preferably from 0.1% to 5% by weight of the composition.
Suitable suds
suppressing systems for use herein may comprise any known antifoam compound,
including
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24
silicone-based antifoam compounds and 2-alkyl alcanol antifoam compounds.
Preferred silicone
antifoam compounds are generally compounded with silica and include the
siloxanes, particularly
the polydimethylsiloxanes having trimethylsilyl end blocking units. Other
suitable antifoam
compounds include the monocarboxylic fatty acids and soluble salts thereof,
which are described
in US 2,954,347. A preferred particulate suds suppressing system is described
in EP-A-0210731.
A preferred suds suppressing system in particulate form is described in EP-A-
0210721.
D) Excluded/Minimized Coacervate Phase-Forming Polymer or
Cationic Deposition Aid
The liquid laundry detergent compositions of the present invention must be
essentially
free of any coacervate phase-forming polymer or cationic deposition aid.
Essentially free means
less than 0.01%, preferably less than 0.005%, more preferably less than 0.001%
by weight of the
composition, and most preferably completely or totally free of any coacervate
phase-forming
polymer and of any cationic deposition aid.
For purposes of this invention, a coacervate phase-forming polymer is any
polymer
material which will react, interact, complex or coacervate with any of the
composition
components to form a coacervate phase. The phrase "coacervate phase" includes
all kinds of
separated polymer phases known by the person skilled in the art such as
disclosed in L. Piculell &
B. Lindman, Adv. Colloid Interface Sci., 41 (1992) and in B. Jonsson, B.
Lindman, K. Holmberg,
& B. Kronberb, "Surfactants and Polymers In Aqueous Solution", John Wiley &
Sons, 1998. The
mechanism of coacervation and all its specific forms are fully described in
"Interfacial Forces in
Aqueous Media", C.J. van Oss, Marcel Dekker, 1994, pages 245 to 271. When
using the phrase
"coacervate phase", it should be understood that such a term is also
occasionally referred to as
"complex coacervate phase" or as "associated phase separation" in the
literature.
Also for purpose of this invention, a cationic deposition aid is a polymer
which has
cationic, functional substituents and which serve to enhance or promote the
deposition onto
fabrics of one or more fabric care agents during laundering operations. Many
but not all cationic
deposition aids are also coacervate phase-forming polymers. Whether or not a
cationic deposition
aid forms a coacervate or whether or not a coacervate phase-forming polymer
acts as a deposition
aids, neither of these two polymer types can be significantly present in the
detergent compositions
of this invention.
E) Other Optional Composition Components
The present compositions may optionally comprise one or more optional
composition
components, such as liquid carriers, detergent builders and chelating agents
including organic
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carboxylate builders such as citrate and fatty acid salts, stabilizers and
structurants such as
hydrogenated castor oil and its derivatives, coupling agents, fabric
substantive perfumes, cationic
nitrogen-containing detersive surfactants, pro-perfumes, bleaches, bleach
activators, bleach
catalysts, enzyme stabilizing systems, soil release polymers, dispersants or
polymeric organic
builders including water-soluble polyacrylates, acrylate / maleate copolymers
and the like, dyes,
colorants, filler salts such as sodium sulfate, hydrotropes such as
toluenesulfonates,
cumenesulfonates and naphthalenesulfonates, photoactivators, hydrolyzable
surfactants,
preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents,
germicides, fungicides,
color speckles, colored beads, spheres or extrudates, sunscreens, fluorinated
compounds, clays,
pearlescent agents, luminescent agents or chemiluminescent agents, anti-
corrosion and/or
appliance protectant agents, alkalinity sources or other pH adjusting agents,
solubilizing agents,
carriers, processing aids, pigments, free radical scavengers, and pH control
agents. Suitable
materials include those described in U.S. Patent Nos. 5,705,464, 5,710,115,
5,698,504, 5,695,679,
5,686,014 and 5,646,101.
