Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR MAKING A DETERGENT BASE COMPOSITION
FIELD OF THE INVENTION
The present invention relates to a process for making a liquid detergent base
composition, a
detergent comprising the base composition and a method of laundering using the
detergent.
BACKGROUND OF THE INVENTION
Recent liquid laundry detergent consumer preferences towards smaller more
concentrated
product forms have resulted in the liquid detergent formulators handling a
whole series of
different constraints. In addition, not only do consumers want smaller
compacted liquid laundry
detergent products but the consumers also want these compacted products to
have the same
performance as traditional uncompacted liquid laundry detergents; this is an
extremely difficult
consumer need to meet.
Compacted liquid laundry detergent products have less space to incorporate
detergent
ingredients; this places great constraint on the detergent formulator,
especially for restricting the
levels of the bulk detergent ingredients like surfactants, builders and
solvents that take up much
of the formulation space. For the detergent ingredients that are incorporated
into these compacted
liquid laundry detergent products, the detergent formulator must greatly
improve the efficiency
of these detergent ingredients, and of the compacted liquid laundry detergent
composition as a
whole.
As well as ensures such compacted liquid laundry detergents have good cleaning
performance,
the detergent formulator must also ensure that such products have good product
storage stability
profile, and desirable rheological properties to ensure that the product can
be handled and dosed
easily by the consumer.
An additional problem associated to compacted detergents is the manufacture
process. The
reduction of ingredients, such as solvents can give rise to undesired phase
formation in the base
composition, such as surfactant middle phases that are difficult to process.
Sometimes, it is desirable to make a base detergent composition which can be
diluted to make
finished detergent compositions rather than making different finished products
from the
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beginning. From a process efficiency view point it would be beneficial to have
a common base
composition that can be later on differentiated to give rise to different
products. Very often this
is not possible because the post-addition of solvent or late differentiation
additives to the base
composition would alter the rheology of the composition making it
unmanageable.
The aim of the present invention is to overcome the above described drawbacks.
SUMMARY OF THE INVENTION
According to a first aspect of the invention, there is provided a process for
making an anhydrous
laundry liquid detergent base composition. By "anhydrous composition" is
herein understood a
composition having preferably less than 30%, more preferably less than 20% and
especially less
than 10% of water by weight thereof. By "base composition" is herein
understood a composition
that can be used either as a finished detergent product or preferably as a
building block for a
finished detergent product.
The process of the invention comprises the steps of:
a) providing a pre-neutralized sulphate detersive surfactant syrup wherein at
least 50%,
preferably at least 60%, more preferably at least 70% and especially 100% of
the sulphate
detersive surfactant is pre-neutralized with an organic neutralizing agent,
preferably with
mono-ethanol amine;
b) adding a neutralizing agent to the pre-neutralized sulphate detersive
surfactant syrup; and
c) subsequently adding a sulphonate detersive surfactant in acid form.
By "pre-neutralized surfactant" is herein understood a surfactant that has
been neutralized before
it takes part in the process for making the detergent base composition, as
opposite to be
neutralized during the process for making the detergent base composition.
Many of the sulphate detersive surfactants are not very stable in the acid
form, preferably they
are neutralized just after the acid form is produced. Furthermore the sulphate
detersive
surfactant, even after it has been neutralized, can be instabilized by the
presence of acid. It has
been found that by adding neutralizing agent to the pre-neutralized sulphate
detersive surfactant
syrup (in addition to the neutralizing agent added for the pre-neutralization)
before any other
acidic material the stability of the sulphate detersive surfactant is
enhanced.
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Step c) is performed after steps a) and b) thus the pre-neutralized sulphate
detersive surfactant is
protected from the acid by the neutralizing agent.
In a preferred embodiment the sulphate detersive surfactant is selected from
alkyl alkoxylated
sulphates, mid-chain branched primary alkyl sulphates and mixtures thereof.
