Note: Descriptions are shown in the official language in which they were submitted.
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WO 00/50549 PCT/US00/04185
CLEANING COMPOSITIONS CONTAINING
SELECTED NONIONIC SURFACTANTS
FIELD OF THE INVENTION
The present invention relates to cleaning compositions containing nonionic
surfactants
selected to improve dissolution of solid products and improve rates of mixing
with water of liquid
products, while maintaining good physical attributes, good performance and
biodegradability.
BACKGROUND OF THE INVENTION
Due to the varied nature of different cleaning compositions, different
surfactants are
better suited for some applications while being less suited or totally
unsuitable for other
applications. Nonionic surfactants, such as alcohol ethoxylates, alkyl
polyglycosides, and alkyl
glucose amides are of considerable importance in detergent products. For
example, under some
conditions, nonionic surfactants aid cleaning of greasy soils and inhibit the
formation of calcium
soap. However, conventional nonionic surfactants designed for effective
cleaning in laundry
products form liquid crystalline phases on mixing with water. These phases can
hinder the rate
of mixing with water and lead to undesirable optical properties of thin films
on solution drying.
For example, conventional nonionics sprayed on the surface of granules to
achieve target density
can give rise to poor granule dissolution and residue in horizontal axis
machine dispensers.
Conventional nonionics formulated at high levels in liquid products can lead
to poor rates of
mixing with water and consumer concern. Conventional nonionics in window and
floor cleaners
can form visible liquid crystalline films on drying that increase the effort
required by the
consumer to achieve a good results.
On account of the foregoing technical constraints as well as consumer needs
and
demands, product compositions are undergoing continual change and improvement.
Moreover
environmental factors such as the need for biodegradable materials, the
restriction of phosphate,
the desirability of providing ever-better cleaning results with less product,
providing less thermal
energy demand, and less water to assist the washing process, have all driven
the need for
improved compositions.
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2
Accordingly, the need remains for new surfactants which are suitable for use
in a variety
of compositions which can provide improve dissolution of solid products like
bars and granular
products, improved rates of mixing with water as with liquid products,
improved streaking and
filming performance as in hard surface cleaners, good cleaning and good
biodegradability.
SUMMARY OF THE INVENTION
This need is met by the present invention wherein detergent compositions
having a
selected nonionic surfactant are provided. The compositions employ the novel
surfactants of the
present invention, either alone or in combination with other surfactants, to
provide improved
dissolution of solid products like granules, improved rates of mixing with
water for liquid
products, and improved dry-down optical properties on hard surfaces, while at
the same time
providing acceptable cleaning performance, foaming properties and aesthetics.
According to the first embodiment a granular laundry detergent composition is
provided.
The granular laundry composition comprises:
a) a butoxycapped nonionic surfactant;
b) a conventional detergent additive; and
c) a co-surfactant;
wherein the composition is in the form of a granule with a bulk density of
from about 100 g/1 to
about 1400 g/1.
According to the second embodiment a nonaqueous heavy duty liquid (HDL)
laundry
detergent composition is provided. The nonaqueous HDL composition in the form
of a stable
suspension of solid, substantially insoluble particulate material dispersed
throughout a structured,
surfactant-containing liquid phase, wherein the comprises:
from about 55% to 98.9% by weight of the composition of a structured,
surfactant-
containing liquid phase formed by combining:
i) from about 1% to 80% by weight of said liquid phase of one or more
nonaqueous
organic diluents; and
ii) from about 20% to 99% by weight of said liquid phase of a surfactant
system
comprising surfactants selected from the group consisting of anionic,
nonionic,
cationic surfactants and combinations thereof;
wherein said surfactant system comprises at least about 10%, by weight of a
butoxycapped
nonionic surfactant.
According to the third embodiment an aqueous heavy duty liquid (HDL) laundry
detergent composition is provided. The aqueous HDL composition comprises:
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3
a) a butoxycapped nonionic surfactant;
b) an amide co-surfactant composition selected from the group consisting of
alkyl
polyhydroxy fatty acid amide, alkyl amidopropyl dimethyl amine and mixtures
thereof;
c) a conventional detergent additive; and
d) an aqueous liquid carrier.
The HDL compositions defined herein may also preferably comprise from about 1%
to
about 80% by weight of the composition of additional detergent ingredients
such as builders,
enzymes, colorants, bleaching agents, bleach activators, and other known
ingredients. In the
nonaqueous compositions adjuvants can be added in the form of particulate
material which ranges
in size from about 0.1 to about 1500 microns, which is substantially insoluble
in the liquid phase
and which is selected from the group consisting of peroxygen bleaching agents,
bleach activators,
colored speckles, organic detergent builders, inorganic alkalinity sources and
mixtures thereof.
According to the fourth embodiment a light duty liquid (LDL) detergent
composition is
provided. The aqueous LDL composition comprises:
a) a butoxycapped nonionic surfactant;
b) a conventional detergent additive;
c) a co-surfactant;
wherein the composition is in the form of a liquid, gel, or liqui-gel and the
pH (as measured as
10% aqueous solution) is from about 5.0 to about 12.5.
According to the fifth embodiment a hard surface cleaning composition is
provided. The
hard surface cleaning composition comprises:
a) a butoxy capped nonionic surfactant;
b) a co-surfactant;
c) a hard surface cleaning composition adjunct ingredient;
wherein said composition is in the form of a liquid, gel or liqui-gel.
