Note: Descriptions are shown in the official language in which they were submitted.
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Co-polymeric compounds comprising one or more active
aldehyde monomeric unit
Field of the invention
The present invention relates to co-polymeric compounds comprising one or
more active aldehyde monomeric unit. More particularly, it relates to
polymeric
compounds of aldehyde active monomeric unit and glyoxylic monomeric unit for
2o use in laundry and cleaning products as well as personal care compositions.
Back~~ound of the invention
Cleaning and laundry products are well-known in the art. However, ~. ,sumer
acceptance of laundry and cleaning products is determined not only by the
performance achieved with these products but also the aesthetics associated
3o therewith. The perfume components are therefore an important aspect of the
successful formulation of such commercial products.
It is also desired by consumers for laundered fabrics to maintain the pleasing
fragrance over time. Indeed, perfume additives make laundry compositions more
aesthetically pleasing to the consumer, and in some cases the perfume imparts
a
pleasant fragrance to fabrics treated therewith. However, the amount of
perfume
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carry-over from an aqueous laundry bath onto fabrics is often marginal and
does
not last long on the fabric. Furthermore, fragrance materials are often very
costly
and their inefficient use in laundry and cleaning compositions and ineffective
delivery to fabrics result in a very high cost to both consumers and laundry
and
cleaning manufacturers. Industry, therefore, continues to seek with urgency
for
more efficient and effective fragrance delivery in laundry and cleaning
products,
especially for improvement in the provision of long-lasting fragrance to the
fabrics.
One solution is to use carrier mechanisms for perfume delivery, such as by
encapsulation. This is taught in the prior art and described in U.S.
5,188,753.
Still another solution is to formulate compounds which provide a delayed
release
of the perfume over a longer period of time than by the use of the perfume
itself
have been provided. Disclosure of such compounds may be found in WO
~5 95104809, WO 95108976 and pending application EP 95303762.9.
However, notwithstanding the advances in the art, there is still a need for a
compound which provides a delayed release of the perfume component.
2o The Applicant has now found that co-polymeric compounds comprising one or
more active aldehyde ingredient also provide a delayed release of the active
such as a perfume.
Another advantage of the invention is that it allows the incorporation of a
high
25 proportion of active aldehyde into a polymeric compound. Preparing a
polymer of
an active aldehyde alone would be highly desirable for the controlled release
of
said active aldehyde. However, it is known to the persons skilled in the art
that
these poly(active aldehyde) can not be easily obtained by direct
polymerisation of
one or more active aldehydes alone. The applicants have found that the
3o polymerisation of a suitable comonomer along with the active aldehydes
allow
them to incorporate a high proportion of one or more active aldehydes into a
polymeric compound. Had the co-monomer not been present, no incorporation of
the aldehyde into a polymeric compound would have taken place, under the
same conditions.
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Still another advantage of the present invention is that by choosing the
suitable
co-monomeric unit and end-capping groups, it provides sufficient stabilisation
of
the linkage bond between the active aldehyde group with its polymeric carrier
so
that the release of the active ingredients upon storage in product is limited,
s without hindering the release of the active ingredients upon use of the
product.
Still another advantage of the invention compounds is their ease of
manufacture
rendering their use most desirable.
Summaryr of the invention
The present invention relates to a co-polymeric compound comprising one or
more active aldehyde ingredient, wherein said compound has the following
empirical formula:
_~Ym-An~_
wherein Y is a comonomeric aldehyde unit of formula R'COH,
2o wherein R' is the organic chain of an active aldehyde,
wherein A is a comonomeric unit capable of polymerising the aldehyde
monomeric unit, and
wherein n and m are each independently indexes of value of at least 1.
In another aspect of the invention, there is provided a laundry and cleaning
composition or personal cleansing composition comprising said compound.
Still another aspect of the invention is a method of delivering residual
fragrance
to a surface which comprises the steps of contacting said surface with a
3o compound of the invention or a composition comprising said compound in
presence of a material so that the copolymer backbone is hydrolysed, thereby
slowly releasing overtime the perfume aldehydes.
Detailed description of the invention
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The essential component of the invention is a co-polymeric compound
comprising one or more active aldehyde ingredient. The compound of the
invention has the following empirical formula:
-~m-An~-
wherein Y is a co-monomeric aldehyde unit of formula R'COH,
wherein R' is the organic chain of an active aldehyde,
wherein A is a co-monomeric unit capable of polymerising the aldehyde
1o monomeric unit, and
wherein n and m are each independently indexes of value of at least 1,
preferably less than 1000, most preferably less than 100.
Preferably, the ratio n/m is greater than 1, most preferably greater than 3.
By "co-monomeric unit", it is meant any suitable comonomer which can be
copolymerised with the aldehyde monomeric unit. Typical of such comonomers
are those having at least two reactive sites and which do not inhibit the
polymerisation or cause the copolymer to depolymerise in alkaline solution.
2o Preferably, these monomeric units are selected from keto carboxylates
R'lOC(CR4R4)qCOOR and among keto carboxylates more preferably glyoxylates
(R'1 =H, q=0) or a-keto malonates (R'1 =COOR, q=0).
For ease of purpose, the copolymer has been schematised under its empirical
formula as a block copolymer. However, it will be obvious for those skilled in
the
art that, in general, by copolymerisation of two or more different monomers,
the
copolymer obtained generally show a completely random distribution of the
monomers along the backbone of the polymer rather than the block distribution
represented above. Any combination possible of the different monomers in the
3o copolymer will not affect the overall controlled release benefit observed
with such
copolymer and are therefore included in the present description.
Preferred co-monomeric unit A capable of polymerising the aldehyde monomeric
unit is keto carboxylate monomeric unit of formula:
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R~~
O
CR4 ~C~R4~q
O"O
i
R
wherein each R is independently selected from hydrogen, alkali metals,
ammonium, alkyl, alkylene, aryl, alkylaryl, or any other chain containing at
least 1
carbon atom;
5 wherein each R'1 is independently selected from hydrogen, hydroxyl, alkyl,
alkylene, aryl, alkylaryl, COOR3, (CR4R4)qCOOR3, OR3, or any other chains
containing at least 1 carbon atom;
wherein each R3 is independently selected from hydrogen, alkali metals,
ammonium, alkyl, alkylene, aryl, alkylaryl, or any other chain containing at
least 1
1o carbon atom, and
wherein each R4 are independently selected from hydrogen, hydroxyl, alkyl,
alkylene, aryl, alkylaryl, COOR3, CH2COOR3, OR3, or any other chain
containing at least 1 carbon atom; and
wherein q is from 0 to 10, preferably from 0 to 4, more preferably 0, 1 or 2.
Most preferred co-monomeric keto carboxylate unit A capable of polymerising
the
aldehyde monomeric unit is a glyoxylic monomeric unit of formula:
wherein each R is independently selected from hydrogen, alkali metals,
ammonium, alkyl, alkylene, aryl, alkylaryl, or any other chain containing at
least 1
carbon atom;
wherein each R'1 is independently selected from hydrogen, hydroxyl, alkyl,
alkylene, aryl, afkylaryl, COOR3, OR3, or any other chains containing at least
1
carbon atom;
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wherein each R3 is independently selected from hydrogen, alkali metals,
ammonium, alkyl, alkylene, aryl, alkylaryl, or any other chain containing at
least 1
carbon atom, and
wherein q is 0.
Preferably, for the above keto carboxylate and glyoxylic monomeric unit, the R
groups are each independently selected from alkali metals, ammonium, C1-Cfi
alkyl chains, and more preferably are selected from methyl and ethyl.
The preferred R'1 groups are each independently selected from hydrogen, -
COOR3, (CR4R4)qCOOR3, aryl group, and C1-C6 alkyl chains, and more
preferably are selected from hydrogen, -COOR3, phenyl, methyl and ethyl.
The preferred R3 groups are each independently selected from hydrogen, alkali
~5 metals, ammonium, aryl group and C1-C6 alkyl chains, and more preferably
are
selected from hydrogen, alkali metals, ammonium, methyl and ethyl.
The preferred R4 are each independently selected from hydrogen, -COOR3, aryl
group and C1-C6 alkyl chains, and more preferably is selected from hydrogen,
2o phenyl, methyl and ethyl.
By alkyl and alkenyl chain, it is understood a chain length of at least 1
carbon,
preferably 1 to 20 carbon atoms, and more preferably is methyl or ethyl.
Of course, it is also understood that the chain and cycles can be optionally
25 substituted or interrupted. Typical of such substitution is a short alkyl
chain such
as methyl, ethyl, or hydroxy group. Typical of such interruption is with an O,
N,
CO, OC(O), CO(O), C(O)N, NC(O) and mixtures thereof.
For the above mentioned compounds, by "organic chain" of an active aldehyde,
it
3o is meant any chain containing at least 1 carbon atom, preferably at least 5
carbon atoms. Preferably, the active aldehyde is respectively selected from a
flavour aldehyde ingredient, a pharmaceutical aldehyde active, a biocontrol
aldehyde agent, a pertume aldehyde component and mixtures thereof. When
more than one organic chain of an active aldehyde is present on the compound
a5 of the invention, each organic chain of an active aldehyde can be different
from
the others, e.g. when there are two organic chain of an active aldehyde, one
can
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be a biocontrol aldehyde agent and the other a pertume aldehyde component, or
one organic chain of an active aldehyde is a pertume aldehyde component and
the other organic chain of an active aldehyde a different perfume aldehyde
component.
Flavour ingredients include spices, flavor enhancers that contribute to the
overall
flavour perception.
Pharmaceutical actives include drugs.
Biocontrol agents include biocides, antimicrobials, bactericides, fungicides,
algaecides, mildewcides, disinfectants, antiseptics, insecticides, vermicides,
plant
growth hormones.
Pertume aldehyde components include components having odoriferous
properties.
Preferably, for the above mentioned compounds, the R' group is the organic
chain of a perfume aldehyde, said aldehyde being selected from 2,6,10-
trimethyl-
9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamic aldehyde, 4-
methoxybenzaldehyde, benzaldehyde, 3-(4-tert butylphenyl)-propanal, 2-methyl-
3-(para-methoxyphenyl propanal, 2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-
yl) butanal, 3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al,
3,7-
dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy] acetaldehyde, 4-
isopropylbenzyaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-
naphthaldehyde, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, 2-methyl-3-
(isopropylphenyl)propanal, 1-decanal; decyl aldehyde, 2,6-dimethyl-5-heptenal,
4-(tricyclo[5.2.1.0(2,6)J-decylidene-8)-butanal, octahydro-4,7-methano-1 H-
indenecarboxaldehyde, 3-ethoxy-4-hydroxy benzaldehyde, para-ethyl-alpha,
3o alpha-dimethyl hydrocinnamatdehyde, alpha-methyl-3,4-(methylenedioxy)-
hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexyl
cinnamic aldehyde, m-cymene-7-carboxaldehyde, alpha-methyl phenyl
acetaldehyde, 7-hydroxy-3,7-dimethyl octanal, Undecenal, 2,4,6-trimethyl-3-
cyclohexene-1-carboxaldehyde, 4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-
carboxaldehyde, 1-dodecanal, 2,4-dimethyl cyclohexene-3-carboxaldehyde, 4-(4-
hydroxy-4-methyl pentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-
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dimethyloctan-1-al, 2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-
octanal,
2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal,
Phenylacetaldehyde, dihydrocinnarnic Aldehyde, 1-methyl-4-(4-methyl-3-
pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or 6 methoxy0hexahydro-4,7-
methanoindan-1 or 2- carboxaldehyde, 3,7-dimethyloctan-1-al, 2,4-dimethyl-3-
cyclohexene-1-carboxaldehyde, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-
methoxy benzaldehyde, 1-methyl-3-(4-methylpentyl)-3-
cyclhexenecarboxaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 7-
hydroxy-3,7-dimethyl-octanal, traps-4-decenal, 2,6-nonadienal, para-
tolylacetaldehyde; 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-
cyclohexen-1-yl)-2-butenal, ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-
cyclohexene carboxaldehyde and 2,4,6-trimethyl-3-cyclohexene carboxaldehyde,
3,7-dimethyl-2-methylene-6-octenal, Phenoxyacetaldehyde, 5,9-dimethyl-4,8-
decadienal, Peony Aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al),
~5 hexahydro-4,7-methanoindan-1-carboxxaldehyde, 2-methyl octanal, alpha-
methyl-4-(1-methyl ethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-
propionaldehyde, para methyl phenoxy acetaldehyde, 2-methyl-3-phenyl-2-
propen-1-al, 3,5,5-trimethyl hexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyde,
3-propyl-bicyclo[2.2.1 ]-hept-5-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-
2o phenyl-1-pentanal, methylnonyl acetaldehyde, benzaldehyde, and mixtures
thereof.
Most preferred aldehydes are selected from 1-octanal, 1-decanal, 1-dodecanal,
methylnonyl acetaldehyde, traps-4-decenal, benzaldehyde and mixture thereof.
25 For the purpose of the invention, mixtures of the above compounds
comprising
one or more active aldehydes may also be used.
Mechanism of release
3o By the present invention, a delayed release of an active ingredient, i.e.
aldehyde
is obtained. Not to be bound by theory, the release is believed to occur by
the
following mechanism:
For copolymers or oligomers of active aldehydes and of suitable comonomers
such as keto carboxylates (in particular glyoxylic esters), the active
aldehydes
35 are released upon breaking down of the acetals bond forming the backbone of
the polymer, leading to the release of the active aldehyde and of the suitable
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comonomers. This can be achieved by either hydrolysis, photochemical
cleavage, enzymatic cleavage or oxidative cleavage-of the bond linking the end-
capping group to the rest of the polymer or any acetal bonds along the polymer
backbone.
P rocess
Preparation of the component is made as follows in the Synthesis Examples. In
general, process for preparing a copolymer comprising one or more active
aldehydes comprises the steps of polymerising one or more active aldehydes
with one or more suitable comonomers, preferably keto carboxylates, most
preferably glyoxylates such as methyl glyoxylate, in presence of a
polymerisation
catalyst, preferably a strong Lewis acid such as boron trifluoride diethyl
etherate
or an anionic catalyst such as sodiomalonates or sodiomethylmalonate esters.
~5 Preferred features of these general processes for manufacturing the present
compounds invention are described hereinafter.