Preferably the
sulphate detersive surfactant comprises an alkyl ethoxylated sulphate, more
preferably a C8_18
alkyl ethoxylated sulphate having an average degree of ethoxylation of from
0.5 to 10, preferably
from 0.5 to 7, more preferably from 0.5 to 5 and most preferably from 0.5 to
4.
In preferred embodiments the sulphate detersive surfactant comprises a mixture
of an alkyl
alkoxylated sulphate, preferably a C8_18 alkyl ethoxylated sulphate and a mid-
chain branched
primary alkyl sulphate wherein the alkyl alkoxylated sulphate and the mid-
chain branched
primary alkyl sulphate are in a weight ratio of at least 2:1, preferably at
least 4:1 and especially in
a ratio of at least 5:1.
At least 50%, preferably at least 70%, more preferably at least 90% and
especially 100% of the
sulphate detersive surfactant present in the syrup has been pre-neutralized
with an organic
neutralizing agent. The organic neutralizing agent is preferably an
alkanolamine. It can be a
primary, secondary or a tertiary amine. Mono-ethanolamine (MEA) is the
preferred
alkanolamine for use herein. The use of an organic neutralizing agent,
preferably mono-
ethanolamine, avoids or reduces the use of water (as compared to inorganic
neutralizing agents)
and contributes to the reduction of volume of the base composition as well as
to a favorable
rheology of the resulting base composition. These two factors (volume
reduction and favorable
rheology) are critical for the preparation of a compact detergent.
In a preferred embodiment the pre-neutralized sulphate detersive surfactant
syrup comprises an
organic solvent, preferably a non-amino functional solvent. This further
contributes to the good
rheological profile of the resulting detergent base. Preferred non-amino
functional solvents for
use herein include primary alcohols, glycols and mixtures thereof. Especially
preferred non-
amino functional solvent is a mixture comprising ethanol and propylene glycol.
In preferred embodiments the process of the invention comprises the step of
adding an organic
solvent after step a) and preferably before step b). This organic solvent can
be the same or
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different to that in the pre-neutralized sulphate detersive surfactant syrup.
Preferred organic
solvent for use herein is a non-amino functional solvent, including alcohols,
glycols and mixtures
thereof. Especially preferred organic solvent to be added between step a) and
b) is a mixture
comprising ethanol propylene glycol and diethylene glycol.
The addition of the organic solvent between steps a) and b) further
contributes to reduction of the
water in the composition and consequently to the reduction of volume and to a
favorable
rheology of the resulting base composition.
The neutralizing agent of step b) can be selected from organic neutralizing
agents, inorganic
neutralizing agents and mixtures thereof. This neutralizing agent can be the
same or different to
that in the pre-neutralized sulphate detersive surfactant syrup. This
neutralizing agent is
preferably an alkanolamine, more preferably mono-ethanolamine (MEA), providing
the benefits
cited herein above.
In preferred embodiments more than 50%, preferably more than 60% and
especially more than
70% of the anionic surfactant in the base composition (i.e. sulphate and
sulphonate detersive
surfactant) is sulphate detersive surfactant. In a preferred embodiment the
sulphate detersive
surfactant and the sulphonate detersive surfactant are in a weight ratio of
from about 4:1 to about
1:1.
The detergent base preferably comprises from 0% to 5%, more preferably less
than 2% and
especially less than 1% by weight of the base of citric acid and any other
materials that have a
large sphere of hydration associated to them. The detergent base delivers
similar amounts of
actives to those delivered in traditional detergents in a smaller dose size
and because the water
content is lower some chemistry that is not necessarily compatible with or in
higher water
content products can be made compatible in lower water products.
According to a second aspect of the invention, there is provided a process for
making a laundry
liquid detergent comprising post-adding to the base composition obtainable and
preferably
obtained by the process of the first aspect of the invention from about 5 to
about 20% of water by
weight of the detergent. The base composition obtainable, and preferably
obtained, by the
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process of the first aspect of the invention is robust enough to withstand
water addition without
negatively influencing the rheology profile of the base composition.