According to the sixth embodiment a shampoo, or personal cleansing composition
is
provided. The shampoo composition comprises:
a) a butoxycapped nonionic surfactant;
b) a co-surfactant;
c) a solvent
d) a shampoo composition adjunct ingredient;
wherein said composition is in the form of a liquid, gel or liqui-gel.
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4
All percentages, ratios and proportions herein are by weight of ingredients
used to
prepare the finished compositions unless otherwise specified. All documents
cited herein are, in
relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
Once again, the present invention is directed toward a low-foaming nonionic
surfactant
for use in detergent compositions. The disclosed compounds of the present
invention may-also
be employed in laundry and skin care compositions.
Selected Nonionic Surfactant System
The essential nonionic surfactants of the present invention must have an X/Y
number of
greater than 1.00, preferably greater than 1.10, more preferably greater than
1.30. The
determination of this X/Y number is described hereinafter. It has been
surprisingly found that
surfactants with an X/Y number greater than 1.00 demonstrate superior cleaning
to nonionic
surfactants with a X/Y number of 1.00 or less. When the nonionic surfactant
contains a glyceryl
ether group then the X/Y number is calculated exclusive of any possible dimers
and trimers. That
is any dimers and trimers present are not used to calculate the X/Y value for
any nonionic
surfactant containing a glyceryl ether group.
Furthermore these surfactants provide suds control and in combination with the
oxide
surfactant provide a level of suds which is suitable for use in an ADW
composition.
Furthermore, the nonionic surfactant of the present invention have minimal
negative interaction
with the cleaning of the oxide surfactant.
Suitable surfactants include ethoxy and propoxy containing ether-capped
poly(oxyalkylated) alcohol surfactants, ethoxy and butoxy containing ether-
capped
poly(oxyalkylated) alcohol surfactants, ethoxy and butoxy containing
alkylalkoxylates, and
ethoxy, propoxy and butoxy containing alkyalkoxylates. However, when the LF'NI
surfactant
contains a glyceryl ether-group then it is preferred that the amount of any
possible dimer or
trimer present be minimized. The amount of dimer and trimer is minimized to
levels such that
these have minimal negative interaction with the cleaning of the oxide
surfactant. The amount of
dimer and trimer present in the glyceryl ether containing surfactant is
dependent upon the
process used to produce the surfactant. The preferred method for minimizing or
eliminating the
formation of dimer and trimer maybe controlled by the stoichiometry of the
reactants or via
typical purification methods (e.g. Chromatography, crystallization,
fictionalization etc.).
One preferred LFNI of the present invention have the formula:
R1 (EO)a(PO)b(BO)~
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wherein R1 is a linear or branched C6 to C20 alkyl, preferably linear or
branched C8 to C18
alkyl, more preferably linear or branched C9 to C 16 alkyl; a is an integer
from 2 to 30, preferably
from 4 to 25, more preferably from 5 to 20 more preferably from 5 to 18; b is
an integer from 0 to
30 preferably from 0 to 25, more preferably from 0 to 20, more preferably from
0 to 10; c is an
5 integer from 1 to 10 preferably from 1 to 9, more preferably from 1 to 7,
more preferably from 1
to 6.
Another preferred LFNI of the present invention has the formula:
R10[CH2CH(R3)O]m[CH2)kCH(OH)[CH2]jOR2
wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic
or aromatic
hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear
aliphatic
hydrocarbon radical having from 1 to 4 carbon atoms; m is an integer having an
average value
from 1 to 40, wherein when m is 2 or greater R3 may be the same or different
and k and j are
integers having an average value of from 1 to 12; further wherein when m is 15
or greater and R~
is H and methyl, at least four of R3 are methyl, further wherein when m is 15
or greater and R3
includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl,
propyl or butyl, further
wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from
ethoxy, propoxy,
butyloxy and mixtures thereof; wherein further, said surfactant has less than
30%, preferably less
than 15% and most preferably less than 5% of dimers and trimers of said
nonionic surfactant.
Another preferred LFI'1I of the present invention has the formula:
R10[CH2CH(R3)O]eR2
wherein R1 is a linear or branched, saturated or unsaturated, aliphatic or
aromatic hydrocarbon
radicals having from 1 to 30 carbon atoms; R2 is a linear or branched,
saturated or unsaturated,
aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms,
optionally
containing from 1 to 5 hydroxy groups; and further optionally substituted with
an ether group; R3
is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon
atoms; a is an integer
having an average value from 1 to 40, wherein R2 can optionally be
alkoxylated, wherein said
alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof.
Suitable surfactants include, but are not limited to,
Surfactant I X/Y value
C9,11P03E013B06 1.41
C9,11 P03E013B03 1.70
C9,11 EO 13B06 1.49
C9,11 EO 13B03 1.88
C9,11 BO 1 EO 13B03 1.72
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WD 00/50549 PCT/US00/04185
6
C9,1 lEO8B03 1.29
C 12,1 SE07B02 1.03
C9,11 E08B02 1.41
C9,11 E08B01 1.58
C12,13E06.ST*BO1 1.10
*: Denotes topped, or narrow selection of EO distribution.
Calculation of X/Y
The LFNI surfactants of the present invention must all have a ratio of
hydrophobic to
hydrophilic, or "X/Y" number of greater than or equal to 1.00.