F) Process for Preparing the Liquid Detergent Compositions
The liquid detergent compositions of the present invention can be prepared in
any suitable
manner and can, in general, involve any order of combining or addition as
known by the person
skilled in the art. As indicated, the silicone blend is generally preformed
and then added to the
balance of the liquid detergent components.
EXAMPLES
The following non-limiting examples are illustrative of the present invention.
The final liquid laundry detergent composition is formulated by combining a
pre-formed
silicone blend, which is optionally emulsified with an emulsifier, with at
least one surfactant and
further at least one additional requisite non-silicone laundry adjunct. The
surfactant and the
laundry adjunct may optionally pre-mixed prior to combination with the,
optionally emulsified,
pre-formed silicone blend.
Fabric cleaning premixes A1 and A2 and A3:
Wt%
(raw materials at 100% activityl
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26
A1 A2 A3
C13-C15 alkylbenzene sulphonic13.0 5.5 5.5
acid
C12-C15 alkyl ethoxy (1.1 eq.) 13.0 13.0
sulphate
C14-C15 E08 (1) 9.0 - _
C 12-C 13 E09 (2) - 2.0 2.0
C12-C14 alkyl dimethyl amineoxide1.5 1.0 1.0
(3)
C 12-C 1 g fatty acid 10.0 2.0 2:0
Citric acid 4.0 4.0 4.0
Diethylene triamine pentamethylene0.3 - -
phosphonic acid
Hydroxyethane dimethylene phosphonic0.1 - -
acid
Ethoxylated polyethylene imine1.0 1.0 1.0
Ethoxylated tetraethylene pentamine1.0 0.5 0.5
Di Ethylene Triamine Penta - 0.5 0.5
acetic acid
Ethoxysulphated hexamethylene - 1.0 1.0
diamine
quat
Fluorescent whitening agent 0.15 0.15 0.15
CaCl2 0.02 0.02 0.02
Propanediol 5.0 6.5 6.5
Ethanol 2.0 2.0 2.0
Sodium cumene sulphonate 2.0 - -
NaOH to pH 7.8 to pH to pH 8.0
8.0
Protease enzyme 0.75 0.75 0.75
Amylase enzyme 0.20 0.20 0.20
Cellulase enzyme 0.05 - -
Boric acid 2.0 0.3
Na-Borate - - 1.5
Poly(N-vinyl-2-pyrrolidone)-poly(N-vinyl-0.1 - -
imidazol) (MW: 35,000)
Tinopal~-AMS-GX - 1.2
Hydrogenated castor oil 0.2 0.3 0.3
Dye 0.001 0.001 0.001
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27
Perfume 0.70 0.70 0.70
Water Balance Balance Balance
(1) Marlipal 1415!8.1 ex Sasol
(2) Neodol 23-9 ex Shell
(3) C12-C14 alkyl dimethyl amineoxide ex P&G, supplied as a 31% active
solution in water
Preparation of Amino-Polysiloxane for the Silicone Blend
1) Preparation of Precursor High in Amino Groups
1,003.3 g (3.86 mol) of aminoethylaminopropylmethyldimethoxysilane, 1,968 g of
a siloxane of
the composition M2D25 and 29.7 g of a 10% strength solution of KOH in methanol
are mixed
with one another in a four-necked flask at room temperature, while stirnng.
139 g (7.72 mol) of
deionized water are added dropwise to the cloudy mixture, and the temperature
rises to 46 °C.
The temperature is increased stepwise to 125 °C in the course of 3
hours, with a methanol-
containing distillate (363 g) being removed from 80 °C. After cooling
back to 116 °C, 139 g of
water are again added and the temperature is subsequently increased to 150
°C in the course of 3
hours, with 238 g of distillate being obtained. After renewed cooling back to
110 °C, addition of
139 g of water and heating to 150 °C in the course of 3 hours, 259 g of
distillate are obtained.
Finally, the constituents which boil up to 150 °C under an oil vacuum
are removed (123 g). 2,383
g of a yellow, clear oil are obtained.
The product obtained is analyzed for reactive group content using NMR
spectroscopy methods.