According to a product aspect of the invention, there is provided a laundry
detergent obtainable
5 and preferably obtained according to the process of the first or second
aspect of the invention.
The detergent is quite compact thereby allowing for the delivery of a very
small dose (volume
wise) providing good cleaning results. Typical volumes of compacted detergents
are below 30
ml, more preferably below 25 ml. The detergent also has a good rheological
profile.
According to the last aspect of the invention, there is provided a method of
laundering fabric
comprising the step of contacting the fabric in a laundry washing machine with
a wash liquor
comprising from about 0.2 to about 1 g/l, preferably from about 0.3 to about
0.8 g/l, of the
detergent of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention envisages a process for making a detergent base
composition, preferably a
laundry liquid detergent base composition. It also envisages a detergent
composition obtainable
according to the process of the invention, and a method of laundering a fabric
using the detergent
composition. The process gives rise to a base composition that is very
versatile in terms of post-
addition of ingredients and presents a good rheological profile. The base can
be used to generate
a concentrated detergent, i.e., a detergent with high level of active
ingredients, or it can be further
diluted if desired.
Process for making the base composition
The process starts with a pre-neutralized sulfate detersive surfactant syrup.
Preferably the syrup
comprises an organic solvent, more preferably a non-amino functional solvent.
Optionally an organic solvent is added to the pre-neutralized sulfate
detersive surfactant syrup
and then the neutralizing agent is added. Once these ingredients are in a
mixing tank mixing is
commenced and the rest of the ingredients are added with agitation, the rest
of the ingredients
include brightener, non-ionic surfactant, dispersant polymer, surfactancy
boosting polymer,
chelant, etc. The temperature of the mixture is below 37 C (this is achieved
by cooling if the
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temperature of the mixture is above 37 C). Finally the sulphonic detersive
surfactant is added to
create the detergent base. The detergent base can be converted into a fully
formulated detergent
by the addition of other detergent ingredients such as enzymes and suds
suppresors.
Preferred sulfate detersive surfactant for use herein includes alkoxylated
and/or un-alkoxylated
alkyl sulfate materials.
Preferred alkoxylated alkyl sulfate materials 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'-0-(C2H40)n-S03M
wherein R is a C8-C20 alkyl group, n is from about 1 to 20, and M is a salt-
forming cation.
Preferably, R is C10-C18 alkyl and n is from about 1 to 15. Most preferably,
R' is a C12-C16
and n is from about 1 to 6.
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 unethoxylated alkyl sulfate materials, i.e., surfactants of the
above ethoxylated
alkyl sulfate formula wherein n=0. Unethoxylated alkyl sulfates may also be
added separately to
the compositions of this invention and used as or in any anionic surfactant
component which may
be present.
Preferred un-alkoxylated alkyl sulfate materials include mid-branched primary
alkyl sulfate
surfactants having an average carbon chain length of from about 14 to about 17
("MBAS
surfactants"). They provide good cleaning properties. MBAS surfactants with a
carbon chain
length of about 16 to 17 (also referred to as "HSAS surfactants") generally
provide better
cleaning than those of other chain-lengths.
Preferably the pre-neutralized sulfate detersive surfactant comprises a C8_18
alkyl ethoxylated
sulphate having an average degree of ethoxylation of from 0.5 to 10,
preferably from 0.5 to 7,
more preferably from 0.5 to 5 and most preferably from 0.5 to 6. At least 50%,
preferably at
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least 70% and especially 100% of the surfactant has being neutralized with
mono-ethanol amine.