The calculation of "X/Y" is as follows. For a given alkoxylated nonionic
surfactant
structure, "X" is defined as the sum of the protons attached to carbon atoms
that are adjacent to
oxygen. "Y" is defined as the sum of all the protons attached to carbon atoms
within said
molecule that are non-adjacent to oxygen. That is,
x x x
I I-1 I
~~O ~z
I I I I
Y Y
A typical example is shown below. For C,3EO,zC,3, X = 52 and Y = 50.
Therefore, X/Y= 52/50= 1.04.
X/Y can also be measured experimentally from integration of the 'H NMR
spectrum.
The "X" protons are represented as the peak area defined by the region of the
spectrum from d
3.0 to 4.0 ppm. The "Y" protons are represented as the peak area defined from
d 0.5 to 2.0 ppm.
X/Y is then calculated by dividing the peak area from 3.0 to 4.0 ppm by the
peak area from 0.5 to
2.0 ppm.
Laundry or Cleaning Adjunct Materials and Methods'
In general, a laundry or cleaning adjunct is any material required to
transform a
composition containing only the minimum essential ingredients into a
composition useful for
laundry or cleaning purposes, such as a LDL, HDL or shampoo. In preferred
embodiments,
laundry or cleaning adjuncts are easily recognizable to those of skill in the
art as being absolutely
characteristic of laundry or cleaning products, especially of laundry or
cleaning products intended
for direct use by a consumer in a domestic environment.
CA 02362945 2003-03-06
.
The precise nature of these additional components, and levels of incorporation
thereof,
will depend on the physical form of the composition and the nature of the
cleaning operation for
which it is to be used.
Preferably, the adjunct ingredients if used with bleach should have good
stability
therewith. Certain preferred detergent compositions herein should be boron-
free and/or
phosphate-free as required by legislation. Levels of adjuncts are from about
0.00001% to about
99.9%, by weight of the compositions. Use levels of the overall compositions
can vary widely
depending on the intended application, ranging for example from a few ppm in
solution to so-
called "direct application" of the neat cleaning composition to the surface to
be cleaned.
Common adjuncts include builders, co-surfactants, enzymes, polymers, bleaches,
bleach
activators, catalytic materials and the like excluding any materials already
defined hereinabove as
part of the essential component of the inventive compositions. ether adjuncts
herein can include
diverse active ingredients or specialized materials, for example, dispersant
polymers (e.g., from
BASF Corp. or Rohm & Haas), color speckles, silvercare, anti-tarnish and/or
anti-corrosion
agents, dyes, fillers, germicides, bactericides, alkalinity sources,
hydrotropes, anti-oxidants,
enzyme stabilizing agents, suds boosters, buffers, anti-fungal agents, mildew
con~ol agents,
insect repellents, anti-corrosive aids, chelants suds suppressors thickeners,
abrasives, pro-
perfumes, perfumes, solubilizing agents, carriers, processing aids, pigments,
and, for liquid
formulations, solvents, as described in detail hereinafter.
Co-surfactants:
'The surfactant system of the compositions according to the present invention
may further
comprise additional surfactants, herein also referred to as cc>-surfactants,
preferably selected
from: anionic surfactants, preferably selected from the group of alkyl
alkoxylated sulfates, alkyl
sulfates, alkyl disulfates, andlor linear alkyl benzenesulfonate surfactants;
cationic surfactants,
2a preferably selected from quaternary ammonium surfactants; nonionic
surfactants, preferably alkyl
ethoxylates, alkyl polyglucosides, polyhydroxy fatty acid amides, and/or amine
or amine oxide
surfactants; arnphoteric surfactants, preferably selected from betaines andlor
polycarboxylates
(for example polyglycinates); and zwStterionic surfactants.
A wide range of these co-surfactants can be used in the cleaning compositions
of the
present invention. A typical listing of anionic, nonionic, ampholytic and
zwitterionic classes, and
species of these co-surfactants, is given in US Patent 3,664,961 issued to
Norris on May 23, 1972.
Amphoteric surfactants are also described in detail in '°Amphoteric
Surfactants, Second Edition",
E.G. Lornax, Editor (published 1996, by Marcel Dekker, Inc.). Suitable
surfactants can be found
in Wp 97/39087; WO 97/39088
CA 02362945 2003-03-06
8
WO 97/39091; WO 98/23712; WO 97/38972; WO 9 7/39089; WO 97/39090; WC)
99/19434; WO
99/18929; WO 99/19435; EP 1 023 042; WO 99119448; EP 1 023 431; WO 99/05243;
WO
99105242; WO 99/05244; WO t)9,~05082; WO 9~?.105084; WO 99/05241; WO 99!07656;
WO
00/23549 and WO 00!23548.
1 to
The compositions of the present invention preferably comprise from about 4.01%
to about
55%, more preferably from about 0.1% to about 45%, more preferably from about
0.25% to about
1;i 30%, more preferably from about 0.5% to about 20%, by weight of co-
surfactants. Selected co-
surfactants are further identified as follows.