A preferred process for preparing copolymers of one or more active aldehydes:
(A)- to bring together under polymerisation conditions one or more active
2o aldehydes with one or more comonomers capable of polymerising the aldehyde
monomeric unit, in presence of a polymerisation initiator; and
(B)- End-capping the resulting copolymer with a suitable chemical group so
that
the in-product stability of the polymer can be optimised to prevent excessive
depolyrnerisation in-product.
As described hereinbefore, the preferred comonomers capable of polymerising
the aldehyde monomeric unit are the a-keto carboxylates, most preferably the
methyl glyoxylate.
3o Suitable initiator for the copolymerisation are know to~ those skilled in
the art and
described in the art such as in US 4,204,052 Column 4, lines 3-15. Preferred
initiators are phosphorus pentoxide, amines, strong Lewis acid such as boron
trifluoride diethyl etherate, hydroxide or cyanide ions or anionic catalyst
such as
sodiomalonates or sodiomethylmalonate esters. Most preferred initiators are
phosphorus pentoxide, amines, strong Lewis acid such as boron trifluoride
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diethyl etherate, or anionic catalyst such as sodiomalonates or
sodiomethylmalonate esters.
The copolymerisation step can be done with or without solvent. Suitable
s solvents include alkyl nitrites, preferably acetonitrile, dimethyl
sulfoxide, acetone,
halogenated alkanes, preferably dichloromethane or chloroform,
tetrahydrofuran,
ethyl acetate and the like. When a solvent is used, the choice of the solvent
is
driven, so that it does not interfere with the copolymerisation and can be
separated from the resulting copolymer with relative ease. These solvents can
1o also be used for the end-capping step (B). Dichloromethane and acetonitrile
are
the preferred solvents for both steps (A) and (B) of the process.
Once the copolymer of one or more active aldehydes and. at least one suitable
comonomer has been prepared, any number of chemically reactive groups can
be added to the copolymer termini, preferably using an ionic catalyst such as
boron trifluoride etherate, trifluoroacetic acid and the like as described in
US
4,204,052 Column 5 line 25 to Column 6 line 28.
The resulting co-polymer has the following empirical formula:
R 1-[Yr,.; A"J-R2
wherein Y, A, m and n are as defined hereinbefore; and
wherein R1 and R2 are end-capping groups.
Particularly suitable end-capping groups include alkyl groups, alkyl groups
2s containing oxygen such as -CH2CHOH or alkoxy, preferably methoxy, or ethers
such as -CH(CH3)-O-CH2CH3, -OCH2CHOH and -OCH(CH3)-O-CH2CH3, and
alkyl groups containing carboxylic acids. Particularly preferred end-capping
groups for the purpose of the invention are alkyl groups containing oxygen,
preferably selected from -CH2CHOH, -CH(CH3)-O-CH2CH3, -OCH2CHOH and
-OCH(CH3)-O-CH2CH3. As will occur to those skilled in the art in light of the
present disclosure, the chemically stable end groups at the polymer termini
can
be like or unlike.
The chemical nature of the chemically reactive group is not important in the
3s proper function of the copolymer in its intended use to release active
aldehydes.
It is only necessary that the chemically reactive group stabilises the
copolymer so
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that to limit the depolymerisation before use. The end-capping group can be
chosen so that depolymerisation upon usage is triggered by either hydrolysis,
photochemical cleavage, enzymatic cleavage or oxidative cleavage of the bond
linking the end-capping group to the rest of the polymer or any acetal bonds
along the polymer backbone.
Laundry and cleaning compositions
The present invention compositions include both laundry and cleaning
compositions which are typically used for laundering fabrics and cleaning hard
1o surfaces such as dishware, floors, bathrooms, toilet, kitchen and other
surfaces
in need of a delayed release of an active alcohol or mixed alcohol/aldehyde.
This
also includes compositions for use in personal cleansing such as shower gels,
deodorants, bars, shampoos.
Preferred are those laundry compositions which result in contacting the
compound of the invention with fabric. Preferably, for use in such laundry and
cleaning products, the active alcohol is a perfume such as geraniol.
These are to be understood to include not only detergent compositions which
2o provide fabric cleaning benefits, but also compositions such as rinse added
fabric
softener compositions and dryer added compositions (e.g. sheets) which provide
softening and/or antistatic benefits as well as hard surface cleaning.
The compounds) of the invention typically comprise from 0.01 % to 10%,
preferably from 0.05% to 5%, and more preferably from 0.1 % to 2%, by weight
of
the composition. Mixtures of the compounds may also be used herein.
Optional ingredients useful for formulating such laundry and cleaning
compositions according to the present invention include one or more of the
3o following.
Fabric Softening Agents:
A fabric softener component may also suitably be used in the laundry and
cleaning compositions of the invention so as to provide softness and
antistastic
properties to the treated fabrics. When used, the fabric softener component
will
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typically be present at a level sufficient to provide softening and antistatic
properties.
Said fabric softening component may be selected from cationic, nonionic,
amphoteric or anionic fabric softening component.
Typical of the cationic softening components are the quaternary ammonium
compounds or amine precursors thereof as defined hereinafter.
1o A)-Quaternary Ammonium Fabric Softening Active Compound
(1 ) Preferred quaternary ammonium fabric softening active compound have the
formula:
+ _
(R)4-m N (CH2)ri Q-R~ X
m
(1)
or the formula:
N ~~---CH-G~ -Q,R~ X
~~4-m
Q - R~ (2)
wherein Q is a carbonyl unit having the formula:
O O O R2 O O R2
-O-C- , -C-O- , -O-C-O- , -N-C- , -C-N-
each R unit is independently hydrogen, C1-Cg alkyl, C1-Cg hydroxyalkyl, and
mixtures thereof, preferably methyl or hydroxy alkyl; each R1 unit is
2o independently linear or branched C11-C22 alkyl, linear or branched C11-C22
alkenyl, and mixtures thereof, R2 is hydrogen, C1-C4 alkyl, C1-C4
hydroxyalkyl,
and mixtures thereof; X is an anion which is compatible with fabric softener
actives and adjunct ingredients; the index m is from 1 to 4, preferably 2; the
index n is from 1 to 4, preferably 2.
An example of a preferred fabric softener active is a mixture of quaternized
amines having the formula:
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+ O
R2-N (CH2hi-O-C-R~ X '
2
wherein R is preferably methyl; R1 is a linear or branched alkyl or alkenyl
chain
comprising at least 11 atoms, preferably at least 15 atoms. In the above
fabric
softener example, the unit -02CR1 represents a fatty acyi unit which is
typically
derived from a triglyceride source. The triglyceride source is preferably
derived
from tallow, partially hydrogenated tallow, lard, partially hydrogenated lard,
vegetable oils andlor partially hydrogenated vegetable oils, such as, canola
oil,
safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil,
rice bran oil,
etc. and mixtures of these oils.
The preferred fabric softening actives of the present invention are the
Diester
andlor Diamide Quaternary Ammonium (DEQA) compounds, the diesters and
diamides having the formula:
(R)4-m N (CHZ~-Q-R1 X'
m
wherein R, R1, X, and n are the same as defined herein above for formulas (1)
and (2), and Q has the formula:
-O-O- or -N-O-.
These preferred fabric softening actives are formed from the reaction of an
amine
with a fatty acyi unit to form an amine intermediate having the formula:
R-N (CH2)ri Z
2
wherein R is preferably methyl, Z is -OH, -NH2, or mixtures thereof; followed
by
quaternization to the final softener active.
Non-limiting examples of preferred amines which are used to form the DEQA
2s fabric softening actives according to the present invention include methyl
bis(2-
hydroxyethyl)amine having the formula:
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CH3
HON OOH
methyl bis(2-hydroxypropyl)amine having the formula:
CH3
N
HO OH
methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:
CH3
HO~N~NH2
,
methyl bis(2-aminoethyl)amine having the formula:
CH3
H2N ~N ~NH2
triethanol amine having the formula:
~OH
HON OOH
1o di(2-aminoethyl) ethanolamine having the formula:
~OH
H2N ~N ~NH2
The counterion, X(-) above, can be any softener-compatible anion, preferably
the anion of a strong acid, for example, chloride, bromide, methylsulfate,
ethylsulfate, sulfate, nitrate and the like, more preferably chloride or
methyl
~ 5 sulfate. The anion can also, but less preferably, carry a double charge in
which
case X(-) represents half a group.
Tallow and canola oil are convenient and inexpensive sources of fatty acyl
units
which are suitable for use in the present invention as R~ units. The following
are
2o non-limiting examples of quaternary ammonium compounds suitable for use in
the compositions of the present invention. The term "tallowyl" as used herein
below indicates the R~ unit is derived from a tallow triglyceride source and
is a
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mixture of fatty acyl units. Likewise, the use of the term canolyl refers to a
mixture of fatty acyl units derived from canola oil.
Table II
5 Fabric Softener Actives
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride
N,N-di(2-talfowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
15 chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N, N-dimethyl
ammonium chloride;
2o N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride;
N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium
chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
Other examples of quaternay ammoniun softening compounds are
methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and
methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium
methylsulfate; these materials are available from Witco Chemical Company
under the trade names Varisoft~ 222 and Varisoft~ 110, respectively.
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16
Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride, where the tallow chains are at least partially unsaturated.
The level of unsaturation contained within the tallow, canola, or other fatty
acyl
s unit chain can be measured by the Iodine Value (IV) of the corresponding
fatty
acid, which in the present case should preferably be in the range of from 5 to
100
with two categories of compounds being disting~rished, having a IV below or
above 25.
~o Indeed, for compounds having the formula:
+ _
(R)4-m N (CH2)n Q-R~ X
m
derived from tallow fatty acids, when the Iodine Value is from 5 to 25,
preferably
15 to 20, it has been found that a cisltrans isomer weight ratio greater than
30170, preferably greater than 50150 and more preferably greater than 70130
~5 provides optimal concentrability.
For compounds of this type made from tallow fatty acids having a Iodine Value
of
above 25, the ratio of cis to mans isomers has been found to be less critical
unless very high concentrations are needed.
Other suitable examples of fabric softener actives are derived from fatty acyl
2o groups wherein the terms "tallowyl" and canolyl" in the above examples are
replaced by the terms "cocoyl, palmyl, lauryl, oleyl, ricinoleyl, stearyl,
palmityl,"
which correspond to the triglyceride source from which the fatty acyl units
are
derived. These alternative fatty acyl sources can comprise either fully
saturated,
or preferably at least partly unsaturated chains.
As described herein before, R units are preferably methyl, however, suitable
fabric softener actives are described by replacing the term "methyl" in the
above
examples in Table II with the units "ethyl, ethoxy, propyl, propoxy,
isopropyl,
butyl, isobutyl and t-butyl.
The counter ion, X, in the examples of Table II can be suitably replaced by
bromide, methylsulfate, formate, sulfate, nitrate, and mixtures thereof. In
fact,
the anion, X, is merely present as a counterion of the positively charged
CA 02310737 2000-OS-18
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17
quaternary ammonium compounds. The scope of this invention is not considered
limited to any particular anion.
For the preceding ester fabric softening agents, the pH of the compositions
s herein is an important parameter of the present invention. Indeed, it
influences
the stability of the quaternary ammonium or amine precursors compounds,
especially in prolonged storage conditions.
The pH, as defined in the present context, is measured in the neat
compositions
at 20 °C. While these compositions are operable at pH of less than 6.0,
for
0 optimum hydrolytic stability of these compositions, the neat pH, measured in
the
above-mentioned conditions, must preferably be in the range of from 2.0 to 5,
preferably in the range of 2.5 to 4.5, preferably 2.5 to 3.5. The pH of these
compositions herein can be regulated by the addition of a Bronsted acid.
Examples of suitable acids include the inorganic mineral acids, carboxylic
acids,
~5 in particular the low molecular weight (C1-C5) carboxylic acids, and
alkylsulfonic
acids. Suitable inorganic acids include HCI, H2S04, HN03 and H3P04.
Suitable organic acids include formic, acetic, citric, methylsulfonic and
ethylsulfonic acid. Preferred acids are citric, hydrochloric, phosphoric,
formic,
methylsulfonic acid, and benzoic acids.
As used herein, when the diester is specfied, it will include the monoester
that is
normally present in manufacture. For softening, under nollow detergent
carry-over laundry conditions the percentage of monoester should be as low as
possible, preferably no more than 2.5%. However, under high detergent
carry-over conditions, some monoester is preferred. The overall ratios of
diester
to monoester are from 100:1 to 2:1, preferably from 50:1 to 5:1, mare
preferably
from 13:1 to 8:1. Under high detergent carry-over conditions, the dilmonoester
ratio is preferably 11:1. The level of monoester present can be controlled in
the
manufacturing of the softener compound.
Mixtures of actives of formula {1) and (2) may also be prepared.
2)-Still other suitable quaternary ammonium fabric softening compounds for use
herein are cationic nitrogenous salts having two or more long chain acyclic
aliphatic Cg-C22 hydrocarbon groups or one said group and an arylalkyl group
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18
which can be used either alone or as part of a mixture are selected from the
group consisting of:
(i) acyclic quaternary ammonium salts having the formula:
R4 +
R8-N._Rs
~s
wherein R4 is an acyclic aliphatic Cg-C22 hydrocarbon group, R5 is a C1-
C4 saturated alkyl or hydroxyalkyl group, R8 is selected from the group
consisting of R4 and R5 groups, and A- is an anion defined as above;
(ii) diamino alkoxylated quaternary ammonium salts having the formula:
O Rs O +
R'-C-NH-R2-N-R2-NH-C-R~ A
I
(CH2CH20)nH
wherein n is equal to 1 to 5, and R1, R2, R5 and A- are as defined above;
(iii) mixtures thereof.
Examples of the above class cationic nitrogenous salts are the well-known
dialkyldi methylammonium salts such as ditallowdimethylammonium chloride,
ditallowdimethylammonium methylsulfate,
2o di(hydrogenatedtallow)dimethylammonium chloride, distearyldimethylammonium
chloride, dibehenyldimethylammonium chloride. Di(hydrogenatedtallow)di
methylammonium chloride and ditallowdimethylammonium chloride are preferred.
Examples of commercially available dialkyldimethyl ammonium salts usable in
the present invention are di(hydrogenatedtallow)dimethylammonium chloride
(trade name Adogen~ 442), ditallowdimethylammonium chloride {trade name
Adogen~ 470, Praepagen~ 3445), distearyl dimethylammonium chloride (trade
name Arosurf~ TA-100), all available from Witco Chemical Company.