In some embodiments, the pre-neutralized sulfate detersive surfactant
comprises a HSAS
surfactant. In other embodiments the pre-neutralized sulfate detersive
surfactant comprises a
mixture of an alkyl ehthoxylated sulphate with a HSAS surfactant, preferably
the alkyl
ehthoxylated sulphate and the HSAS surfactant are in a weight ratio of at
least 2:1, more
preferably at least 5:1 and specially at least 10:1. Preferably at least 50%,
more preferably at
least 70% and especially at least 90% of the sulfate detersive surfactant is
neutralized with mono-
ethanolamine.
Preferably the pre-neutralized sulfate detersive surfactant syrup comprises a
non-aminofunctional
solvent. As used herein, "non-aminofunctional solvent" refers to any solvent
which contains no
amino functional groups. Non-aminofunctional solvent include, for example: CI-
Cs alkanols
such as methanol, ethanol and/or propanol and/or 1-ethoxypentanol; C2-C6
diols; Cs-Cs
alkylene glycols; Cs-Cs alkylene glycol mono lower alkyl ethers; glycol
dialkyl ether; lower
is molecular weight polyethylene glycols; C3-C9 triols such as glycerol;
and mixtures thereof.
More specifically non-aminofunctional solvent are liquids at ambient
temperature and pressure
(i.e. 210 C. and I atmosphere), and comprise carbon, hydrogen and oxygen. When
present, non-
aminofunctional solvent may comprise from about 0% to about 25%, more
specifically from
about 1 to about 20%, even more specifically from about 5% to about 15% by
weight of the
syrup. The addition of the non-aminofunctional solvent would contribute to the
favorable
rheological profile of the base composition.
Preferred sulphonic detersive surfactant is a C10_16 alkyl benzene sulfonic
acid, preferably Cii_
14 alkyl benzene sulfonic acid. Preferably the alkyl group is linear and such
linear alkyl benzene
sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS,
are well known
in the art. Such surfactants and their preparation are described for example
in U.S. Patents
2,220,099 and 2.477,383.
Detergent composition
Detersive Surfactant
Compositions suitable for use herein comprises from 5% to 70% by weight,
preferably from 10%
to 60% by weight, more preferably from 20% to 50% by weight, of a certain kind
of detersive
surfactant component. Such an essential detersive surfactant component must
comprise anionic
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surfactants (sulphate and sulphonic detersive surfactants as described herein
before), nonionic
surfactants, or combinations of these two surfactant types. Preferably the
detergent comprises
from about 10% to about 40%, preferably from about 15% to 30% by weight of the
detergent of
an alkoxylated sulfate detersive surfactant. Preferably the detergent
comprises from 5% to 20%,
more preferably from 7 to 15% by weight of the detergent of a sulphonate
detersive surfactant.
Preferably the detergent comprises from 0.1% to 10%, more preferably from 1 to
5% by weight
of the detergent of a non-ionic detersive surfactant. Preferably the detergent
comprises from 0 to
10%, more preferably from 1 to 5% by weight of the detergent of a fatty acid.
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, ethylene oxide (E0)-propylene oxide (PO) block polymers, and amine
oxide
surfactants. Preferred for use in the liquid detergent products herein are
those nonionic
surfactants which are normally liquid.
Preferred nonionic surfactants for use herein include the alcohol allcoxylate
nonionic surfactants.
Alcohol alkoxylates are materials which correspond to the general formula:
R 1(CmH2m0)n01-1
wherein 10. is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12.
Preferably R1 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.
The alkoxylated fatty alcohol materials useful in the liquid detergent
compositions herein will
frequently have a hydrophilic-lipophilic balance (14I,B) which ranges from
about 3 to 17. More
preferably, the FILB 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 tradenames
NeodolTm and DobanolTM by the Shell Chemical Company.