(1) Anionic Co-surfactants:
Nonlimiting examples of anionic co-surfactants useful herein, typically at
levels from
about 0.1% to about 50%, by weight, include the conventional C;11-Clg alkyl
benzene sulfonates
2G ("LAS") and primary, branched-chain and random Clp-C20 alkyl sulfates
("AS"), the Clp-C18
secondary (2,3) alkyl sulfates of the formula CH3(GH2)x(CHOS03 M+} CH3 and CH3
(CH2)y(CHOS03 M+) CH2CH3 whcrc x and (y + 1 ) are integers of at least about
7, preferably at
least about 9, and M is a water-solubilizing canon, especially sodium,
unsaturated sulfates such as
oleyl sulfate, the C 1 p-C 1 g alpha-sulfonated fatty acid esters, the C 10-
C18 sulfated alkyl
26 polyglycosides, the Clp-Clg alkyl alkoxy sulfates ("AI;xS"; especially EO 1-
7 ethoxy sulfates),
and Clp-Clg alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates). The
C12-Clg bctaines and sulfobetaines ("sultaines"), C10-CIg amine oxides, and
the like, can also
be included in the overall compositions. C lp-C2p conventional soaps may also
be used. If high
sudsing is desired, the branched-chain Clp-Cls soaps may he used. Other
conventional useful
30 anionic co-surfactants are listed in standard texts.
Other ~ suitable anionic surfactants that can be used ate alkyl ester
sulfonate surfactants
including linear esters of Cg-C2p carboxylic acids (1.e., fatty acids) which
are sulfonated with
gaseous SO3 according to "The Journal of the American Oil Chemists Society",
52 (1975), pp.
CA 02362945 2003-03-06
9
323-329. Suitable starting materials would include natural fatty substances as
derived from
tallow, palm oil, etc.
Another type of useful surfactants aa~e the so-called dianionics. These are
surfactants
which have at least two anionic groups present on the surfactant molecule.
Some suitable
dianionic surfactants are further described in
WO 98!00498; WO 98/00503; ~S 5,958,858; WO 98/05742; and WO 98/05749.
Additionally and preferably, the surfactant may be a branched alkyl sulfate,
branched alkyl
alkoxylate, or branched alkyl alkoxylate sulfate. These surfactants are
further described in
WO 99/19434; WO 99/18929; WO 99119435; El' 1 023 042; WO 99!19448; EP 1 023
431; WO
97/39087; WO 97/39088; WO 97!39091; WO 98123712; Wc:) 97!38972; WO 97/39089and
WO
~ 5 97/39090. Mixtures of these branched surfactants with conventional linear
surfactants are also
suitable for use in the present compositions.
i!0
Additionally, the surfactant may be a modified alkylbenzene sulfonate
surfactants, or
MLAS. Suitable MLAS surfactants can be found in
WO 99/05243; WO 99/05242; W<J 99/05244; WO 99/0S/)82; WO 99/05084; WO
99/05241; WO
25 99107656; WO 00/23549 and WO 0012364$. Mixtures of these branched
surfactants with
conventional linear surfactants are also suitable for use in the present
compositions.
The anionic surfactants useful in the LDL of the present invention are
preferably selected
from the group consisting of, linear alkylbenzene sulfonate, alpha olefin
sulfonate, paraffin
sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate,
alkyl sulfonates, alkyl
alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, and
mixtures thereof. An
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WO 00/50549 PCT/US00/04185
effective amount, typically from about 0.5% to about 90%, preferably about 5%
to about 50%,
more preferably from about 10 to about 30%, by weight of anionic detersive
surfactant can be
used in the LDL compositions of the present invention.
When included therein, the laundry detergent compositions of the present
invention
5 typically comprise from about 0.1% to about 50%, preferably from about 1% to
about 40% by
weight of an anionic surfactant.
(2) Nonionic Co-surfactants:
Nonlimiting examples of nonionic co-surfactants useful herein typically at
levels from
about 0.1 % to about 50%, by weight include the alkoxylated alcohols (AE's)
and alkyl phenols,
10 polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C 10-
C 1 g glycerol ethers,
and the like.
Examples of commercially available nonionic surfactants of this type include:
TergitolTM 15-S-9 (the condensation product of C 11-C 15 linear alcohol with 9
moles ethylene
oxide) and TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary
alcohol
with 6 moles ethylene oxide with a narrow molecular weight distribution), both
marketed by
Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C15
linear
alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation
product of C12-C13
linear alcohol with 3 moles of ethylene oxide), NeodolTM 45-7 (the
condensation product of
C14-C15 linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the
condensation
product of C 14-C 15 linear alcohol with 5 moles of ethylene oxide) marketed
by Shell Chemical
Company; KyroTM EOB (the condensation product of C 13-C 15 alcohol with 9
moles ethylene
oxide), marketed by The Procter & Gamble Company; and Genapol LA 030 or 050
(the
condensation product of C 12-C 14 alcohol with 3 or S moles of ethylene oxide)
marketed by
Hoechst. The preferred range of HLB in these AE nonionic surfactants is from 8-
17 and most
preferred from 8-14. Condensates with propylene oxide and butylene oxides may
also be used.
Another class of preferred nonionic co-surfactants for use herein are the
polyhydroxy
fatty acid amide surfactants of the formula.
R2-' i-N -Z
O R~
wherein R1 is H, or C1~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a
mixture thereof,
R2 is CS_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative thereof.
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Typical examples include the C 12-C 1 g and C 12-C 14 N-methylglucamides. See
U.S. 5,194,639
and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see
U.S. 5,489,393.
Also useful as a nonionic co-surfactant in the present invention are the
alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647,
Llenado, issued January
21, 1986.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about 10 to
about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2; t is from 0
to about 10, preferably 0; and x is from about 1.3 to about 10, preferably
from about 1.3 to about
3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably
derived from glucose.