Dibehenyldimethylammonium chloride is sold under the trade name Kemamine
Q-2802C by Humko Chemical Division of Witco Chemical Corporation.
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19
Dimethylstearylbenzyl ammonium chloride is sold under the trade names Varisoft
~ SDC by Witco Chemical Company and Ammonyx~ 490 by Onyx Chemical
Company.
Bl-Amine Fabric Softening Active Compound
Suitable amine fabric softening compounds for use herein, which may _be in
amine form or cationic form are selected from:
(i)- Reaction products of higher fatty acids with a polyamine selected from
the
1o group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines
and
mixtures thereof. These reaction products are mixtures of several compounds in
view of the multi-functional structure of the polyamines.
The preferred Component (i) is a nitrogenous compound selected from the group
consisting of the reaction product mixtures or some selected components of the
mixtures.
One preferred component (i) is a compound selected from the group consisting
of substituted imidazoline compounds having the formula:
N
R7~
N
R8-NH-C-R7
I I
O
wherein R7 is an acyclic aliphatic C1~-C21 hydrocarbon group and R$ is a
2o divalent C1-C3 alkylene group.
Component (i) materials are commercially available as: Mazamide~ 6, sold by
Mazer Chemicals, or Ceranine~ HC, sold by Sandoz Colors & Chemicals; stearic
hydroxyethyl imidazoline sold under the trade names of Alkazine~ ST by Alkaril
Chemicals, Inc., or Schercozoline~ S by Scher Chemicals, Inc.; N,N"-
ditallowalkoyldiethylenetriamine; 1-tallowamidoethyl-2-tallowimidazoline
(wherein
in the preceding structure R1 is an aliphatic C15-C17 hydrocarbon group and R8
is a divalent ethylene group).
3o Certain of the Components (i) can also be first dispersed in a Bronsted
acid
dispersing aid having a pKa value of not greater than 4; provided that the pH
of
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the final composition is not greater than 6. Some preferred dispersing aids
are
hydrochloric acid, phosphoric acid, or methylsulfonic- acid.
Both N,N"-ditallowalkoyldiethylenetriamine and 1-tallow(amidoethyl)-2-
s tallowimidazoline are reaction products of tallow fatty acids and
diethylenetriamine, and are precursors of the cationic fabric softening agent
methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see "Cationic
Surface Active Agents as Fabric Softeners," R. R. Egan, Journal of the
American
Oil Chemicals' Society, January 1978, pages 118-121). N,N"-ditallow
alkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be
obtained from Witco Chemical Company as experimental chemicals. Methyl-1-
tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by Witco Chemical
Company under the tradename Varisoft~ 475.
~5 (ii)-softener having the formula:
N
R~
C
O ~ ~ -)
N ~ ?C~
Rs
R' C G Rz
wherein each R2 is a C1-g alkylene group, preferably an ethylene group; and G
is an oxygen atom or an -NR- group; and each R, R1, R2 and R5 have the
definitions given above and A- has the definitions given above for X-.
2o An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium
chloride
wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an
ethylene
group, G is a NH group, R5 is a methyl group and A- is a chloride anion.
(iii)- softener having the formula:
H H
\N-R2-N
N~ N aA0
R1 R'
wherein R, R1, R2, and A- are defined as above.
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21
An example of Compound (iii) is the compound having the formula:
~ H H~
N-CH2CH2-N I Cl
N
R~ Rt
wherein R1 is derived from oleic acid.
s Additional fabric softening materials may be used in addition or
alternatively to
the cationic fabric softener. These may be selected from nonionic, amphoteric
or
anionic fabric softening material. Disclosure of such materials may be found
in
US 4,327,133; US 4,421,792; US 4,426,299; US 4,460,485; US 3,644,203; US
4,661,269; U.S 4,439,335; U.S 3,861,870; US 4,308,151; US 3,886,075; US
10 4,233,164; US 4,401,578; US 3,974,076; US 4,237,016 and EP 472,178.
Typically, such nonionic fabric softener materials have an HLB of from 2 to 9,
more typically from 3 to 7. Such nonionic fabric softener materials tend to be
readily dispersed either by themselves, or when combined with other materials
15 such as single-long-chain alkyl cationic surfactant described in detail
hereinafter.
Dispersibility can be improved by using more single-long-chain alkyl cationic
surfactant, mixture with other materials as set forth hereinafter, use of
hotter
water, and/or more agitation. In general, the materials selected should be
relatively crystalline, higher melting, (e.g. >40°C) and relatively
water-insoluble.
Preferred nonionic softeners are fatty acid partial esters of polyhydric
alcohols, or
anhydrides thereof, wherein the alcohol, or anhydride, contains from 2 to 18,
preferably from 2 to 8, carbon atoms, and each fatty acid moiety contains from
12
to 30, preferably from 16 to 20, carbon atoms. Typically, such softeners
contain
2s from one to 3, preferably 2 fatty acid groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol,
poly
(e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose,
erythritol,
pentaerythritol, sorbitol or sorbitan. Sorbitan esters and polyglycerol
3o monostearate are particularly preferred.
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22
The fatty acid portion of the ester is normally derived from fatty acids
having from
12 to 30, preferably from 16 to 20, carbon atoms, typical examples of said
fatty
acids being lauric acid, myristic acid, palmitic acid, stearic acid and
behenic acid.
Highly preferred optional nonionic softening agents for use in the present
invention are the sorbitan esters, which are esterified dehydration products
of
sorbitol, and the glycerol esters.
Commercial sorbitan monostearate is a suitable material. Mixtures of sorbitan
stearate and sorbitan palmitate having stearate/palmitate weight ratios
varying
1o between 10:1 and 1:10, and 1,5-sorbitan esters are also useful.
Glycerol and polygiycerol esters, especially glycerol, diglycerol,
triglycerol, and
polyglycerol mono- and/or di-esters, preferably mono-, are preferred herein
(e.g.
polyglycerol monostearate with a trade name of Radiasurf 7248}.
Useful glycerol and polyglycerol esters include mono-esters with stearic,
oleic,
palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters
of
stearic, oleic, palmitic, lauric, isostearic, behenic, andlor myristic acids.
It is
understood that the typical mono-ester contains some di- and tri-ester, etc.
The "glycerol esters" also include the polyglycerol, e.g., diglycerol through
octaglycerol esters. The polyglycerol polyols are formed by condensing
glycerin
or epichiorohydrin together to link the glycerol moieties via ether linkages.
The
mono- andlor diesters of the polyglycerol polyols are preferred, the fatty
acyl
groups typically being those described hereinbefore for the sorbitan and
glycerol
esters.
Further fabric softening components suitable for use herein are the softening
clays, such as the low ion-exchange-capacity ones described in EP-A
0,150,531.
Of course, the term "softening active" can also encompass mixed softening
active agents.
Preferred among the classes of softener compounds disclosed herein before are
the diester or diamido quaternary ammonium fabric softening active compound
(DEQA).
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23
The fabric softener compounds herein are present-at levels of from 1 % to 80%
of
compositions herein, depending on the composition execution which can be
dilute with a preferred level of active from 5% to 15%, or concentrated, with
a
preferred level of active from 15% to 50%, most preferably 15% to 35% by
weight
of the composition.
Fully formulated laundry and cleaning compositions such as a softening
composition preferably contain, in addition to the hereinbefore described
components, one or more of the following ingredients.
(A) Briahteners
The compositions herein can also optionally contain from 0.005% to 5% by
weight of certain types of hydrophilic optical brighteners which also provide
a dye
~5 transfer inhibition action. If used, the compositions herein will
preferably
comprise from 0.001 % to 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
R~ R2
N H H N
N O>-N O C C N N
/ N H H N
R2 S~3M S~3M R~
2o wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
25 cation such as sodium, the brightener is 4,4',-bis((4-anilino-6-(N-2-bis
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
tradename
Tinopal-UNPA-GX~ by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the
preferred hydrophilic optical brightener useful in the rinse added
compositions
3o herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[{4-
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24
anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-
stilbenedisulfonic acid disodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal 5BM-GX~ by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such
as sodium, the brightener is 4,4'-bis[(4-anifino-6-morphilino-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal AMS-GX~ by
Ciba Geigy Corporation.
(B) Dispersibility Aids
Relatively concentrated compositions containing both saturated and unsaturated
diester quaternary ammonium compounds can be prepared that are stable
without the addition of concentration aids. However, the compositions of the
present invention may require organic andlor inorganic concentration aids to
go
to even higher concentrations andlor to meet higher stability standards
depending on the other ingredients. These concentration aids which typically
can be viscosity modifiers may be needed, or preferred, for ensuring stability
under extreme conditions when particular softener active levels are used. The
2o surfactant concentration aids are typically selected from the group
consisting of
(1) single long chain alkyl cationic surfactants; (2) nonionic surfactants;
(3) amine
oxides; (4) fatty acids; and (5) mixtures thereof. These aids are described in
WO
94120597, specifically on page 14, line 12 to page 20, line 12, which is
herein
incorporated by reference.
2s When said dispersibility aids are present , the total level is from 2% to
25%,
preferably from 3% to 17%, more preferably from 4% to 15%, and even more
preferably from 5% to 13% by weight of the composition. These materials can
either be added as part of the active softener raw material, (1), e.g., the
mono-
long chain alkyl cationic surfactant andlor the fatty acid which are reactants
used
3o to form the biodegradable fabric softener active as discussed hereinbefore,
or
added as a separate component. The total level of dispersibility aid includes
any
amount that may be present as part of component (I).
(1) Mono-Alkyl Cationic Quaternar)i Ammonium Compound
35 When the mono-alkyl cationic quaternary ammonium compound is present, it is
typically present at a level of from 2% to 25%, preferably from 3% to 17%,
more
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WO 99116803 PCT/US97I17932
preferably from 4% to 15%, and even more preferably from 5% to 13% by weight
of the composition, the total mono-alkyl cationic quaternary ammonium
compound being at least at an effective level.
Such mono-alkyl cationic quaternary ammonium compounds useful in the
5 present invention are, preferably, quaternary ammonium salts of the general
formula:
[R N+(R5)3] X- _
wherein
R4 is Cg-C22 alkyl or alkenyl group, preferably C10-C1g alkyl or alkenyl
group;
more preferably C1p-C14 or C1g-C1g alkyl or alkenyl group;
each R5 is a C1-Cg alkyl or substituted alkyl group (e.g., hydroxy alkyl),
preferably C1-C3 alkyl group, e.g., methyl (most preferred), ethyl, propyl,
and the
like, a benzyl group, hydrogen, a polyethoxylated chain with from 2 to 20
oxyethylene units, preferably from 2.5 to 13 oxyethylene units, more
preferably
15 from 3 to 10 oxyethylene units, and mixtures thereof; and
X- is as defined hereinbefore for (Formula (I)).
Especially preferred dispersibility aids are monolauryl trimethyl ammonium
chloride and monotallow trimethyl ammonium chloride available from Witco under
the trade names Adogen~ 412 and Adogen~ 471, monooleyl or monocanola
2o trimethyl ammonium chloride available from Wtco under the tradename Adogen
~ 417, monococonut trimethyl ammonium chloride available from Witco under
the trade name Adogen~ 461, and monosoya trimethyl ammonium chloride
available from Witco under the trade name Adogen~ 415.
The R4 group can also be attached to the cationic nitrogen atom through a
group
25 containing one, or more, ester, amide, ether, amine, etc., linking groups
which
can be desirable for increased concentratability of component {I), etc. Such
linking groups are preferably within from one to three carbon atoms of the
nitrogen atom.
Mono-alkyl cationic quaternary ammonium compounds also include Cg-C22 alkyl
3o choline esters. The preferred dispersibifity aids of this type have the
formula:
R1 C(O)-O-CH2CH2N+(R)3 X-
wherein R1, R and X- are as defined previously.
Highly preferred dispersibility aids include C12-C14 coco choline ester and
C16-
C1 g tallow choline ester.
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26
Suitable biodegradable single-long-chain alkyl dispersibility aids containing
an
ester linkage in the long chains are described in- U.S. 4,840,738, said patent
being incorporated herein by reference.
When the dispersibility aid comprises alkyl choline esters, preferably the
s compositions also contain a small amount, preferably from 2% to 5% by weight
of
the composition, of organic acid. Organic acids are described in EP.404,471,
which is herein incorporated by reference. Preferably the organic acid is
selected from the group consisting of glycolic acid, acetic acid, citric acid,
and
mixtures thereof.
Ethoxylated quaternary ammonium compounds which can serve as the
dispersibility aid include ethylbis(polyethoxy ethanol)alkylammonium ethyl-
sulfate
with 17 moles of ethylene oxide, available under the trade name Variquat~ 66
from Witco Corporation; polyethylene glycol (15) oleammonium chloride,
available under the trade name Ethoquad~ 0125 from Akzo; and polyethylene
~5 glycol (15) cocomonium chloride, available under the trade name Ethoquad~
C/25 from Akzo.
Quaternary compounds having only a single long alkyl chain, can protect the
cationic softener from interacting with anionic surfactants and/or detergent
builders that are carried over into the rinse from the wash solution.
(2) Nonionic Surfactant (Alkoxylated Materials)
Suitable nonionic surfactants to serve as the viscosityldispersibility
modifier
include addition products of ethylene oxide and, optionally, propylene oxide,
with
fatty aicohols, fatty acids, fatty amines, etc. They are referred to herein as
ethoxylated fatty alcohols, ethoxylated fatty acids, and ethoxylated fatty
amines.
Any of the alkoxylated materials of the particular type described hereinafter
can
be used as the nonionic surfactant. In general terms, the nonionics herein,
when
used alone, in liquid compositions are at a level of from 0% to 5%, preferably
from 0.1% to 5%, more preferably from 0.2% to 3%. Suitable compounds are
3o substantially water-soluble surfactants of the general formula:
R2 - Y - (C2H40)z - C2H40H
wherein R2 for both solid and liquid compositions is selected from the group
consisting of primary, secondary and branched chain alkyl and/or acyl
hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl
groups; and primary, secondary and branched chain alkyl- and
alkenyl-substituted phenolic hydrocarbyl groups; said hydrocarbyl groups
having
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27
a hydrocarbyl chain length of from 8 to 20, preferably from 10 to 18 carbon
atoms. More preferably the hydrocarbyl chain length for liquid compositions is
from 16 to 18 carbon atoms and for solid compositions from 10 to 14 carbon
atoms. In the general formula for the ethoxylated nonionic surfactants herein,
Y
is typically -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R-, preferably -O-, and in
which R2, and R, when present, have the meanings given hereinbefore, andlor
R can be hydrogen, and z is at least 8, preferably at least 10-11. Performance
and, usually, stability of the softener composition decrease when fewer ethoxy-
late groups are present.