Such methods involve the following parameters:
1 ) Instrument Type: Bruker DPX-400 NMR spectrometer
2) Frequency: 400 MHz
3) Standard: Tetramethylsilane (TMS)
4) Solvent: CDC13 (deuterated chloroform)
5) Concentration: for H-1 0.2%; for Si-29 20%
6 Pulse Sequence: ZGIZT"' (Bruker) for Si-29-nmr spectra with 10 second
relaxation delay time
Using NMR having these characteristics, the following analysis is obtained:
M1.95D OH 0.025D OCH3 0.025D * 7.97D36.9
where D* = SiCH2CH2CH2NHCH2CH2NH2,
2) Preparation of Aminosilicone with Low Reactive/Curable Groun Content
200.6 g (47.7 mmol) of the precursor high in amino groups as prepared in Step
1); 101 g (152.3
mmol) of a siloxane of the composition M2D6.9, 6,321 g of D4 and 1.66 g of 10%
strength KOH
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28
in ethanol are initially introduced into a four-necked flask at room
temperature, while stirring, and
the mixture is heated at 180 °C for 3 hours. After cooling back to 120
°C, a further 1.66 g of 10%
strength KOH in ethanol are added. The mixture is then heated at 180 °C
for a further 3 hours
(the viscosity of a sample taken at this point in time is 2,940 mPas, 20
°C). A water-pump
vacuum is applied at 180 °C, so that D4 boils under reflux for 10
minutes. 60 g of D4, which
contains included drops of water, are removed in a water separator. This
procedure is repeated
after 2, 4 and 6 hours. After cooling back to 30 °C, 0.36 g of acetic
acid is added to neutralize the
catalyst. All the constituents which boil up to 150 °C are then removed
under an oil vacuum.
5,957 g of a colorless aminosiloxane with a viscosity of 4,470 mPas (20
°C) and the composition,
determined by NMR spectroscopy as described above, of
MzD * a. ~ sDaa~
where D* = SiCH2CH2CH2NHCH2CH~NH2
are obtained. Such a material has a nitrogen content of 0.34% by weight and a
percent ratio of
terminal curablelreactive groups of essentially 0%.
Preparation of the silicone emulsion (Emulsion E11: 15.0 g of the Step 2
aminosilicbne are added
to 45.0 g of PDMS 0.6 m/s2 (600,000 centistokes at 20 °C; GE~ Visc-
600M) and mixed with a
normal laboratory blade mixer (type: IKA Labortechnik Eurostar power control-
visc lab mixer)
for at least 1 hour.
14.3g of the blend of Step 2 aminosilicone with PDMS 0.6mlsa are added to
7.15g of Neodol 25-3
ex Shell (ethoxylated alcohol nonionic emuslifier) and the mixture is stirred
for 15 minutes with a
normal laboratory blade mixer (type: IKA Labortechnik Eurostar power control-
visc lab mixer) at
250RPM.
3 equal partitions of 7.14g water are added with each time 10 minutes stirring
at 250RPM in-
between.
A final 7.14g water is added and the stirring speed is increased to 400RPM.
The mixture is stirred
at this speed for 40 minutes.
Preparation of the silicone emulsion (Emulsion E21: 15.0 g of the Step 2
aminosilicone are added
to 45.0 g of PDMS 0.6 m/s2 (600,000 centistokes at 20 °C; GE~ Visc-
600M) and mixed with a
normal laboratory blade mixer (type: IKA Labortechnik Eurostar power control-
visc lab mixer)
for at least I hour.
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29
30.0g of the blend of Step 2 aminosilicone with PDMS 0.6m/sz are added to
4.308 of Crill 4
sorbitan oleate ex Croda and mixed with a normal laboratory blade mixer at
300RPM for 15
minutes.
11.6g of Crodet 5100 PEG-100 stearate (25% in water) ex Croda are added and
the mixture is
stirred for 15 minutes at 1000RPM.