To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed
first and there
reacted with glucose, or a source of glucose, to form the glucoside
(attachment at the 1-position).
The additional glycosyl units can then be attached between their 1-position
and the preceding
glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-
position. Compounds
of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075
996 and 0 094 118.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are
also suitable for use as the nonionic surfactant of the surfactant systems of
the present invention,
with the polyethylene oxide condensates being preferred. These compounds
include the
condensation products of alkyl phenols having an alkyl group containing from
about 6 to about
14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a
straight-chain or
branched-chain configuration with the alkylene oxide. In a preferred
embodiment, the ethylene
oxide is present in an amount equal to from about 2 to about 25 moles, more
preferably from
about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
Commercially available
nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF
Corporation;
and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas
Company.
These surfactants are commonly referred to as alkylphenol alkoxylates (e.g.,
alkyl phenol
ethoxylates).
The condensation products of ethylene oxide with a hydrophobic base formed by
the
condensation of propylene oxide with propylene glycol are also suitable for
use as the additional
nonionic surfactant in the present invention. The hydrophobic portion of these
compounds will
preferably have a molecular weight of from about 1500 to about 1800 and will
exhibit water
insolubility. The addition of polyoxyethylene moieties to this hydrophobic
portion tends to
CA 02362945 2003-03-06
12
increase the water solubility of the.molecule as a whole, and the liquid
character of the product is
retained up to the point where the polyoxycthylene content is about 50% of the
total weight of the
condensation product, which corresponds to condensation with up to about 40
moles of ethylene
oxide. Examples of compounds of this type znclude certain of the commercially-
available
PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the nonionic surfactant
system of the
present invention, are the condensation products of ethylene oxide with the
product resulting
from the reaction of propylene oxide and ethylenediamine. The hydrophobic
moiety of these
products consists of the reaction product of efhyienediamine and excess
propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000. This
hydrophobic moiety is
condensed with ethylene oxide to the extent that the condensation product
contains from about
40% to about 80% by weight of polyoxyethylene and has a molecular weight of
from about 5,000
to about 11,000. Examples of this type of nonionic surfactant include certain
of the commercially
available TetronicTM compounds, marketed by BASF.
Alsu preferred nonionics are amine oxide surfactants. The compositions of the
present
invention may comprise amine oxide in accordance with the general formula I:
R 1 (EO)x{PO~,(BO)zN(O)(CH2R )2.qH2O {)).
In general, it can be seen that the structure (f) provides one long-chain
moiety
R1(EO)X(PO~,(BO)z and two short chain moieties, CH2R'. R' is preferably
selected from
hydrogen, methyl and -CH20H. In general R ~ is a primary or branched
hydrocarbyl moiety
which can be saturated or unsaturated, preferably, R l is a primary alkyl
moiety. When x+y+z =
0, R1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
When x+y+z is
different from 0, R1 may be somewhat longer, having a chainlength in the range
C12-C24~ The
general formula also encompasses amine oxides wherein x+y+z = 0, RI = Cg-Cl g,
R' = H and q
= 0-2, preferably 2. These amine oxides are illustrated by C12-14
alkyldimethyl amine oxide,
hexadecyl dimethyiamine oxide, octadecylamine oxide and their hydrates,
especially the
dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594.
The invention also encompasses amine oxides wherein x+y+2 is different from
zero,
specifically x+y+z is from about 1 to about 10, Rl is a primary allryl group
containing 8 to about
24 carbons, preferably from about 12 to about 16 carbon atoms; in these
embodiments y + z is
preferably 0 and x is preferably from about 1 to about 6, mare preferably from
about 2 to about 4;
EU represents ethyleneoxy; PO represents propyleneoxy; and BC) represents
butyleneoxy. Such
amine oxides can be prepared by conventional synthetic methods, e.g., by the
reaction of
CA 02362945 2001-08-13
WO 00/50549 PCT/US00/04185
13
alkylethoxysulfates with dimethylamine followed by oxidation of the
ethoxylated amine with
hydrogen peroxide.
Highly preferred amine oxides herein are solutions at ambient temperature.
Amine oxides
suitable for use herein are made commercially by a number of suppliers,
including Akzo Chemie,
Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-
Othmer review
article for alternate amine oxide manufacturers.
Whereas in certain of the preferred embodiments R' is H, there is some
latitude with
respect to having R' slightly larger than. H. Specifically, the invention
further encompasses
embodiments wherein R' is CH20H, such as hexadecylbis(2-hydroxyethyl)amine
oxide,
tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide
and oleylbis(2-
hydroxyethyl)amine oxide, dodecyldimethylamine oxide dihydrate.
Preferred amines for use herein include amines according to the formula:
Rl-X-(CH2)n-N(R3)(R4)
wherein Rl is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging group which is
selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are
individually
selected from H, C1-C4 alkyl, or (CH2-CH2-O(RS)) wherein RS is H or methyl.
These preferred amines include the following:
Rl-(CH2)2-NH2
Rl-O-(CH2)3-NH2
Rl-C(O)-NH-(CH2)3-N(CH3)2
Rl-N[CH2-CH(OH)-RS]2
wherein Rl is a C6-C12 alkyl group and RS is H or CH3.
In a highly preferred embodiment, the amine is described by the formula:
R1-C(O)-~-(CH2)3-N(CH3)2
wherein Rl is Cg-C12 alkyl.