Another type of nonionic surfactant which is liquid and which may be utilized
in the
compositions of this invention comprises the ethylene oxide (E0) - propylene
oxide (PO) block
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polymers. Materials of this type are well known nonionic surfactants which
have been marketed
under the tradename PluronicTM. These materials are formed by adding blocks of
ethylene oxide
moieties to the ends of polypropylene glycol chains to adjust the surface
active properties of the
resulting block polymers. EO-PO block polymer nonionics of this type are
described in greater
detail in Davidsohn and Milwidsky; Synthetic Detergents, 7th Ed.; Longman
Scientific and
Technical (1987) at pp. 34-36 and pp. 189-191 and in U.S. Patents 2,674,619
and 2,677,700.
Yet another suitable type of nonionic surfactant useful herein comprises the
amine oxide
surfactants. Amine oxides are mateials which are often referred to in the art
as "semi-polar"
nonionics. Amine oxides have the formula: R(E0)x(PO)y(B0)zN(0)(CH2R')2.qH20.
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 C17-C16 primary alkyl. R' is a short-chain moiety preferably
selected from
hydrogen, methyl and -CH7OH. When x+y+z is different from 0, E0 is
ethyleneoxy, PO is
propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated
by C19-14
alkyldimethyl amine oxide. Preferably the detergent of the invention comprises
from about 0.5%
to about 5%, more preferably from 0.8%to 3% by weight of the detergent of an
amine oxide
surfactant.
In the liquid detergent compositions herein, the essential detersive
surfactant component may
comprise combinations of anionic and nonionic surfactant materials. When this
is the case, the
weight ratio of anionic to nonionic is at least 2:1, preferably 5:1 and
especially 10:1. The
detergent composition comprises from 0% to 5%, more preferably less than 2%
and especially
less than 1% by weight of the detergent of citric acid. It is also preferred
that the detergent
composition has a low level (i.e. below 5% and more preferably below 2% by
weight of the
detergent) or it is free of fatty acid.
Preferably the liquid detergent compositions herein have a pH of from about 7
to about 9, more
preferably from 8 to 8.5 as measured in 5% aqueous solution at 20 C.
Laundry washing adjuncts
The detergent compositions herein, preferably in liquid form, comprise from
0.1% to 30% by
weight, preferably from 0.5% to 20% by weight, more preferably from 1% to 10%
by weight, of
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one or more of certain kinds of laundry washing adjuncts. Such laundry washing
adjuncts can be
selected from detersive enzymes, builders, chelants, soil release polymers,
soil suspending
polymers, optical brighteners, dye transfer inhibition agents, bleach,
whitening agents, suds
suppressors, fabric care benefit agents, solvents, stabilizers, buffers,
structurants, dyes and
5 perfumes and combinations of these adjunct types. All of these materials
are of the type
conventionally utilized in laundry detergent products.
The composition preferably comprises from 1 to 10% by weight of the
composition of polymer.
Suitable polymers include dispersant polymers such as polyamines, preferably
polyethylene
10 imines, most preferably alkoxylated polyethylene imines, preferably the
composition comprise
from about 1% to about 5% by weight of the composition of an alkoxylated
polyethylene imine.
Other preferred polymers include surfactancy boosting polymer. The composition
may comprise
a surfactancy boosting polymer. Preferred polymers are amphiphilic alkoxylated
grease cleaning
polymers and/or random graft co-polymers. Amphiphilic alkoxylated grease
cleaning polymers
refer to any alkoxylated polymers having balanced hydrophilic and hydrophobic
properties such
that they remove grease particles from fabrics and surfaces. Specific
embodiments of the
amphiphilic alkoxylated grease cleaning polymers suitable for use herein
comprise a core
structure and a plurality of alkoxylate groups attached to that core
structure.