5.1g water is added dropwise in a time span of 10 minutes, upon stirnng at
1000RPM, and after
the addition of the water, the mixture is stirred for another 30 minutes at
1000RPM.
27.0g of a 1.45% sodium carboxymethyl cellulose solution are added and the
mixture is stirred for
15 minutes at SOORPM. .
Preparation of the silicone emulsion (Emulsion E31: 15.0 g of the Step 2
aminosilicone are added
to 45.0 g of PDMS 0.1 m/s2 (100,000 centistokes at 20 °C; GE~ Visc-
100M) and mixed with a
normal laboratory blade mixer (type: IKA Labortechnik Eurostar power control-
visc lab mixer)
for at least 1 hour. .
19.25g of of the blend of Step 2 aminosilicone with PDMS 0.1 mls2 is mixed
with 1.15g of
Neodol 25-3 ex Shell and 4.6g of Slovasol 458 ex Sasol (ethoxylated alcohol
nonionic) and stirred
for 10 minutes at 300RPM.
lO.Og water is added and the mixture is stirred for 30 minutes at 300 RPM.
3 equal partitions of S.Og water are added, with 10 minutes stirring at 300RPM
after each water
addition.
Preparation of the silicone emulsion (Emulsion E41: 6.0 g of GE~ SF1923
aminosilicone are
added to 54.0 g of PDMS 0.6 m/sa (600,000 centistokes at 20 °C; GE~
Visc-600M) and mixed
with a normal laboratory blade mixer (type: IKA Labortechnik Eurostar power
control-visc lab
mixer) for at least 1 hour.
19.258 of of the blend of Step 2 aminosilicone with PDMS 0.6 m/sa is mixed
with 4.68 of Neodol
25-3 ex Shell and 1.158 of Slovasol 458 ex Sasol and stirred for 10 minutes at
300RPM.
10.08 water is added and the mixture is stirred for 30 minutes at 300 RPM.
3 equal partitions of S.Og water are added, with 10 minutes stirring at 300RPM
after each water
addition.
Final detergent compositions
Combination of the two premixes A1 & E1 (Entry 1) or A1 & E2 (Entry 21 or A1 &
E3 (Entry 31
or A1 & E4 (Entry 4) or A2 & E1 (Entry 51 or A2 & E2 (Entry 6) or A2 & E3
(Entry 71 or A2 &
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E4~Entry 8) or A3 & E1 (Entry 9) or A3 & E2 (Entry 10) or A3 & E3 (Entr~)~ or
A3 & E4
lEntry 121 to form the final liquid laundry detereent composition:
104.98 of premix E1 is added to 1500 g of either premixes A1 or A2 or A3 and
stirred for 15 min
at 3501tPM with a normal laboratory blade mixer.
78.08 of premix E2 is added to 1500 g of either premixes A1 or A2 or A3 and
stirred for 15 min
at 3501tPM with a normal laboratory blade mixer.
For all emulsions E1, E2, E3 and E4 the mean particle size in the A1, A2 or A3
products is in the
2 p,m - 20 ~.m range.
The liquid laundry detergent compositions of composition Entries 1 to 12 all
demonstrate
excellent product stability as fully formulated composition as well as in
diluted form during a
laundering cycle. The liquid laundry detergent compositions of composition
Entries 1 to 12 all
provide excellent fabric cleaning and fabric care performance when added to
the drum of an
automatic washing machine wherein fabric are there and thereinafter laundered
in conventional
manner.
The compositions of Entries 1 to 12 are particularly advantageous with respect
to fabric
softening benefits imparted to fabrics treated therewith; this is especially
true for colored fabrics
on which the observed fabric softening benefits are even more enhanced in
comparison to the
fabric softening benefits provided onto white fabrics. The compositions of
Entries 1, 2, 3, 10, 1 l,
and 12 are also advantageous with respect to anti-abrasion benefits and to
anti-pilling benefits
provided for fabrics treated therewith. The compositions of Entries 1, 2, 3,
10, 11, and 12 are
particularly advantageous with respect to color care benefits imparted to
fabrics treated therewith.