Particularly preferred amines include those selected from the group consisting
of octyl
amine, hexyl amine, decyl amine, dodecyl amine, Cg-C12 bis(hydroxyethyl)amine,
Cg-C12
bis(hydroxyisopropyl)amine, and Cg-C12 amido-propyl dimethyl amine, and
mixtures.
(3) Cationic Co-surfactants:
Nonlimiting examples of cationic co-surfactants useful herein typically at
levels from
about 0.1% to about 50%, by weight include the choline ester-type quats and
alkoxylated
quaternary ammonium (AQA) surfactant compounds, and the like. Most preferred
for aqueous
liquid compositions herein are soluble cationic co-surfactants which do not
readily hydrolyze in
the product.
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WO 00/50549 PCT/US00/04185
14
Cationic co-surfactants useful as a component of the surfactant system is a
cationic
choline ester-type quat surfactant which are preferably water dispersible
compounds having
surfactant properties and comprise at least one ester (i.e. -COO-) linkage and
at least one
cationically charged group. Suitable cationic ester surfactants, including
choline ester
surfactants, have for example been disclosed in U.S. Patents Nos. 4,228,042,
4,239,660 and
4,260,529.
Cationic ester surfactants include those having the formula:
Rs R2
RtLOL(C~nO~b~ a (~u (CH2)m (~v (CH2)t N ~ R3 M
Ra
wherein R1 is a CS-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-
.N+(R6R~Rg)(CH2)s; X and Y, independently, are selected from the group
consisting of COOS.
0C0, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y
is a
COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R~ and Rg are
independently
selected from the group consisting of alkyl, alkenyl, hydroxyalkyl,
hydroxyalkenyl and alkaryl
groups having from 1 to 4 carbon atoms; and RS is independently H or a C1-C3
alkyl group;
wherein the values of m, n, s and t independently lie in the range of from 0
to 8, the value of b
lies in the range from 0 to 20, and the values of a, a and v independently are
either 0 or 1 with the
proviso that at least one of a or v must be l; and wherein M is a counter
anion.
Preferably R2, R3 and R4 are independently selected from CH3 and -CH2CH20H.
Preferably M is selected from the group consisting of halide, methyl sulfate,
sulfate, and
nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
Preferred water dispersible cationic ester surfactants are the choline esters
having the
formula:
O CH3
R1COCH2CH2N ~ CH3 M
CH3
wherein R1 is a C11-C19 linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl
choline ester
quaternary methylammonium halides (R1=C1~ alkyl), palmitoyl choline ester
quaternary
methylammonium halides (R1=C15 alkyl), myristoyl choline ester quaternary
methylammonium
halides (R1=C13 alkyl), lauroyl choline ester quaternary methylammonium
halides (R1=C11
alkyl), cocoyl choline ester quaternary methylammonium halides (Rl=C11-C13
alkyl), tallowyl
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WO 00/50549 PCT/US00/04185
choline ester quaternary methylammonium halides (Rl=C15-C17 alkyl), and any
mixtures
thereof.
The particularly preferred choline esters, given above, may be prepared by the
direct
esterification of a fatty acid of the desired chain length with
dimethylaminoethanol, in the
5 presence of an acid catalyst. The reaction product is then quaternized with
a methyl halide,
preferably in the presence of a solvent such as ethanol, propylene glycol or
preferably a fatty
alcohol ethoxylate such as C l0-C 1 g fatty alcohol ethoxylate having a degree
of ethoxylation of
from 3 to 50 ethoxy groups per mole forming the desired cationic material.
They may also be
prepared by the direct esterification of a long chain fatty acid of the
desired chain length together
10 with 2-haloethanol, in the presence of an acid catalyst material. The
reaction product is then
quaternized with trimethylamine, forming the desired cationic material.
In a preferred aspect these cationic ester surfactant are hydrolysable under
the conditions
of a laundry wash method.
Cationic co-surfactants useful herein also include alkoxylated quaternary
ammonium
15 (AQA) surfactant compounds (referred to hereinafter as "AQA compounds")
having the formula:
Rl /ApR3
I \N+ X -
~A,qR 4
wherein Rl is an alkyl or alkenyl moiety containing from about 8 to about 18
carbon atoms,
preferably 10 to about 16 carbon atoms, most preferably from about 10 to about
14 carbon atoms;
R2 is an alkyl group containing from one to three carbon atoms, preferably
methyl; R3 and R4
can vary independently and are selected from hydrogen (preferred), methyl and
ethyl; X- is an
anion such as chloride, bromide, methylsulfate, sulfate, or the like,
sufficient to provide electrical
neutrality. A and A' can vary independently and are each selected from Cl-C4
alkoxy, especially
ethoxy (i.e., -CH2CH20-), propoxy, butoxy and mixed ethoxy/propoxy; p is from
0 to about 30,
preferably 1 to about 4 and q is from 0 to about 30, preferably 1 to about 4,
and most preferably
to about 4; preferably both p and q are 1. See also: EP 2,084, published May
30, 1979, by The
Procter & Gamble Company, which describes cationic co-surfactants of this type
which are also
useful herein..
The levels of the AQA surfactants used to prepare finished laundry detergent
compositions typically xange from about 0.1% to about 5%, preferably from
about 0.45% to
about 2.5%, by weight.
CA 02362945 2003-03-06
16
Heavy duty liquid detergent compositions herein, especially those designed for
fabric
laundering, may also comprise a non-aqueous carrier medium as described in
more detail
hereinafter.