~o The nonionic surfactants herein are characterized by an HLB
(hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8 to 15. Of
course, by defining R2 and the number of ethoxylate groups, the HLB of the
surfactant is, in general, determined. However, it is to be noted that the
nonionic
ethoxylated surfactants useful herein, for concentrated liquid compositions,
~5 contain relatively long chain R2 groups and are relatively highly
ethoxylated.
While shorter alkyl chain surfactants having short ethoxylated groups can
possess the requisite HLB, they are not as effective herein.
Nonionic surfactants as the viscosity/dispersibility modifiers are preferred
over
the other modifiers disclosed herein for compositions with higher levels of
2o perfume.
Examples of nonionic surfactants follow. The nonionic surfactants of this
invention are not limited to these examples. In the examples, the integer
defines
the number of ethoxy (EO) groups in the molecule.
25 (3) Arnine Oxides
Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of 8
to
22 carbon atoms, preferably from 10 to 18 carbon atoms, more preferably from 8
to 14 carbon atoms, and two alkyl moieties selected from the group consisting
of
alkyl groups and hydroxyalkyl groups with 1 to 3 carbon atoms.
3o Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide, dipropyl-
tetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-
hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
35 (C) Stabilizers
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28
Stabilizers can be present in the compositions of the present invention. The
term
"stabilizer," as used herein, includes antioxidants -and reductive agents.
These
agents are present at a level of from 0% to 2%, preferably from 0.01% to 0.2%,
more preferably from 0.035% to 0.1 % for antioxidants, and more preferably
from
0.01 % to 0.2% for reductive agents. These assure good odor stability under
long
term storage conditions. Antioxidants and reductive agent stabilizers are
especially critical for unscented or low scent products (no or low perfume).
Examples of antioxidants that can be added to the compositions of this
invention
include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate,
available
from Eastman Chemical Products, inc., under the trade names Tenox~ PG and
Tenox~ S-1; a mixture of BHT (butylated hydroxytoluene}, BHA (butylated
hydroxyanisofe), propyl gallate, and citric acid, available from Eastman
Chemical
Products, Inc., under the trade name Tenox~-6; butylated hydroxytoluene, avail-
able from UOP Process Division under the trade name Sustane~ BHT; tertiary
butylhydroquinone, Eastman Chemical Products, Inc., as Tenox~ TBHQ; natural
tocopherois, Eastman Chemical Products, Inc., as Tenox~ GT-11GT-2; and
butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain
esters (C$-C22) of gallic acid, e.g., dodecyl gallate; Irganox~ 1010; Irganox~
1035; Irganox~ B 1171; Irganox~ 1425; Irganox~ 3114; (rganox~ 3125; and
2o mixtures thereof; preferably Irganox~ 3125, Irganox~ 1425, Irganox~ 3114,
and
mixtures thereof; more preferably Irganox~ 3125 alone or mixed with citric
acid
andlor other chelators such as isopropyl citrate, Dequest~ 2010, available
from
Monsanto with a chemical name of 1-hydroxyethylidene-1, 1-diphosphonic acid
{etidronic acid), and Tiron~, available from Kodak with a chemical name of 4,5-
dihydroxy-m-benzene-sulfonic acidlsodium salt, and DTPA~, available from
Aldrich with a chemical name of diethylenetriaminepentaa'cetic acid.
(D) Soil Release Agent
In the present invention, an optional soil release agent can be added. The
3o addition of the soil release agent can occur in combination with the
premix, in
combination with the acid/water seat, before or after electrolyte addition, or
after
the final composition is made. The softening composition prepared by the
process of the present invention herein can contain from 0% to 10%, preferably
from 0.2% to 5%, of a soil release agent. Preferably, such a soil release
agent is
a polymer. Polymeric soil release agents useful in the present invention
include
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29
copolymeric blocks of terephthalate and polyethylene oxide or polypropylene
oxide, and the like.
A preferred soil release agent is a copolymer having blocks of terephthalate
and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units of ethylene terephthalate and polyethylene oxide terephthalate
at
a molar ratio of ethylene terephthalate units to polyethylene oxide
terephthalate
units of from 25:75 to 35:65, said polyethylene oxide terephthalate containing
polyethylene oxide blocks having molecular weights of from 300 to 2000. The
molecular weight of this polymeric soil release agent is in the range of from
5,000
1o to 55,000.
Another preferred polymeric soil release agent is a crystallizable polyester
with
repeat units of ethylene terephthalate units containing from 10% to 15% by
weight of ethylene terephthalate units together with from 10% to 50% by weight
of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol
of
~5 average molecular weight of from 300 to 6,000, and the molar ratio of
ethylene
terephthalate units to polyoxyethylene terephthalate units in the
crystallizable
polymeric compound is between 2:1 and 6:1. Examples of this polymer include
the commercially available materials Zelcon 4780~ (from Dupont) and Milease T
~ (from ICI).
2o Highly preferred soil release agents are polymers of the generic formula:
O O O O
X-(OCH2CH2)p(O- -C-R14 C~ -OR15)u(O-~-R14_p~-O)(CH2CH20-)n-X
in which each X can be a suitable capping group, with each X typically being
selected from the group consisting of H, and alkyl or acyl groups containing
from
1 to 4 carbon atoms. p is selected for water solubility and generally is from
6 to
25 113, preferably from 20 to 50. a is critical to formulation in a liquid
composition
having a relatively high ionic strength. There should be very little material
in
which a is greater than 10. Furthermore, there should be at least 20%,
preferably at least 40%, of material in which a ranges from 3 to 5.
The R14 moieties are essentially 1,4-phenylene moieties. As used herein, the
3o term "the R14 moieties are essentially 1,4-phenylene moieties" refers to
compounds where the R14 moieties consist entirely of 1,4-phenylene moieties,
or are partially substituted with other arylene or alkarylene moieties,
alkylene
moieties, alkenylene moieties, or mixtures thereof. Arylene and alkarylene
moieties which can be partially substituted for 1,4-phenylene include 1,3
35 phenylene, 1,2-phenylene, 1, 8-naphthylene, 1,4-naphthylene, 2,2-
biphenylene,
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WO 99/16803 PCTIUS97/17932
4,4-biphenylene, and mixtures thereof. Alkylene and alkenylene moieties which
can be partially substituted include 1,2-propylene; 1,4-butylene, 1,5-
pentylene,
1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene,
and mixtures thereof.
5 For the R14 moieties, the degree of partial substitution with moieties other
than
1,4-phenylene should be such that the soil release properties of the compound
are not adversely affected to any great extent. Generally the degree of
partial
substitution which can be tolerated will depend upon the backbone length of
the
compound, i.e., longer backbones can have greater partial substitution for 1,4-
phenylene moieties. Usually, compounds where the R14 comprise from 50% to
100% 1,4-phenylene moieties (from 0% to 50% moieties other than 1,4-
phenylene) have adequate soil release activity. For example, polyesters made
according to the present invention with a 40:60 mole ratio of isophthalic (1,3-
phenyfene) to terephthalic (1,4-phenylene) acid have adequate soil release
~5 activity. However, because most polyesters used in fiber making comprise
ethylene terephthalate units, it is usually desirable to minimize the degree
of
partial substitution with moieties other than 1,4-phenylene for best soil
release
activity. Preferably, the R14 moieties consist entirely .of (i.e., comprise
100%)
1,4-phenylene moieties, i.e., each R14 moiety is 1,4-phenylene.
2o For the R15 moieties, suitable ethylene or substituted ethylene moieties
include
ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene,
and mixtures thereof. Preferably, the R15 moieties are essentially ethylene
moieties, 1,2-propylene moieties, or mixtures thereof. Inclusion of a greater
percentage of ethylene moieties tends to improve the soil release activity of
25 compounds. Surprisingly, inclusion of a greater percentage of 1,2-propylene
moieties tends to improve the water solubility of compounds.
Therefore, the use of 1,2-propylene moieties or a similar branched equivalent
is
desirable for incorporation of any substantial part of the soil release
component
in the liquid fabric softener compositions. Preferably, from 75% to 100%, are
1,2
3o propylene moieties.
The value for each p is at least 6, and preferably is at least 10. The value
for
each n usually ranges from 12 to 113. Typically the value for each p is in the
range of from 12 to 43.
A more complete disclosure of soil release agents is contained in U.S. Pat.
Nos.:
4,661,267; 4,711,730; 4,749,596; 4,818,569; 4,877,896; 4,956,447; and
4,976,879, all of said patents being incorporated herein by reference.
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31
These soil release agents can also act as scum dispersants.
(E) Scum Dislaersant
In the present invention, the premix can be combined with an optional scum
dispersant, other than the soil release agent, and heated to a temperature at
or
above the melting points) of the components.
The preferred scum dispersants herein are formed by highly ethoxylating
hydrophobic materials. The hydrophobic material can be a fatty alcohol, fatty
acid, fatty amine, fatty acid amide, amine oxide, quaternary ammonium
1o compound, or the hydrophobic moieties used to form soil release polymers.
The
preferred scum dispersants are highly ethoxylated, e.g., more than 17,
preferably
more than 25, more preferably more than 40, moles of ethylene oxide per
molecule on the average, with the polyethylene oxide portion being from 7fi%
to
97%, preferably from 81 % to 94%, of the total molecular weight.
The level of scum dispersant is sufficient to keep the scum at an acceptable,
preferably unnoticeable to the consumer, level under the conditions of use,
but
not enough to adversely affect softening. For some purposes it is desirable
that
the scum is nonexistent. Depending on the amount of anionic or nonionic
detergent, etc., used in the wash cycle of a typical laundering process, the
2o efficiency of the rinsing steps prior to the introduction of the
compositions herein,
and the water hardness, the amount of anionic or nonionic detergent surfactant
and detergency builder (especially phosphates and zeolites) entrapped in the
fabric (laundry) will vary. Normally, the minimum amount of scum dispersant
should be used to avoid adversely affecting softening properties. Typically
scum
dispersion requires at least 2%, preferably at least 4% (at least 6% and
preferably at least 10% for maximum scum avoidance) based upon the level of
softener active. However, at levels of 10% (relative to the softener material)
or
more, one risks loss of softening efficacy of the product especially when the
fabrics contain high proportions of nonionic surfactant which has been
absorbed
3o during the washing operation.
Preferred scum dispersants are: Brij 700; Varonic U-250~; Genapol T-500~,
Genapol T-800~; Plurafac A-79~; and Neodol 25-50~.
(F) Bactericides
3s Examples of bactericides used in the compositions of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-vitro-propane-1,3-diol sold by Inolex
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32
Chemicals, located in Philadelphia, Pennsylvania, under the trade name
Bronopol~, and a mixture of 5-chloro-2-methyl=4-isothiazoline-3-one and 2-
methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade
name Kathon 1 to 1,000 ppm by weight of the agent.
(G) Perfume
The present invention can contain any softener compatible perfume. Suitable
perfumes are disclosed in U.S. Pat. 5,500,138, said patent being incorporated
herein by reference.
As used herein, perfume includes fragrant substance or mixture of substances
including natural (i.e., obtained by extraction of flowers, herbs, leaves,
roots,
barks, wood, blossoms or plants), artificial (i.e., a mixture of different
nature oils
or oil constituents) and synthetic (i.e., synthetically produced) odoriferous
substances. Such materials are often accompanied by auxiliary materials, such
~5 as fixatives, extenders, stabilizers and solvents. These auxiliaries are
also
included within the meaning of "perfume", as used herein. Typically, perfumes
are complex mixtures of a plurality of organic compounds.
Examples of perfume ingredients useful in the perfumes of the present
invention
compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl
2o cinnamic aidehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-
dimethyl-cis
2,6-octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; 3,7-
dimethyl-
3-octanol; 3,7-dimethyl-franc-2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol;
3,7-
dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 4-(4-
hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; tricyclodecenyl
25 propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2-(para-iso-
propylphenyl)-propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4-(para-
hydroxyphenyl)-butan-2-one; 1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-
one;
para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-
hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.
3o Additional examples of fragrance materials include, but are not limited to,
orange
oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether;
methyl-beta-naphthylketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-
butylcyclohexyl acetate; alpha,alpha-dimethylphenethyl acetate;
35 methylphenylcarbinyl acetate; Schiffs base of 4-(4-hydroxy-4-methylpentyl)-
3-
cyclohexene-1-carboxaldehyde and methyl anthranilate; cyclic ethylenegiycol
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WO 99/16803 PCTIUS97/17932
33
diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrite; ionone
gamma
methyl; ionone alpha; ionone beta; petitgrain; - methyl cedrylone; 7-acetyl-
1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; ionone methyl;
methyl-1,6,10-trimethyl-2,5;9-cyclododecatrien-1-yl ketone; 7-acetyl-
1,1,3,4,4,6-
hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;
6-
acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl
indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-
hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;
16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-
hexamethylcyclopenta-gamma-2-benzopyrane; ambroxane; dodecahydro-
3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol; 5-(2,2,3-trimethylcyclopent-
3-
enyl)-3-methyipentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-
buten-
1-0l; caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexyl
acetate;
patchouli; olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam;
and
~5 condensation products of: hydroxycitronellal and methyl anthranilate;
hydroxycitronellal and indol; phenyl acetaldehyde and indol; 4-(4-hydroxy-4-
methyl pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthraniiate.
More examples of perfume components are geraniol; geranyl acetate; linalool;
linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate;
dihydromyrcenol;
2o dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl
acetate; 2-phenylethanol; 2-phenylethyi acetate; benzyl alcohol; benzyl
acetate;
benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol;
trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate;
vetiveryl acetate; vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal; 2-
methyl-3-
25 (p-isopropylphenyl)-propanal; 3-(p-tert-butylphenyl)-propanal; 4-(4-methyl-
3-
pentenyl)-3-cyclohexenecarbaldehyde; 4-acetoxy-3-pentyltetrahydropyran;
methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-
cyclopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate;
phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal;
3o geranonitriie; citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol;
cedryl
methylether; isolongifolanone; aubepine nitrite; aubepine; heliotropine;
eugenol;
vanillin; diphenyl oxide; hydroxycitronellal ionones; methyl ionones;
isomethyl
ionomes; irones; cis-3-hexenol and esters thereof; indane musk fragrances;
tetralin musk fragrances; isochroman musk fragrances; macrocyclic ketones;
35 macrolactone musk fragrances; ethylene brassylate.