The core structure may comprise a polyalkylenimine structure comprising, in
condensed form,
repeating units of formulae (I), (II), (III) and (IV):
#
/
\ i A1 /
*/N¨A1¨# #¨N #¨Ni #-N
\ \
Al *
\Al
\it \
#
(I) (II) (III) (IV)
wherein # in each case denotes one-half of a bond between a nitrogen atom and
the free binding
position of a group Al of two adjacent repeating units of formulae (I), (II),
(III) or (IV); * in each
case denotes one-half of a bond to one of the alkoxylate groups; and Al is
independently selected
from linear or branched C2-C6-alkylene; wherein the polyalkylenimine structure
consists of 1
repeating unit of formula (I), x repeating units of formula (II), y repeating
units of formula (III)
and y+1 repeating units of formula (IV), wherein x and y in each case have a
value in the range
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of from 0 to about 150; where the average weight average molecular weight, Mw,
of the
polyalkylenimine core structure is a value in the range of from about 60 to
about 10,000 g/mol.
The core structure may alternatively comprise a polyalkanolamine structure of
the condensation
products of at least one compound selected from N-(hydroxyalkyl)amines of
formulae (I.a)
and/or (I.b),
R1-
1 4 R4*
ROH ROH
AõA R2
AõA R5
N 0.a) N (I.b)
I )<R2* I R5*
HO A HO R6 HO
R3*>
R
wherein A are independently selected from Ci-C6-alkylene; Rl, Rt*, R2, R2*,
R3, R3*, R4, R4*, Rs
and R5* are independently selected from hydrogen, alkyl, cycloalkyl or aryl,
wherein the last
three mentioned radicals may be optionally substituted; and R6 is selected
from hydrogen, alkyl,
cycloalkyl or aryl, wherein the last three mentioned radicals may be
optionally substituted.
The plurality of alkylenoxy groups attached to the core structure are
independently selected from
alkylenoxy units of the formula (V)
4A2 0 ] m [ CH2 CH2 0 ]n [ A3 0-]¨R
P
(V)
wherein * in each case denotes one-half of a bond to the nitrogen atom of the
repeating unit of
formula (I), (II) or (IV); A2 is in each case independently selected from 1,2-
propylene, 1,2-
butylene and 1,2-isobutylene; A3 is 1,2-propylene; R is in each case
independently selected from
hydrogen and Ci-C4-alkyl; m has an average value in the range of from 0 to
about 2; n has an
average value in the range of from about 20 to about 50; and p has an average
value in the range
of from about 10 to about 50.
Specific embodiments of the amphiphilic alkoxylated grease cleaning polymers
may be selected
from alkoxylated polyalkylenimines having an inner polyethylene oxide block
and an outer
polypropylene oxide block, the degree of ethoxylation and the degree of
propoxylation not going
above or below specific limiting values.
Specific embodiments of the alkoxylated
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polyalkylenimines according to the present invention have a minimum ratio of
polyethylene
blocks to polypropylene blocks (nip) of about 0.6 and a maximum of about
1.5(x+2y+1)1/2.
Alkoxykated polyalkyenimines having an nip ratio of from about 0.8 to about
1.2(x+2y+1)1/2
have been found to have especially beneficial properties.
The alkoxylated polyalkylenimines according to the present invention have a
backbone which
consists of primary, secondary and tertiary amine nitrogen atoms which are
attached to one
another by alkylene radicals A and are randomly arranged. Primary amino
moieties which start
or terminate the main chain and the side chains of the polyalkylenimine
backbone and whose
remaining hydrogen atoms are subsequently replaced by alkylenoxy units are
referred to as
repeating units of formulae (I) or (IV), respectively. Secondary amino
moieties whose remaining
hydrogen atom is subsequently replaced by alkylenoxy units are referred to as
repeating units of
formula (II). Tertiary amino moieties which branch the main chain and the side
chains are
referred to as repeating units of formula (III).
Since cyclization can occur in the formation of the polyalkylenimine backbone,
it is also possible
for cyclic amino moieties to be present to a small extent in the backbone.
Such
polyalkylenimines containing cyclic amino moieties are of course alkoxylated
in the same way as
those consisting of the noncyclic primary and secondary amino moieties.