SHAMPOO COMPOSTTIONS:
The shampoo compositions of the present invention typically can comprise the
following
ingredients, components, or limitations described herein. As used herein,
"water soluble" refers
to any material that is sufficiently soluble in water to form a substantially
clear solution to the
naked eye at a concentration of 0.1% in water, i.e. distilled or equivalent,
at 25°C.
The shampoo compositions of the present invention contain a shampoo
composition
adjunct ingredient which is preferably selected from anti-dandruff agents
(preferably platelet
pyridinethione salt crystals, sulfur, octopirox, selenium sulfide,
ketoconazole and pyridinethione
salts), co-surfactants (preferably selected from anionic surfactant, nonionic
surfactant, cationic
surfactant, amphoteric surfactant. zwitterionic surfactants, and mixtures
thereof), silicone hair
conditioning agent, polyalkylene glycols, suspending agent, water, water
soluble cationic
polymeric conditioning agents, hydrocarbon conditioning agents, foam boosters,
preservatives,
thickeners, cosurfactants, dyes, perfumes, solvents, stylrng polymers, anti-
static agents,
deposition polymers, styling polymers and solvent, dispersed phase polymers,
non-volatile
hydrocarbons conditioning agents, silicone conditioning agents, suspending
agent, cationic
spreading agents phase separation initiators and pediculocides and mixtures
thereof. These and
other suitable materials for incorporation into the shampoo compositions of
the present invention
can be found in Wp 99i 18929 and EP 1 U23 0~~2.
1 DL compositions
The compositions of the present invention can also be in the form of LDL
compositions.
These LDL compositions include additives typically used in LDL formulations,
such as diamines,
divalent ions, suds boosting polymers, soil release polymers, polymeric
dispersants,
polysaccharides, abrasives, bactericides, tarnish inhibitors, builders,
enzymes, dyes, perfumes,
thickeners, antioxidants, processing aids, suds boosters, buffers, antifungal
or mildew control
agents, insect repeilants, anti-corrosive aids, and chelants.
3(1 Diamines - Since the habits and practices of the users of detergent
compositions show
considerable variation, the composition will preferably contain at least about
0.1%, more
preferably at least about 0.2%, even more preferably, at least about
0.25°1°, even more preferably
still, at least about 0.5% by weight of said composition of diamine. The
composition will also
preferably contain no more than about 15%, more preferably no more than about
10%, even more
CA 02362945 2001-08-13
WO 00/50549 PCT/US00/04185
17
preferably, no more than about 6%, even more preferably, no more than about
5%, even more
preferably still, no more than about 1.5% by weight of said composition of
diamine.
It is further preferred. that the compositions of the present invention be
"malodor" free.
That is, that the odor of the headspace does not generate a negative olfactory
response from the
consumer.
Preferred organic diamines are those in which pKl and pK2 are in the range of
about 8.0
to about 11.5, preferably in the range of about 8.4 to about 11, even more
preferably from about
8.6 to about 10.75. Preferred materials for performance and supply
considerations are 1,3-
bis(methylamine)-cyclohexane, 1,3 propane diamine (pKl=10.5; pK2=8.8), 1,6
hexane diamine
(pKl=11; pK2=10), 1,3 pentane diamine (Dytek EP) (pKl=10.5; pK2=8.9), 2-methyl
1,5 pentane
diamine (Dytek A) (pKl=11.2; pK2=10.0). Other preferred materials are the
primary/primary
diamines with alkylene spacers ranging from C4 to C8. In general, it is
believed that primary
diamines are preferred over secondary and tertiary diamines.
Definition of pKl and pK2 - As used herein, "pKal" and "pKa2" are quantities
of a type
collectively known to those skilled in the art as "pKa" pKa is used herein in
the same manner as
is commonly known to people skilled in the art of chemistry. Values referenced
herein can be
obtained from literature, such as from "Critical Stability Constants: Volume
2, Amines" by Smith
and Mantel, Plenum Press, NY and London, 1975. Additional information on pKa's
can be
obtained' from relevant company literature, such as information supplied by
Dupont, a supplier of
diamines. More detailed information of pKa's can be found in US Pat App No.
The diamines useful herein can be defined by the following structure:
R2wN.Cx~A~C~.N.K4
R3 ' Rs
wherein R2_5 are independently selected from H, methyl, -CH3CH2, and ethylene
oxides; CX and
C" are independently selected from methylene groups or branched alkyl groups
where x+y is from
about 3 to about 6; and A is optionally present and is selected from electron
donating or
withdrawing moieties chosen to adjust the diamine pKa's to the desired range.
If A is present,
then x and y must both be 1 or greater.
Alternatively the preferred diamines can be those with a molecular weight less
than or
equal to 400 g/mol. It is preferred that these diamines have the formula:
CA 02362945 2001-08-13
WO 00/50549 PCT/US00/04185
18
R6 R6
R6 ~N-X-N ~R
6
wherein each R6 is independently selected from the group consisting of
hydrogen, C 1-C4 linear
or branched alkyl, alkyleneoxy having the formula:
-(R~~)mR8
wherein R~ is C2-C4 linear or branched alkylene, and mixtures thereof; R8 is
hydrogen, C1-C4
alkyl, and mixtures thereof; m is from 1 to about 10; X is a unit selected
from:
i) C3-C 10 linear alkylene, C3-C 10 branched alkylene, C3-C 10 cyclic
alkylene, C3
C10 branched cyclic alkylene, an alkyleneoxyalkylene having the formula:
(R7p~7-
wherein R~ and m are the same as defined herein above;
ii) C3-C10 linear, C3-C10 branched linear, C3-C10 cyclic, C3-C10 branched
cyclic
alkylene, C6-C10 arylene, wherein said unit comprises one or more electron
donating or electron withdrawing moieties which provide said diamine with a
pKa greater than about 8; and
iii) mixtures of (i) and (ii)
provided said diamine has a pKa of at least about 8.