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34
The perfumes useful in the present invention compositions are substantially
free
of halogenated materials and nitromusks.
Suitable solvents, diluents or carriers for perfumes ingredients mentioned
above
are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether,
dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of
such
solvents, diluents or carriers incorporated in the perfumes is preferably kept
to
the minimum needed to provide a homogeneous perfume solution.
Perfume can be present at a level of from 0% to 10%, preferably from 0.1 % to
5%, and more preferably from 0.2% to 3%, by weight of the finished
composition.
Fabric softener compositions of the present invention provide improved fabric
perfume deposition.
(H) Chelatinq A.q~ents
The compositions and processes herein can optionally employ one or more
~ 5 copper andlor nickel chelating agents ("chelators"). Such water-soluble
chelating
agents can be selected from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures thereof, all as hereinafter defined. The whiteness andlor brightness
of
fabrics are substantially improved or restored by such chelating agents and
the
2o stability of the materials in the compositions are improved.
Amino carboxylates useful as chelating agents herein include ethylenedi-
aminetetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates,
nitrilotri-
acetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-N,N'-
diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates,
25 triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA),
and ethanoldiglycines, including their water-soluble salts such as the alkali
metal,
ammonium, and substituted ammonium salts thereof and mixtures thereof.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at least low levels of total phosphorus are
3o permitted in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates), diethylenetriamine-N,N,N',N",N"-pentakis(methane
phosphonate) (DETMP) and 1-hydroxyethane-1,1-diphosphonate (HEDP).
Preferably, these amino phosphonates to not contain alkyl or alkenyl groups
with
more than 6 carbon atoms.
35 The chelating agents are typically used in the present rinse process at
levels
from 2 ppm to 25 ppm, for periods from 1 minute up to several hours' soaking.
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WO 99/16803 PCT/U597/17932
The preferred EDDS chelator used herein (also known as ethylenediamine-N,N'-
disuccinate) is the material described in U.S. Patent 4,704,233.
As can be seen from the foregoing, a wide variety of chelators can be used
herein. Indeed, simple polycarboxyfates such as citrate, oxydisuccinate, and
the
5 like, can also be used, although such chelators are not as effective as the
amino
carboxylates and phosphonates, on a weight basis. Accordingly, usage levels
may be adjusted to take into account differing degrees of chelating
effectiveness.
The chelators herein will preferably have a stability constant (of the fully
ionized
chelator) for copper ions of at least 5, preferably at least 7. Typically, the
chelators will comprise from 0.5% to 10%, more preferably from 0.75% to 5%, by
weight of the compositions herein. Preferred chelators include DETMP, DETPA,
NTA, EDDS and mixtures thereof.
(I)-Enzyme
15 The compositions and processes herein can optionally employ one or more
enzymes such as lipases, proteases, cellulase, amylases and peroxidases. A
preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of
enzyme will further provide a color care benefit to the treated fabric.
Cellulases
usable herein include both bacterial and fungal types, preferably having a pH
20 optimum between 5 and 9.5. U.S. 4,435,307 discloses suitable fungal
cellulases
from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-
producing fungus belonging to the genus Aeromonas, and cellulase extracted
from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and
25 DE-OS-2.247.832. CAREZYME~ and CELLUZYME~ (Novo) are especially
useful. Other suitable ceUulases are also disclosed in WO 91/17243 to Novo,
WO 96134092, WO 96/34945 and EP-A-0,739,982. In practical terms for current
commercial preparations, typical amounts are up to 5 mg by weight, more
typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent
3o composition. Stated otherwise, the compositions herein will typically
comprise
from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme
preparation. In the particular cases where activity of the enzyme preparation
can
be defined otherwise such as with cellulases, corresponding activity units are
preferred (e.g. CEVU or cellulase Equivalent Viscosity Units). For instance,
the
35 compositions of the present invention can contain cellulase enzymes at a
level
equivalent to an activity from 0.5 to 1000 CEVU/gram of composition. Cellulase
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36
enzyme preparations used for the purpose of formulating the compositions of
this
invention typically have an activity comprised -between 1,000 and 10,000
CEVUlgram in liquid form, around 1,000 CEVU/gram in solid form.
(J) Liquid carrier
Another optional, but preferred, ingredient is a liquid carrier. The
liquid_carrier
employed in the instant compositions is preferably at Least primarily water
due to
its low cost, relative availability, safety, and environmental compatibility.
The
level of water in the liquid carrier is preferably at least 50%, most
preferably at
least 60%, by weight of the carrier. Mixtures of water and low molecular
weight,
e.g., <200, organic solvent, e.g., lower alcohols such as ethanol, propanol,
isopropanol or butanol are useful as the carrier liquid. Low molecular weight
alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol,
etc.), and
higher polyhydric (polyols) alcohols.
(K) Other Optional Ingredients
The present invention can include optional components conventionally used in
textile treatment compositions, for example: colorants; preservatives;
surfactants;
anti-shrinkage agents; fabric crisping agents; spotting agents; germicides;
2o fungicides; anti-oxidants such as butylated hydroxy toluene, anti-corrosion
agents, and the like.
The present invention can also include other compatible ingredients, including
those as disclosed in W096102625, W096121714, and W096121715.
Various other optional adjunct ingredients may also be used to provide fully
25 formulated detergent compositions. The following ingredients are described
for
the convenience of the formulator, but are not intended to be limiting
thereof.
Detersive Surfactants
Non-limiting examples of surfactants useful herein typically at levels from 1
% to
30 55%, by weight, include the conventional C11-C1g alkyl benzene sulfonates
("LAS") and primary, branched-chain and random C1p-C20 alkyl sulfates ("AS"),
the C10-C1g secondary (2,3) alkyl sulfates of the formula
CHg(CH2)x(CHOS03-M+) CH3 and CHg(CH2)y(CHOS03 M+) CH2CHg where x
and (y + 1 ) are integers of at least 7, preferably at least 9, and M is a
water
35 solubilizing cation, especially sodium, unsaturated sulfates such as oleyl
sulfate,
the C10-C1g alkyl alkoxy sulfates ("AExS"; especially x up to 7 EO ethoxy
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37
sulfates), C10-C1g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C10-18 9lYcerol ethers, the C10-C1g alkyl
polyglycosides and their corresponding sulfated polyglycosides, and C12-C18
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric surtactants such as the C12-C1g alkyl ethoxylates ("AE") including
the so-called narrow peaked alkyl ethoxylates and Cg-C12 alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18
betaines and sulfobetaines ("sultaines"), C10-C1 g amine oxides, cationic
surfactants and the like, can also be included in the overall compositions.
The
~o C10-C1g N-alkyl polyhydroxy fatty acid amides can also be used. Typical
examples include the C12-C1g N-methylglucamides. See WO 9,206,154. Other
sugar-derived surtactants include the N-alkoxy polyhydroxy fatty acid amides,
such as C10-C1 g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl
C12-C1 g glucamides can be used for low sudsing. C1 p-C20 conventional soaps
~5 may also be used. If high sudsing is desired, the branched-chain C1p-C1g
soaps
may be used. Mixtures of anionic and nonionic surfactants are especially
useful.
Other conventional useful surfactants are listed in standard texts.
Builders
2o Detergent builders can optionally be included in the compositions herein to
assist
in controlling mineral hardness. Inorganic as well as organic builders can be
used. Builders are typically used in fabric laundering compositions to assist
in the
removal of particulate soils.
25 The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least 1 % builder, preferably from 1 % to 80%. Liquid
formulations typically comprise from 5% to 50%, more typically 5% to 30%, by
weight, of detergent builder. Granular formulations typically comprise from 1
% to
30 80%, more typically from 5% to 50% by weight, of the detergent builder.
Lower or
higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the
alkali metal, ammonium and alkanolammonium salts of polyphosphates
35 (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including
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38
bicarbonates and sesquicarbonates}, sulphates, and aluminosilicates. However,
non-phosphate builders are required in some locales. Importantly, the
compositions herein function surprisingly well even in the presence of the so-
called "weak" builders (as compared with phosphates) such as citrate, or in
the
so-called "underbuilt" situation that may occur with zeolite or layered
silicate
builders.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.0:1 to 3.2:1 and layered silicates,
such
as the layered sodium silicates described in U.S. 4,664,839. NaSKS-6 is the
trademark for a crystalline layered silicate marketed by Hoechst (commonly
abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate
builder does not contain aluminum. NaSKS-6 has the delta-Na2Si08 morphology
form of layered silicate. It can be prepared by methods such as those
described
~5 in DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered
silicate for use herein, but other such layered silicates, such as those
having the
general formula NaMSix02x+1 ~yH20 wherein M is sodium or hydrogen, x is a
number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably
0
can be used herein. Various other layered silicates from Hoechst include
2o NaSKS-5, NaSKS-7 and NaSKS-11; as the alpha, beta and gamma forms. As
noted above, the delta-Na2Si05 (NaSKS-6 form) is most preferred for use
herein.
Other silicates may also be useful such as for example magnesium silicate,
which
can serve as a crispening agent in granular formulations, as a stabilizing
agent
for oxygen bleaches, and as a component of suds control systems.
25 Examples of carbonate builders are the alkaline earth and alkali metal
carbonates
as disclosed in DE 2,321,001.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty
granular
3o detergent compositions, and can also be a significant builder ingredient in
liquid
detergent formulations. Aluminosilicate builders include those having the
empirical formula:
Mz/nI(A102)z(Si02)y]~xH20
wherein z and y are integers usually of at least 6, the molar ratio of z to y
is in the
35 range from 1.0 to 0, and x is an integer from 0 to 264, and M is a Group IA
or !IA
element, e.g., Na, K, Mg, Ca with valence n.
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39
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S.
3,985,669.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful
herein are available under the designations Zeolite A, Zeolite P (B), Zeolite
MAP
and Zeolite X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Nal2[(A102)12(Si02)121~xH20
wherein x is from 20 to 30, especially 27. This material is known as Zeolite
A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the
aluminosilicate has a particle size of 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds.
As used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate
builder
can generally be added to the composition in acid form, but can also be added
in
2o the form of a neutralized salt. When utilized in salt form, alkali metals,
such as
sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders encompasses the
ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S.
3,128,287, U.S. 3,635,830. See also "TMS/TDS" builders of U.S. 4,663,071.
Suitable ether polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S. 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid,
the various alkali metal, ammonium and substituted ammonium salts of
polyacetic
acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as
well as
polycarboxylates such as mellitic acid, pyromellitic, succinic acid,
oxydisuccinic
CA 02310737 2000-OS-18
WO 99116$03 PCT/US97117932
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic
acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
5 salt), are polycarboxylate builders of particular importance for heavy duty
liquid
detergent formulations due to their availability from renewable resources and
their
biodegradability. Citrates can also be used in granular compositions,
especially
in combination with zeolite and/or layered silicate builders. Oxydisuccinates
are
also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-
dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is
~5 dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred builders of this group, and are described in EP 0,200,263.
2o Other suitable polycarboxylates are disclosed in U.S 4,144,226 and in U.S.
3,308,067. See also U.S. 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxylic acids such as oleic acid andlor its
salts, can also be incorporated into the compositions alone, or in combination
25 with the aforesaid builders, especially citrate andlor the succinate
builders, to
provide additional builder activity. Such use of fatty acids will generally
result in a
diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in
the
3o formulation of bars used for hand-laundering operations, the various alkali
metal
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders
such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates
(see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and
35 3,422,137) can also be used.
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41
Bleaching Compounds - Bleaching Agents and Bleach Activators
The detergent compositions herein may optionally- contain bleaching agents or
bleaching compositions containing a bleaching agent and one or more bleach
activators. When present, bleaching agents will typically be at levels of from
1
to 30%, more typically from 5% to 20%, of the detergent composition,
especially
for fabric laundering. If present, the amount of bleach activators will
typically be
from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching
composition
comprising the bleaching agent-plus-bleach activator.
1o The bleaching agents used herein can be any of the bleaching agents useful
for
detergent compositions in textile cleaning or other cleaning purposes that are
now known or become known. These include oxygen bleaches as well as other
bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or
tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include magnesium monoperoxyphthalate
hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonyiamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents
are disclosed in U.S 4,483,781, U.S 740,446, EP 0,133,354, and U.S 4,412,934.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid as described in U.S 4,634,551.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent
"percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,
manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from 500 micrometers to 1,000 micrometers, not more
than 10% by weight of said particles being smaller than 200 micrometers and
not
more than 10% by weight of said particles being larger than 1,250 micrometers.
Optionally, the percarbonate can be coated with silicate, borate or water-
soluble
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42
surfactants. Percarbonate is available from various commercial sources such as
FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably combined with bleach activators, which lead to the in situ
production in
aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. Various non-limiting examples of
activators are disclosed in U.S 4,915,854, and U.S 4,412,934. The
nonanoyloxybenzene sulfonate (NOBS), 3,5,5-tri-methyl hexanoyl oxybenzene
sulfonate (ISONOBS) and tetraacetyl ethylene diamine (TAED) activators are
typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for
other
typical bleaches and activators useful herein.
~5 Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from 6 to 12 carbon atoms, R2 is an
alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or
alkaryl
containing from 1 to 10 carbon atoms, and L is any suitable leaving group. A
20 leaving group is any group that is displaced from the bleach activator as a
consequence of the nucleophilic attack on the . bleach activator by the
perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
25 octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzene
sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as
described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators
3o disclosed by Hodge et al in U.S. Patent 4,966,723. A highly preferred
activator of
the benzoxazin-type is:
O
II
CEO
al
..~ o
N
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43
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O O
O C-C H2-C HZ O C-C H2-C H2
Rs-C-N\C H2-C H2 C H2 Rs-C-NBC H - ~ H
2 2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam,
nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl
valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and
mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October
8, 1985, incorporated herein by reference, which discloses acyl caprolactams,
including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art
and can be utilized herein. One type of non-oxygen bleaching agent of
particular
interest includes photoactivated bleaching agents such as the sulfonated zinc
and/or aluminum phthalocyanines. See U.S. 4,033,718. If used, detergent
compositions will typically contain from 0.025% to 1.25%, by weight, of such
bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well-known in the art and include, for example,
the manganese-based catalysts disclosed in U.S. 5,246,621, U.S. 5,244,594;
U.S. 5,194,416; U.S. 5,114,606; and EP 549,271A1, 549,272A1, 544,440A2, and
544,490A1; Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-
trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mnll l2 (u-O)1 (u-OAc)2(1,4,7-
trimethyl-1,4,7-triazacyclononane)2_(CI04)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)1(u-OAc)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-
(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include
those disclosed in U.S. Pat. 4,430,243 and U.S. 5,114,611. The use of
manganese with various complex ligands to enhance bleaching is also reported
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44
in the following US Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per
ten million of the active bleach catalyst species in the aqueous washing
liquor,
and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1
ppm
to 500 ppm, of the catalyst species in the laundry liquor.