The polyalkylenimine backbone consisting of the nitrogen atoms and the groups
Al, has an
average molecular weight Mw of from about 60 to about 10,000 g/mole,
preferably from about
100 to about 8,000 g/mole and more preferably from about 500 to about 6,000
g/mole.
The sum (x+2y+1) corresponds to the total number of alkylenimine units present
in one
individual polyalkylenimine backbone and thus is directly related to the
molecular weight of the
polyalkylenimine backbone. The values given in the specification however
relate to the number
average of all polyalkylenimines present in the mixture. The sum (x+2y+2)
corresponds to the
total number amino groups present in one individual polyalkylenimine backbone.
The radicals Al connecting the amino nitrogen atoms may be identical or
different, linear or
branched C2-C6-alkylene radicals, such as 1,2-ethylene, 1,2-propylene, 1,2-
butylene, 1,2-
isobutylene,1,2-pentanediyl, 1,2-hexanediy1 or hexamethylen. A preferred
branched alkylene is
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1,2-propylene. Preferred linear alkylene are ethylene and hexamethylene. A
more preferred
alkylene is 1,2-ethylene.
The hydrogen atoms of the primary and secondary amino groups of the
polyalkylenimine
backbone are replaced by alkylenoxy units of the formula (V).
4A2 0 k [ CH2 CH2 0 Li [ A3 0 I-LR
(V)
In this formula, the variables preferably have one of the meanings given
below:
A2 in each case is selected from 1,2-propylene, 1,2-butylene and 1,2-
isobutylene;
preferably A2 is 1,2-propylene. A3 is 1,2-propylene; R in each case is
selected from hydrogen
and Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl
and tert.-butyl;
preferably R is hydrogen. The index m in each case has a value of 0 to about
2; preferably m is 0
or approximately 1; more preferably m is 0. The index n has an average value
in the range of
from about 20 to about 50, preferably in the range of from about 22 to about
40, and more
preferably in the range of from about 24 to about 30. The index p has an
average value in the
range of from about 10 to about 50, preferably in the range of from about 11
to about 40, and
more preferably in the range of from about 12 to about 30.
Preferably the alkylenoxy unit of formula (V) is a non-random sequence of
alkoxylate blocks.
By non-random sequence it is meant that the l-A2-0-1m is added first (i.e.,
closest to the bond to
the nitrgen atom of the repeating unit of formula (I), (II), or (III)), the l-
CH2-CH2-0-111 is added
second, and the l-A3-0-Ip is added third.
This orientation provides the alkoxylated
polyalkylenimine with an inner polyethylene oxide block and an outer
polypropylene oxide
block.
The substantial part of these alkylenoxy units of formula (V) is formed by the
ethylenoxy units -
lCH2-CH2-0)111- and the propylenoxy units 4CH2-CH2(CH3)-011,-. The alkylenoxy
units may
additionally also have a small proportion of propylenoxy or butylenoxy units
4A2-01m-, i.e. the
polyalkylenimine backbone saturated with hydrogen atoms may be reacted
initially with small
amounts of up to about 2 mol, especially from about 0.5 to about 1.5 mol, in
particular from
about 0.8 to about 1.2 mol, of propylene oxide or butylene oxide per mole of
NH- moieties
present, i.e. incipiently alkoxylated.
CA 02795931 2012-10-09
WO 2011/133378 PCT/US2011/032419
14
This initial modification of the polyalkylenimine backbone allows, if
necessary, the viscosity of
the reaction mixture in the alkoxylation to be lowered. However, the
modification generally does
not influence the performance properties of the alkoxylated polyalkylenimine
and therefore does
not constitute a preferred measure.
Preferably the composition comprise from about 0.1% to about 5%, more
preferably from about
0.25% to about 2.5% by weight of the composition of an amphiphilic alkoxylated
grease cleaning
polymer.