~o Other preferred optional ingredients include enzyme stabilisers, polymeric
soil
release agents, materials effective for inhibiting the transfer of dyes from
one
fabric to another during the cleaning process {i.e., dye transfer inhibiting
agents),
polymeric dispersing agents, suds suppressors, optical brighteners or other
brightening or whitening agents, chelating agents, fabric softening clay, anti-
static
~5 agents, other active ingredients, carriers, hydrotropes, processing aids,
dyes or
pigments, solvents for liquid formulations and solid fillers for bar
compositions.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
2o ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are
preferred for solubilizing surfactant, but polyols such as those containing
from 2
to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol,
ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The
compositions may contain from 5% to 90%, typically 10% to 50% of such
carriers.
Granular detergents can be prepared, for example, by spray-drying (final
product
density 520 g/I) or agglomerating (final product density above 600 gll) the
Base
Granule. The remaining dry ingredients can then be admixed in granular or
powder form with the Base Granule, for example in a rotary mixing drum, and
the
liquid ingredients (e.g., nonionic surfactant and pertume) can be sprayed on.
The detergent compositions herein will preferably be formulated such that,
during
use in aqueous cleaning operations, the wash water will have a pH of between
6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at
pH 9-11. Techniques for controlling pH at recommended usage levels include the
use of buffers, alkalis, acids, etc., and are well-known to those skilled in
the art.
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Method of use
Also provided herein is a method for providing a delayed release of an active
alcohol which comprises the step of contacting the surface to be treated with
a
5 material, preferably an aqueous medium comprising a compound or composition
of the invention.
By "surface", it is meant any surface onto which the compound can deposit.
Typical examples of such material are fabrics, hard surfaces such as dishware,
1o floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed
release
of an active alcohol such as that with litter.
By "delayed release" is meant release of the active component (e.g perfume)
over a longer period of time than by the use of the active (e.g., perfume)
itself.
In the composition examples, the abbreviated component identifications have
the
following meanings:
Abbreviations used in Examples
2o In the detergent compositions, the abbreviated component identifications
have
the following meanings:
DEQA : Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride
DTDMAC : Ditallow dimethylammonium chloride
Fatty acid : Stearic acid of IV=0
Electrolyte : Calcium chloride
PEG : Polyethylene Glycol 4000
Carezyme : cellulytic enzyme sold by NOVO Industries A/S
LAS : Sodium linear C11-13 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
CxyAS : Sodium C 1 x - C 1 y alkyl sulfate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl
sulfate
CxyEzS : Sodium C1x-C1y alkyl sulfate condensed
with z
moles of ethylene oxide
3o CxyEz : C1x-C1y predominantly linear primary
alcohol
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46
condensed with an average of z moles of ethylene
oxide
QAS : R2.N+(CH3)2(C2H4~H) with R2 = C12 - C14
QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = Cg - C11
APA : Cg - C10 amido propyl dimethyl amine
Soap : Sodium linear alkyl carboxylate derived from
an -
80/20 mixture of tallow and coconut fatty acids
STS : Sodium toluene sulphonate
CFAA : C12-C14 (coco) alkyl N-methyl glucamide
TFAA : C16-C1g alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12~2~H20 having a primary
particle size in the range from 0.1 to 10
micrometers (weight expressed on an anhydrous
basis)
NaSKS-6 : Crystalline layered silicate of formula 8-
2o Na2Si205
Citric acid : Anhydrous citric acid
Borate : Sodium borate
Carbonate : Anydrous sodium carbonate with a particle
size
between 200Nm and 900Nm
2sBicarbonate : Anhydrous sodium bicarbonate with a particle
size distribution between 400Nm and 1200Nm
Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1)
Sulfate : Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
Citrate : Tri-sodium citrate dehydrate of activity 86.4%
with a particle size distribution between 425Nm
and 850Nm
MAIAA : Copolymer of 1:4 maleiclacrylic acid, average
molecular weight about 70,000
35MA/AA (1) : Copolymer of 4:6 maleic/acrylic acid, average
molecular weight about 10,000
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47
AA : Sodium polyacrylate polymer of average
molecular weight 4,500
CMC : Sodium carboxymethyl cellulose
Cellulose ether : Methyl cellulose ether with a degree of
polymerization of 650 available from Shin
Etsu
Chemicals _
Protease : Proteolytic enzyme, having 3.3% by weight
of
active enzyme, sold by NOVO Industries A/S
under the tradename Savinase
~o Protease I : Proteolytic enzyme, having 4% by weight
of
active enzyme, as described in WO 95110591,
sold by Genencor Int. Inc.
Alcalase : Proteolytic enzyme, having 5.3% by weight
of
active enzyme, sold by NOVO Industries AIS
Cellulase : Cellulytic enzyme, having 0.23% by weight
of
active enzyme, sold by NOVO Industries AIS
under the tradename Carezyme
Amylase : Amyloiytic enzyme, having 1.6% by weight
of
active enzyme, sold by NOVO Industries A/S
2o under the tradename Termamyl 120T
Lipase : Lipolytic enzyme, having 2.0% by weight of
active enzyme, sold by NOVO Industries AIS
under the tradename Lipolase
Lipase (1) : Lipolytic enzyme, having 2.0% by weight
of
active enzyme, sold by NOVO Industries A/S
under
the tradename Lipolase Ultra
Endolase : Endoglucanase enzyme, having 1.5% by weight
of
active enzyme, sold by NOVO Industries AIS
PB4 : Sodium perborate tetrahydrate of nominal
formula
3o NaB02.3H20.H202
PB1 : Anhydrous sodium perborate bleach of nominal
formula NaB02.H202
Percarbonate : Sodium percarbonate of nominal formula
2Na2C03.3H202
NOBS : Nonanoyloxybenzene sulfonate in the form
of the
sodium salt
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48
NAC-OBS : (6-nonamidocaproyl) oxybenzene sulfonate
TAED : Tetraacetylethylenediamine
DTPA : Diethylene triamine pentaacetic acid
DTPMP : Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under the
Tradename bequest 2060 _
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S)
isomer in the form of its sodium salt.
Photoactivated : Sulfonated zinc phthlocyanine encapsulated
in bleach
(1) dextrin soluble polymer
Photoactivated : Sulfonated alumino phthlocyanine encapsulated
in
bleach (2) dextrin soluble polymer
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
~5 triazin-2-yl)amino) stilbene-2:2'-disulfonate
HEDP : 1,1-hydroxyethane diphosphonic acid
PEGx : Polyethylene glycol, with a molecular weight
of x
(typically 4,000)
PEO : Polyethylene oxide, with an average molecular
2o weight of 50,000
TEPAE : Tetraethylenepentaamine ethoxylate
VI : Polyvinyl imidazole, with an average molecular
weight of 20,000
PVP : Polyvinylpyrolidone polymer, with an average
25 molecular weight of 60,000
PVNO : Polyvinylpyridine N-oxide polymer, with an
average molecular weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole, with an average molecular weight
30 of 20,000
QEA : bis({C2Hb0){C2H40)n)(CH3) -N+-C6H12-N+_
(CH3) bis((C2H50)-(C2H40))n, wherein n =
from 20 to 30
SRP 1 : Anionically end capped poly esters
35 SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short block polymer
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49
PEI : Polyethyleneimine with an average molecular
weight of 1800 and an average ethoxylation
degree of 7 ethyleneoxy residues per nitrogen
Silicone antifoam : Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said _
dispersing agent of 10:1 to 100:1
Opacifier : Water based monostyrene latex mixture, sold by
BASF Aktiengesellschaft under the tradename
Lytron 621
Wax : Paraffin wax
The following are synthesis examples of compounds according to the invention::
~5 I-Synthesis of a copolyrmer of methyrl alyoxyrlate and dodecanal end
capped with ethyl vinyl ether
Methyl 2-hydroxy-2-methoxyacetate {120 g, 1 mol, 1 eq) is placed in a 250 ml
three necks round-bottom flask, fitted with a Vigreux column, a thermometer
and
a funnel, all glassware having been washed with diluted acid and dried
20 previously. To this is slowly added, in three portions, with stirring,
phosphorus
pentoxide (71 g, 0.5 mol, 0.5 eq), being careful not to allow the temperature
to
rise above 90°C. At the end of addition, the mixture is allowed to stir
for an hour
before heat is applied and the methyl glyoxylate distilled under a nitrogen
blanket. 67 g of methyl glyoxylate (bp 106-107°C) is recovered upon
distillation.
2s To a solution of freshly distilled methyl glyoxylate {10.2 g, 0.116 mol),
dodecanal
(10.67 g, 0.058 mol) in dichloromethane (10 ml) is added a freshly made
solution
of dimethyl sodiomethylmalonate in THF {0.5 ml of a 0.05 moll solution). The
mixture is stirred at 20°C for an hour then trifluoroacetic acid (0.18
ml, 2.3 mmol)
is added, followed by ethyl vinyl ether (3.5 ml, 36.6 mmol). The mixture is
stirred
3o at 20°C for 18 hours then sodium carbonate (0.5 g, 4.6 mmol, 2 eq
compared to
trifluoroacetic acid) is added. The resulting mixture is stirred for 30
minutes
before being diluted with 30 ml of dichloromethane and washed with water (25
ml). The aqueous phase is then extracted with dichloromethane (20 ml). Both
organic phases are combined and dried over sodium sulfate. After filtration
and
3s concentration on the rotaevaporator, a colourless gum (15.5 g) is obtained.
CA 02310737 2000-OS-18
WO 99116803 PCT/US97117932
II-Synthesis of a copolymer of methyl glyroxylate and traps-4-decenal, end-
cal~ped with eth~rl vinyl ether
To a solution of freshly distilled methyl glyoxylate (30 g, 0.349 mol), traps-
4
decenal (2.63 g, 0.017 mol) in dichloromethane (30 ml) is added boron
triffuoride
5 diethyl etherate (1 ml). The mixture is stirred at 0°C for one and a
half hour
before trifluoroacetic acid (1.08 ml, 14 mmol) is added, followed by a
dropwise
addition at 0°C of ethyl vinyl ether (10.5 ml). The mixture is stirred
at 20°C for 18
hours then sodium carbonate (1.5 g, 14 mmol) is added. The resulting mixture
is
stirred for 30 minutes before being diluted with 30 ml of dichloromethane and
washed with water (40 ml). The aqueous phase is then extracted with
dichloromethane (30 ml). Both organic phases are combined and dried over
sodium sulfate. After filtration and concentration on the rotaevaporator, a
dark
brown gum (30 g) is obtained.
~5 III-Synthesis of a terpolymer of methyl alyoxyrlate traps-4-decenal and
benzaldehvde, end-cauped with ethyrl vin~rl ether
To a solution at 0°C of freshly distilled methyl glyoxylate (30 g,
0.349 mol), trans-
4-decenal (2.63 g, 0.017 mol) and benzaldehyde (0.19 g, 1.75 mmol) in
dichloromethane (30 ml) is added boron trifluoride diethyl etherate (1 ml).
The
2o mixture is stirred at 0°C for one and a half hour before
trifluoroacetic acid (1.08
ml, 14 mmol) is added, followed by a dropwise addition at 0°C of ethyl
vinyl ether
(10.5 ml). The mixture is stirred at 0°C for 30 minutes and then at
20°C for 18
hours before sodium carbonate (3 g, 28 mmol) is added. The resulting mixture
is
stirred for 30 minutes before being diluted with 30 ml of dichloromethane and
25 washed with water (30 ml). The aqueous phase is then extracted with
dichloromethane (30 ml). Both organic phases are combined and dried over
sodium sulfate. After filtration and concentration on the rotaevaporator, a
brown
gum (27 g) is obtained.
3o IV-Synthesis of a terpolyrmer of methyl glyoxylate, meth~,rl non~l
acetaldehyde (2-methyl undecanal~, traps-4-decenal and benzaldeh~rde.
end-capped with ethyl vinyrl ether
To a solution at 0°C of freshly distilled methyl glyoxylate (15 g, 0.17
mol), methyl
nonyl acetaldehyde (6.28 g, 34 mmol), traps-4-decenal (1.75 g, 11.4 mmol) and
35 benzaldehyde (1.21 g, 11.4 mmol) in dichloromethane (50 ml} is added boron
trifluoride diethyl etherate (0.28 ml, 2.2 mmol). The mixture is stirred at
0°C for
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51
one and a half hour before trifluoroacetic acid (1.29 ml, 17 mmol) is added,
followed by a dropwise addition at -10°C of ethyl vinyl ether (4 ml, 42
mmol),
under nitrogen. The mixture is stirred at -10°C for 30 minutes and then
at 20°C
for 18 hours, under nitrogen, before sodium carbonate (3 g, 28 mmol) is added.
The resulting mixture is stirred for 30 minutes before being diluted with 30
ml of
dichloromethane and washed with water (30 ml). The aqueous phase is then
extracted with dichloromethane (30 ml). Both organic phases are combined and
dried over sodium sulfate. After filtration and concentration on the
rotaevaporator, a straw colour gum (23 g) is obtained.