Suitable random graft co-polymers typically comprise: (i) hydrophilic backbone
comprising
monomers selected from the group consisting of: unsaturated C1_C6 carboxylic
acids, ethers,
alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic
anhydride, saturated
polyalcohols such as glycerol, and mixtures thereof; and (ii) hydrophobic side
chain(s) selected
from the group consisting of: C4_C25 alkyl group, polypropylene, polybutylene,
vinyl ester of a
saturated C1-C6 mono-carboxylic acid, Ci_C 6 alkyl ester of acrylic or
methacrylic acid, and
mixtures thereof.
The polymer preferably has the general formula:
- - _
X i 0 0
y _ m 0
¨ n ¨
= =
R 1 C(0)0 ______________________
= o
o
R21 1
R302C
= =
= = P
R4 ____________________
1 1
q
Z ,
wherein X, Y and Z are capping units independently selected from H or a Ci_6
alkyl; each Rl is
independently selected from methyl and ethyl; each R2 is independently
selected from H and
CA 02795931 2013-05-06
methyl; each R3 is independently a C14 alkyl; and each R4 is independently
selected from
pyrrolidone and phenyl groups. The weight average molecular weight of the
polyethylene oxide
backbone is typically from about 1,000 g/mol to about 18,000 g/mol, or from
about 3,000 g/mol
to about 13,500 g/mol, or from about 4,000 g/mol to about 9,000 g/mol. The
value of m, n, o, p
5 and q is selected such that the pendant groups comprise, by weight of the
polymer at least 50%,
or from about 50% to about 98%, or from about 55% to about 95%, or from about
60% to about
90%. The polymer useful herein typically has a weight average molecular weight
of from about
1,000 to about 100,000 g/mol, or preferably from about 2,500 g/mol to about
45,000 g/mol, or
from about 7,500 g/mol to about 33,800 g/mol, or from about 10,000 g/mol to
about 22,500
10 g/mol.
Example
Process for making a base detergent:
A 10 liter batch tank with an aspect ratio of about 1.3 (height to diameter)
is fitted with an
15 impeller mixer and is charged with the following:
1.) pre-neutralized sulphate detersive surfactant syrup composed of MEA:C12-15
E03S03H, ethanol and propylene glycol
2.) pre-neutralized sulphate detersive surfactant syrup composed of MEA:C16_17
Highly
Soluble Alkyl Sulfate, ethanol and propylene glycol
3.) organic solvent composed of ethanol; propylene glycol and diethylene
glycol.
4.) neutralizing agent (mono-ethanolamine)
Stirring is commenced at this point and additions are continued
5.) brightener premix composed of brightener chromaphore active, C12-
14(E0)9011 non-
ionic surfactant; mono-ethanolamine and water
6.) MEA-Boric acid premix composed of Boric acid, mono-ethanolamine and water
7.) Amine Oxide composed of C12-14 dimethylamine N-oxide and water
8.) Ethoxylated Polyamine Dispersant polymer (80 wt% active, 20 wt% water)
9.) Amphiphilic alkoxylated grease cleaning polymer (100% active)
10.) Diethylene triamine penta acetic acid penta sodium salt (DTPA) premix (50
wt% DTPA,
50wt% water)
CA 02795931 2013-12-04
16
11.) 1,2-dihydroxybenzene-3,5-disulfonic acid premix (50 wt% active)
12.) Calcium formate premix (10 wt%active)
Cooling is applied if needed during the next addition steps to maintain a
maximum
temperature of less than 37 C
13.) C12-18 Fatty acid
14.) C11.8 HLAS (alkyl benzene sulphonate)
Process for making a detergent composition
The base detergent is converted to finished detergent by continued stirring
and addition of:
15.) water
16.) perfume
17.) Hueing dye premix (0.32% active chromaphore)
18.) enzyme premix
19.) Suds supression polymer
20.) structurant
21.) Mica pearlescent particles
The detergent presents a good rheological profile and it is very stable.
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 ram"