V-Synthesis of a coaolymer of m~thvl glyoxyrlate, methyrl none
acetaldehyde, trans-4-decenal and benzaldeh~rde, end-capped with ethylene
oxide
To a solution at 0°C of freshly distilled methyl glyoxylate (15 g, 0.17
mol), methyl
nonyl acetaldehyde (6.28 g, 34 mmol), trans-4-decenal (1.75 g, 11.4 mmol) and
benzaldehyde (1.21 g, 11.4 mmol) in dichloromethane (50 ml) is added boron
trifluoride diethyl etherate {0.65 ml, 5.1 mmol). The mixture is stirred at
0°C for
two and a half hour before trifluoroacetic acid (0.7 ml, 9 mmol) is added,
followed
by a dropwise addition at -10°C of ethylene oxide (1.5 ml, 30 mmol),
under
2o nitrogen. The mixture is stirred at -10°C for 30 minutes and then at
20°C for 18
hours, under nitrogen, before sodium carbonate (1.5 g, 14 mmol) is added. The
resulting mixture is stirred for 30 minutes before being diluted with 30 ml of
dichioromethane and washed with water (30 ml). The aqueous phase is then
extracted with dichloromethane (30 ml). Both organic phases are combined and
dried over sodium sulfate. After filtration and concentration on the
rotaevaporator, a very light yellow gum (13 g) is obtained.
VI-Synthesis of a copolyrmer of methyl ~lyroxlrlate, meth~,rl nonyt
acetaldehyde and trans-4-decenal, end-capped with ethylene oxide
3o To a solution at 0°C of freshly distilled methyl glyoxylate (15 g,
0.17 mol), methyl
nonyl acetaldehyde (8.38 g, 45.5 mmol} and trans-4-decenal (1.75 g, 11.4 mmol)
in dichloromethane (50 ml) is added boron trifluoride diethyl etherate (0.65
ml,
5.1 mmol). The mixture is stirred at 0°C for two and a half hour before
trifluoroacetic acid (0.7 ml, 9 mmol) is added, followed by a dropwise
addition at -
10°C of ethylene oxide (1.5 ml, 30 mmol), under nitrogen. The mixture
is stirred
at -10°C for 30 minutes and then at 20°C for 18 hours, under
nitrogen, before
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sodium carbonate (1.5 g, 14 mmol) is added. The resulting mixture is stirred
for
30 minutes before being diluted with 30 ml of dichloromethane and washed with
water (30 ml). The aqueous phase is then extracted with dichloromethane (30
ml). Both organic phases are combined and dried over sodium sulfate. After
filtration and concentration on the rotaevaporator, a very light yellow gum
(19 g)
is obtained.
VII-Synthesis of a copolymer of methyl ~~Iyoxylate and traps-4-decenal,
using phosphorus pentoxide as catalyst
o To a solution of freshly distilled methyl glyoxylate (7.96 g, 90 mmol) and
traps-4-
decenal (4.65 g, 30 mmol) in tetrahydrofuran (30 ml) is added phosphorus
pentoxide (1.70 g, 12 mmol). The mixture is stirred under argon at 20°C
for 24
hours before removal of the tetrahydrofuran on the rotaevaporator and its
replacement with dichloromethane (50 ml). Sodium carbonate (1.0 g, 9.4 mmol)
is then added and the resulting mixture is stirred for 30 minutes before being
diluted with 30 ml of dichloromethane and washed with water (30 ml). The
aqueous phase is then extracted with dichloromethane (30 ml). Both organic
phases are combined and dried over magnesium sulfate. After filtration and
concentration on the rotaevaporator, a light yellow gum (10.9 g) is obtained.
In the following formulation examples all levels are quoted as % by weight of
the
composition unless otherwise stated:
Example 1
The following high density granular laundry detergent compositions A to F were
prepared in accord with the invention:
A B C D E F
LAS 8.0 8.0 8.0 2.0 6.0 6.0
TAS - 0.5 - 0.5 1.0 0.1
C46(S)AS 2.0 2.5 - - - -
C25AS - - - 7.0 4.5 5.5
C68AS 2.0 5.0 7.0 - - -
C25E5 - - 3.4 10.0 4.6 4.6
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C25E7 3.4 3.4 1.0 - - -
C25E3S - - - 2.0 5.0 4.5
QAS - 0.8 - _ _ _
QAS (I) - - - 0.8 0.5 1.0
Zeolite A 18.1 18.0 14.1 18.1 20.0 18.1
Citric acid - - - 2.5 - 2.5
Carbonate 13.0 13.0 27.0 10.0 10.0 13.0
SKS-6 - - - 10.0 - 10.0
Silicate 1.4 1.4 3.0 0.3 0.5 0.3
Citrate - 1.0 - 3.0 - -
Sulfate 26.1 26.1 26.1 6.0 - -
Mg sulfate 0.3 - - 0.2 - 0.2
MA/AA 0.3 0.3 0.3 4.0 1.0 1.0
CMC 0.2 0.2 0.2 0.2 0.4 0.4
PB4 9.0 9.0 5.0 - - -
Percarbonate - - - - 18.0 18.0
TAED 1.5 0.4 1.5 - 3.9 4.2
NAC-OBS - 2.0 1.0 - - -
DTPMP 0.25 0.25 0.25 0.25 - -
SRP 1 - - - 0.2 - 0.2
EDDS - 0.25 0.4 - 0.5 0.5
CFAA - 1.0 - 2.0 - -
HEDP 0.3 0.3 0.3 0.3 0.4 0.4
QEA - _ _ 0.2 - 0.5
Protease I - - 0.26 1.0 - -
Protease 0.2fi 0.26 - - 1.5 1.0
Cellulase 0.3 - - 0.3 0.3 0.3
Amylase 0.1 0.1 0.1 0.4 0.5 0.5
Lipase (1) 0.3 - - 0.5 0.5 0.5
Photoactivated 15 ppm 15 ppm 15 ppm - 20 ppm 20 ppm
bleach (ppm)
PVNOIPVPVI - - - 0.1 - -
Brightener 1 0.09 0.09 0.09 - 0.09 0.09
Perfume 0.3 0.3 0.3 0.4 0.4 0.4
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Co-polymeric 0.3 0.3 0.3 0.4 0.4 0.4
compound (*)
Silicone antifoam0.5 0.5 0.5 - 0.3 0.3
Misc/minors to
100%
Density in gllitre850 850 850 850 850 850
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 2
The following granular laundry detergent compositions G to L of particular
utility
under European machine wash conditions were prepared in accord with the
invention:
G H I J K L
LAS 5.5 7.5 5.0 5.0 6.0 7.0
TAS 1.25 1.86 - 0.8 0.4 0.3
C24AS/C25AS - 2.24 5.0 5.0 5.0 2.2
C25E3S - 0.76 1.0 1.5 3.0 1.0
C45E7 3.25 - - - - 3.0
TFAA - - 2.0 - - -
C25E5 - 5.5 - - - -
QAS 0.8 - - - - -
QAS I ) - 0. 7 1. 0 0. 5 1. 0 0. 7
STPP 19.7 - _ _ _ _
Zeolite A - 19.5 25.0 19.5 20.0 17.0
NaSKS-6/citric - 10.6 - 10.6 - -
acid
(79:21 )
NaSKS-6 - - 9.0 - 10.0 10.0
Carbonate 6.1 21.4 9.0 10.0 10.0 18.0
Bicarbonate - 2.0 7.0 5.0 - 2.0
Silicate 6.8 - - 0.3 0.5 -
Citrate - - 4.0 4.0 - -
Sulfate 39.8 - - 5.0 - 12.0
Mg sulfate - - 0.1 0.2 0.2 -
MA/AA 0.5 1.6 3.0 4.0 1.0 1.0
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CMC 0.2 0.4 1.0 1.0 0.4 0.4
PB4 5.0 12.7 - - _ _
Percarbonate - - - - 18.0 15.0
TAED 0.5 3.1 - - 5.0 -
NAC-OBS 1.0 3.5 - - - 2.5
DTPMP 0.25 0.2 0.3 0.4 - 0.2
HEDP - 0.3 - 0.3 0.3 0.3
QEA - - 1.0 1.0 1.0 -
Protease I - - - 0.5 1.2 -
Protease 0.26 0.85 0.9 1.0 - 0.7
Lipase {1) 0.15 0.15 0.3 0.3 0.3 0.2
Cellulase 0.28 0.28 0.2 0.2 0.3 0.3
Amylase 0.1 0.1 0.4 0.4 0.6 0.2
PVNO/PVPVI - - 0.2 0.2 - -
PVP 0.9 1.3 - _ - 0.9
SRP 1 - - 0.2 0.2 0.2 -
Photoactivated 15 ppm 27 ppm - - 20 ppm 20 ppm
bleach (1) (ppm)
Photoactivated 15 ppm - - _ _ _
bleach (2) (ppm)
Brightener 1 0.08 0.19 - - 0.09 0.15
Brightener 2 - 0.04 - - _ _
Pertume 0.3 0.3 0.4 0.3 0.4 0.3
Co-polymeric 0.3 0.3 0.4 0.3 0.4 0.3
compound (*)
Silicone antifoam0.5 2.4 0.3 0.5 0.3 2.0
Minors/misc to
100%
Density in g/litre750 750 750 750 750 750
{*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 3
5 The following detergent formulations of particular utility under European
machine
wash conditions were prepared in accord with the invention.
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M N 10 P
Blown powder
LAS 6.0 5.0 11.0 6.0
TAS 2.0 - - 2.0
Zeolite A 24.0 - - 20.0
STPP - 27.0 24.0 -
Sulfate 4.0 6.0 13.0 -
MA/AA 1.0 4.0 6.0 2.0
Silicate 1.0 7.0 3.0 3.0
CMC 1.0 1.0 0.5 0.6
Brightener 1 0.2 0.2 0.2 0.2
Silicone antifoam 1.0 1.0 1.0 0.3
DTPMP 0.4 0.4 0.2 0.4
Spray on
Brightener 0.02 - - 0.02
C45E7 - - - 5.0
C45E2 2.5 2.5 2.0 -
C45E3 2.6 2.5 2.0 -
Perfume 0.5 0.3 0.5 0.2
Co-polymeric 0.5 0.3 0.5 0.2
compound (*)
Silicone antifoam 0.3 0.3 0.3 -
Dry additives
- - - 1.0
EDDS 0.3 - - -
Sulfate 2.0 3.0 5.0 10.0
Carbonate 6.0 13.0 15.0 14.0
Citric acid 2.5 - - 2.0
QAS II 0.5 - - 0,5
SKS-6 10.0 - - -
Percarbonate 18.5 - - -
PB4 - 18.0 10.0 21.5
TAED 2.0 2.0 - 2.0
NAC-OBS 3.0 2.0 4.0 -
Protease 1.0 1.0 1.0 1.0
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Lipase - 0.4 . - 0.2
Lipase (1 ) 0.4 - 0.4
Amylase 0.2 0.2 0.2 0.4
Brightener 1 0.05 - - 0.05
Misclminor to 100%
(*) Co-polymeric compound as made in any one of Synthesis Examples 1 to VII.
Exam~~le 4
The following granular detergent formulations were prepared in accord with the
invention.
Q R S T U V
Blown powder
LAS 23.0 8.0 7.0 9.0 7.0 7.0
TAS - - - - 1.0 -
C45AS 6.0 6.0 5.0 8.0 - -
C45AES - 1.0 1.0 1.0 - -
C45E35 - - - - 2.0 4.0
Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
MAIAA - 0.5 - - - 2.0
MAlAA ( 1 ) 7. 0 - _ _ _ _
AA - 3.0 3.0 2.0 3.0 3.0
Sulfate 5.0 6.3 14.3 11.0 15.0 19.3
Silicate 10.0 1.0 1.0 1.0 1.0 1.0
Carbonate 15.0 20.0 10.0 20.7 8.0 6.0
PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0
DTPA - 0.9 0.5 - - 0.5
Brightener 2 0.3 0.2 0.3 - 0.1 0.3
Spray on
C45E7 - 2.0 - - 2.0 2.0
C25E9 3.0 - - - - -
C23E9 - - 1.5 2.0 - 2.0
Perfume 0.3 0.3 0.3 2.0 0.3 0.3
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Co-polymeric 0.3 0.3 0.3 2.0 0.3 0.3
compound (*)
Agglomerates
C45AS - 5.0 5.0 2.0 - 5.0
LAS - 2.0 2.0 - - 2.0
Zeolite A - 7.5 7.5 8.0 - 7.5
Carbonate - 4.0 4.0 5.0 - 4.0
PEG 4000 - 0.5 0.5 - - 0.5
Misc (water etc.) - 2.0 2.0 2.0 - 2.0
Dry additives
QAS (I) - - - - 1.0 -
Citric acid - - - - 2.0 -
PB4 - - - - 12.0 1.0
PB1 4.0 1.0 3.0 2.0 - -
Percarbonate - - - - 2.0 10.0
Carbonate - 5.3 1.8 - 4.0 4.0
NOES 4.0 - 6.0 - - 0.6
Methyl cellulose 0.2 - - - - -
SKS-6 8.0 - - - - -
STS - - 2.0 - 1.0 -
Cumene sulfonic acid- 1.0 - - - 2.0
Lipase 0.2 - 0.2 - 0.2 0.4
Cellulase 0.2 0.2 0.2 0.3 0.2 0.2
Am lase 0.2 - 0.1 - 0.2 -
Protease 0.5 0.5 0.5 0.3 0.5 0.5
PVPVI - - - - 0.5 0.1
PVP - _ _ - 0.5 -
PVNO - - 0.5 0.3 - -
QEA - - - - 1.0 -
SRP1 0.2 0.5 0.3 - 0.2 -
Silicone antifoam 0.2 0.4 0.2 0.4 0.1 -
Mg sulfate - - 0.2 - 0.2 -
Misclminors to 100%
(*) Co-polymeric compound as made in any one of Synthesis Examples t to VII.
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Examele 5
The following nil bleach-containing detergent formulations of particular use
in the
washing of coloured clothing, according to the present invention were
prepared:
s
W X Y
Blown Powder
Zeolite A 15.0 15.0 -
Sulfate 0.0 5.0 -
LAS 3.0 3.0 -
DTPMP 0.4 0.5 -
CMC 0.4 0.4 -
MAIAA 4.0 4.0 -
Agg lomerates
C45AS - - 11.0
LAS 6.0 5.0 -
TAS 3.0 2.0 -
Silicate 4.0 4.0 -
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
Co-polymeric compound (*) 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Alcalase 0.5 0.3 0.9
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Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sulfate 0.0 9.0 0.0
Misclminors to 100% 100.0 100.0 100.0
Density (g/litre) 700 700 700
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 6
The following granular detergent formulations were prepared in accord with the
invention.
Z AA BB
Base granule
Zeolite A 30.0 22.0 24.0
Sulfate 10.0 5.0 10.0
MA/AA 3.0 - -
AA - 1.6 2.0
MA/AA ( 1 ) - 12. 0 -
LAS 14.0 10.0 9.0
C45AS 8.0 7.0 9.0
C45AES - 1.0 1.0
Silicate - 1.0 0.5
Soap - 2.0 -
Brightener 1 0.2 0.2 0.2
Carbonate 6.0 9.0 10.0
PEG 4000 - 1.0 1.5
DTPA - 0.4 -
Spray on
C25E9 - - -
C45E7 1.0 1.0 -
C23E9 - 1.0 2.5
Perfume 0.2 0.3 0.3
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Co-polymeric compound (*) 0.2 0.3 0.3
Dry additives
Carbonate 5.0 10.0 18.0
PVPVI/PVNO 0.5 - 0.3
Protease 1.0 1.0 1.0
Lipase 0.4 - -
Amylase 0.1 - -
Cellulase 0.1 0.2 0.2
NOBS - 4.0
PB1 1.0 5.0 1.5
Sulfate 4.0 5.0 -
SRPI - 0.4 -
Sud supressor - 0.5 0.5
Misclminor to 100%
(*) Co-polymeric compound as made in any one of Synthesis Examples t to VII.
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Example 7
The following granular detergent compositions were prepared in accord with the
invention.
CC DD EE
Blown powder
Zeolite A 20.0 - 15.0
STPP - 20.0 -
Sulphate - - 5.0
Carbonate - - 5.0
TAS - - 1.0
LAS 6.0 6.0 6.0
C68AS 2.0 2.0 -
Silicate 3.0 8.0 -
MAIAA 4.0 2.0 2.0
CMC 0.6 0.6 0.2
Brightener 1 0.2 0.2 0.1
DTPMP 0.4 0.4 0.1
STS - - 1.0
Spray on
C45E7 5.0 5.0 4.0
Silicone antifoam 0.3 0.3 0.1
Perfume 0.2 0.2 0:3
Co-polymeric compound 0.2 0.2 0.3
(*)
Dry additives
QEA - - 1.0
Carbonate 14.0 9.0 10.0
PB1 1.5 2.0 -
PB4 18.5 13.0 13.0
TAED 2.0 2.0 2.0
QAS (I) - - 1.0
Photoactivated bleach 15 ppm 15 ppm 15ppm
SKS-6 - - 3.0
Protease 1.0 1.0 0.2
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Lipase 0.2 0.2 0.2
Amylase 0.4 0.4 0.2
Cellulase 0.1 0.1 0.2
Sulfate 10.0 20.0 5.0
Misclminors to 100%
Density (gllitre) 700 700 700
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 8
The following detergent compositions, according to the present invention were
prepared:
FF GG HH
Blown Powder
Zeolite A 15.0 15.0 15.0
Sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DTPMP 0.4 0.2 0.4
EDDS - 0.4 0.2
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
Co-polymeric compound (*) 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
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Bicarbonate - 3.0 -
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
PEO - - 0.2
Bentonite clay - - 10.0
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Misc/minors to 100% 100.0 100.0 100.0
Density (gllitre) 850 850 850
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 9
The following detergent formulations, according to the present invention were
prepared:
II JJ KK LL
LAS 20.0 14.0 24.0 20.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -
C23E56.5 - - 1.0 -
C45E7 - 1.0 - -
C45E3S 1.0 2.5 1.0 -
STPP 36.0 18.0 30.0 22.0
Silicate 9.0 5.0 9.0 8.0
Carbonate 13.0 7.5 10.0 5.0
Bicarbonate - 7.5 - -
PB1 3.0 1.0 - -
PB4 - 1.0 - _
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NOBS 2.0 1.0 - -
DTPMP - 1.0 - -
DTPA 0.5 - 0.2 0.3
SRP 1 0.3 0.2 - 0.1
MA/AA 1.0 1. 5 2.0 0.5
CMC 0.8 0.4 0.4 0.2
PEI - - 0.4 -
Sodium sulfate 25.0 10.0 20.0 30.0
Mg sulfate 0.2 - 0.4 0.9
Protease 0.8 1.0 0.5 0.5
Amylase 0.5 0.4 - 0.25
Lipase 0.2 - 0.1 -
Cellulase 0.15 - - 0.05
Photoactivated 30ppm 20ppm - 10ppm
bleach (ppm)
Perfume 0.3 0.3 0.1 0.2
Co-polymeric 0.3 0.3 0.1 0.2
compound (*)
Brightener 1/2 0.05 0.2 0.08 0.1
Misclminors
to 100%
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 10
The following liquid detergent formulations were prepared in accord with the
5 invention (levels are given as parts per weight).
MM NN 00 PP QQ
LAS 11.5 8.8 - 3.9 -
C25E2.5S - 3.0 18.0 - 16.0
C45E2.25S 11.5 3.0 - 15.7 -
C23E9 - 2.7 1.8 2.0 1.0
C23E7 3.2 - - - -
CFAA - - 5.2 - 3.1
TPKFA 1.6 - 2.0 0.5 2.0
Citric acid (50%) 6.5 1.2 2.5 4.4 2.5
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Calcium formate 0.1 0.06 0.1 - -
Sodium formate 0.5 0.06 0.1 0.05 0.05
Sodium cumene sulfonate4.0 1.0 3.0 1.18 -
Borate 0.6 - 3.0 2.0 2.9
Sodium hydroxide 5.8 2.0 3.5 3.7 2.7
Ethanol 1.75 1.0 3.6 4.2 -2.9
1, 2 propanediol 3.3 2.0 8.0 7.9 5.3
Monoethanolamine 3.0 1.5 1.3 2.5 0.8
TEPAE 1.fi - 1.3 1.2 1.2
Protease 1.0 0.3 1.0 0.5 0.7
Lipase - - 0.1 - -
Cellulase - - 0.1 0.2 0.05
Amylase - - - 0.1 -
SRP1 0.2 - 0.1 - -
DTPA - - 0.3 - -
PVNO - - 0.3 - 0.2
Brightener 1 0.2 0.07 0.1 - -
Silicone antifoam 0.04 0.02 0.1 0.1 0.1
Co-polymeric compound 0.04 0.02 0.1 0.1 0.1
(*)
Waterlminors
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 11
The following liquid detergent formulations were prepared in accord with the
invention (levels are given in parts per weight):
RR SS n UU W
AS 10.0 13.0 - 25.0 -
C25AS 4.0 1.0 10.0 - 13.0
C25E3S 1.0 - 3.0 - 2.0
C25E7 6.0 8.0 2.5 - -
TFAA - - 4.5 - 6.0
APA - 1.4 - 3.0 1.0
TPKFA 2.0 - 7.0 - 15.0
Citric acid 2.0 3.0 1.5 1.0 1.0
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Dodecenylltetradecenyl 12.0 10.0 - 15.0 -
succinic acid
Rape seed fatty acid 4.0 2.0 - 1.0 -
Ethanol 4.0 4.0 2.0 7.0 2.0
1,2 Propanediol 4.0 4.0 7.0 6.0 8.0
Monoethanolamine - - 5.0 - -
Triethanolamine - - - - -
TEPAE 0.5 - 0.2 - -
DTPMP 1.0 1.0 1.0 2.0 1.2
Protease 0.5 0.5 0.25 - 0.5
Alcalase - - - 1.5 -
Lipase - 0.10 0.01 - -
Amylase 0.25 0.25 0.5 0.25 0.9
Cellulase - - 0.05 - -
Endolase - - 0.10 - -
SRP2 0.3 - 0.1 - -
Boric acid 0.1 0.2 2.0 1.0 1.5
Calcium chloride - 0.02 0.01 - -
Bentonite clay - - - 4.0 4.0
Brightener 1 - 0.4 - 0.1 0.2
Sud supressor 0.1 0.3 0.1 0.4 -
Opacifier 0.5 0.4 0.3 0.8 0.7
Co-polymeric compound 0.5 0.4 0.3 0.8 0.7
(*)
Waterlminors to 100%
NaOH up to pH 8.0 8.0 7.7 8.0 7.5
(*) Co-polymeric compound as made in any one of Synthesis Examples I to Vll.
Example 12
The following liquid detergent compositions were prepared in accord with the
invention (levels are given in parts per weight).
WW XX
~-AS 27.6 18.9
C45AS 13.8 5.9
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C13E8 3.0 3.1
Oleic acid 3.4 - 2.5
Citric acid 5.4 5.4
Sodium hydroxide 0.4 3.6
Calcium formate 0.2 0.1
Sodium formate - 0.5
Ethanol 7.0 -
Monoethanolamine 16.5 8.0
1,2 propanediol 5.9 5.5
Xylene sulfonic acid - 2.4
TEPAE 1.5 0.8
Protease 1.5 0.6
PEG - 0.7
Brightener 2 0.4 0.1
Perfume 0.5 0.3
Co-polymeric compound (*) 0.5 0.3
Waterlminors
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 13
The following laundry bar detergent compositions were prepared in accord with
the invention (levels are given in parts per weight).
YY ZZ AB AC AD AE
LAS - - 19.0 15.0 21.0 -
C28AS 30.0 13.5 - - - 22.5
Sodium laurate 2.5 9.0 - - - -
Zeolite A 2.0 1.25 - - - 1.25
Carbonate 20.0 3.0 13.0 8.0 10.0 10.0
Calcium carbonate 27.5 39.0 35.0 - - 40.0
Sulfate 5.0 5.0 3.0 5.0 3.0 5.0
TSPP 5.0 - - - - -
STPP 5.0 15.0 10.0 - - 10.0
Bentonite clay - 10.0 - - 5.0 -
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DTPMP - 0.7 0.6 - 0.6 0.7
CMC - 1.0 1.0 1.0 1.0 1.0
Talc - - 10.0 15.0 10.0 -
Silicate - - 4.0 5.0 3.0 -
PVNO 0.02 0.03 - 0.01 - -
MAIAA 0.4 1.0 - - 0.2 0.4
SRP1 0.3 0.3 0.3 0.3 0.3 0.3
Protease - 0.12 - 0.08 0.08 0.1
Lipase - 0.1 - 0.1 - -
Amylase - - 0.8 - - -
Cellulase - 0.15 - - 0.15 -
PEO - 0.2 - 0.2 0.3 0.3
Perfume 1.0 0.5 0.3 0.2 0.4 0.4
Co-polymeric compound 1.0 0.5 0.3 0.2 0.4 0.4
(*)
Mg sulfate - - 3.0 3.0 3.0 -
Brightener 0.15 0.10 0.15 - - 0.1
Photoactivated bleach - 15.0 15.0 15.0 15.0 15.0
(ppm)
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 14
The following fabric softening compositions are in accordance with the present
invention
Component AF AG AH AI AJ AK
DTDMAC - - - - 4.5 15.0
DEQA 2.6 2.9 18.0 19.0 -
Fatty acid 0.3 - 1.0 - -
Hydrochloride 0.02 0.02 0.02 0.02 0.02 0.02
acid
PEG - - 0.6 0.6 - 0.6
Perfume 1.0 1.0 1.0 1.0 1.0 1.0
Silicone antifoam0.01 0.01 0.01 0.01 0.01 0.01
Co-polymeric 0.4 0.6 0.8 0.8 0.6 0.8
compound (*)
Electrolyte (ppm)- - 600 1200 - 1200
Dye (ppm} 10 10 50 50 10 50
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Carezyme CEVU/g ~ - ~ - ~ - 50 - -
Water and minors to balance to 100
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 15
5 The following compositions for use as dryer-added sheets are in accordance
with
the invention
AL AM AN AO AP AQ
DOEQA 40 25 - - - -
DHEQA - - 20 - - -
DTDMAMS - - - 20 12 60
SDASA 30 30 20 30 20 -
Glycosperse S-20- - 10 - - -
Glycerol - - - 20 10 -
Monostearate
Clay 4 4 3 4 4 -
Perfume 0.7 1.1 0.7 1.6 2.6 1.4
Co-polymeric 0.8 0.5 0.8 0.8 0.5 1.20
compound (*)
Stearic acid
to balance
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 16
The following hard surface cleaning compositions AX to AZ are in accordance
with
the present invention
AR AS AT
Dobanol23-3~ 3.20 3.20 1.28
Lutensol A030~ 4.80 4.80 1.92
Dobanol C7-11 E06~ 8.0 8.0 3.20
Topped Palm Kernal Fatty acid, 0.80 0.80 0.40
Na salt
C8 Alkyl sulphate, Na salt 2.0 2.0 0.8
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Paraffin sulphonate, Na salt 3.0 3.0 1.20
Cumene sulphonate, Na salt 3.0 3.0 1.20
Perfume 0.8 0.8 0.6
Branched alcohol, Isofol 16~ - - 0.30
Co-polymeric compound (*) 1.86 2.49 0.6
NaOH up to pH 10 pH 10 pH 10
Water and Minors up to 100%
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
Example 17
The following dishwashing machine compositions according to the invention were
prepared.
AU AV AW AX AY AZ BA
Citrate 15.0 15.0 15.0 15.0 15.0 15.0 -
480N 6.0 6.0 6.0 6.0 6.0 6.0 -
Carbonate 17.5 17.5 17.5 17.5 17.5 17.5 -
STPP _ _ _ _ _ - 38.0
Silicate (as Si0 8.0 8.0 8.0 8.0 8.0 8.0 14.0
)
Metasilicate (as 1.2 1.2 1.2 1.2 1.2 1.2 2.5
Si0 )
PB1 (Av0) 1.2 1.2 1.5 1.5 1.5 2.2 1.2
TAED 2.2 2.2 2.2 - - 2.2 2.2
BzP _ _ - 0.8 - _ _
Cationic precursor - - - - 3.3 - -
Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Bismuth nitrate - 0.2 0.2 0.2 0.3 0.4 0.2
BDIMA _ _ _ _ _ _ 0.5
PMT - - - - - - 0.5
Protease 0.04 0.04 0.04 0.04 0.04 0.04 0.04
Amylase 0.03 0.03 0.03 0.03 0.03 0.03 -
BSA _ _ _ _ _ - 0.03
DETPMP 0.13 0.13 0.13 0.13 0.13 0.13 -
HEDP 1.0 1.0 1.0 1.0 1.0 1.0 -
Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5
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Co-polymeric 0.5 0.5 0.5 1.86 1.86 1.86 1.86
compound (*)
Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3
misc inc Moisture
to balance
(*) Co-polymeric compound as made in any one of Synthesis Examples I to VII.