Examples of preferred diamines include the following:
dimethyl aminopropyl amine, 1,6-hexane diamine, 1,3 propane diamine, 2-methyl
1,5 pentane
diamine, 1,3-Pentanediamine, 1,3-diaminobutane, 1,2-bis(2-aminoethoxy)ethane,
Isophorone
diamine, 1,3-bis(methylamine)-cyclohexane and mixtures thereof.
Polymeric Suds Stabilizer - The compositions of the present invention may
optionally
contain a polymeric suds stabilizer. These polymeric suds stabilizers provide
extended suds
volume and suds duration without sacrificing the grease cutting ability of the
liquid detergent
compositions. These polymeric suds stabilizers are selected from:
i) homopolymers of (N,N-dialkylamino)alkyl acrylate esters having the
formula:
CA 02362945 2003-03-06
19
Rr
R
~N-~CHz)n'U~O
R
wherein each R is independently hydrogen, CI-C8 alkyl, and mixtures thereof,
R'
is hydrogen, CI-C6 alkyl, and mixtures thereof, n is from 2 to about 6; and
ii) copolymers of (i) and
Ra
HO O
wherein R' is hydrogen, Cl-C6 alkyl, and mixtures thereof, provided that the
ratio of (ii) to (i) is
from about 2 to 1 to about 1 to 2; The molecular weight of the polymeric suds
boosters,
determined via conventional gel permeation chromatography, is from about 1,000
to about
2,000,000, preferably from about 5,000 to about 1,000,000, more preferably
from about 10,000 to
about 750,000, more preferably from about 20,000 to about 500,000, even more
preferably from
about 35,000 to about 200,000. The polymeric suds stabilizer can optionally be
present in the
form of a salt, either an inorganic or organic salt, for example the citrate,
sulfate, or nitrate salt of
(N,N-dimethylamino)alkyl acrylate ester.
One preferred polymeric suds stabilizer is (N,N-dimethylamino)alkyl acryiate
esters,
1.5 namely
CH3
CH~'~~O
When present in the compositions, the polymeric suds booster may be present in
the
composition from about 0.01% to about 15%, preferably from about 0.05% to
about 10%, more
preferably from about 0.1% to about 5°,~0, by weight.
Other suitable polymeric suds stabilizers, including protenacious suds
stabilizers and
zwitterionic suds stabilizers, can be found in
WU 99/27058; WU 99/27054.; '~VU 99/27053 and WO 99/271>57.
t
CA 02362945 2003-03-06
Also suitable are the cationic copolymer stabilizers, which can be found
in US Patent 4454060.
Enzymes - Detergent compositions of the present invention may further comprise
one or
wore enzymes which provide cleaning performance benefits. Said enzymes include
enzymes
5 selected from eellulases, hemicellulases, peroxidases, proteases, gluco-
amylases, amylases,
lipases, cutinases, pectinases, xylanases, reductases, oxidases,
phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, f3-glucanases,
arabinosidases or
mixtures thereof. A preferred combination is a detergent composition having a
cocktail of
conventional applicable enzymes like protease, amylase, lipase, cutinase
andlor cellulase.
10 Enzymes when present in the compositions, at from about 0.0001°n to
about 5% of active enzyme
by weight of the detergent composition.
Proteolytic Enzyme - The proteolytic enzyme can be of animal, vegetable or
microorganism (preferred) origin. The proteases for use in the detergent
compositions herein
include (but are not limited to) trypsin, subtilisin, chymotrypsin and
elastase-type proteases.
15 Preferred for use herein are subtilisin-type proteolytic enzymes.
Particularly preferred is
bacterial serine proteolytic enzyme obtained from Bacillus subtilis and/or Ba
' lus licheniformis.
Suitable proteohrtic enzymes include Novo Industri A;'S Alcalase~ (preferred),
Espcrase~~
Savinase~ (Copenhagen, Denmark), Gist-brocades' Maxatase~, Maxacal~ and
Maxapem 15~
(protein engineered Maxacal~) (Delft, Netherlands), and subtilisin HPN and
BPN'(preferred),
20 which are commercially available. Prefen-ed proteolytic enzymes are also
modified bacterial
serine proteases, such as those made by Genencor International, Inc. (San
Francisco, California)
which are described in Ewopean Patent 251,446H, granted T)eccmber 28, 1994
(particularly
pages 17, 24 and 98) and which are also called herein "Protease B". U.S.
Patent 5,030,378,
Venegas, issued July 9, 1991, refers to a modified bacterial serine
proteolytic enzyme (Genencor
International) which is called "Protease A" herein (same as BPN'). In
particular see columns 2
and 3 of U.S. Patent 5,030,378 for a complete description, including amino
sequence, of Protease
A and its variants. Other proteases arc sold under the tradenames: Primase,
Durazym, Opticlean
and Optimase. Preferred proteolytic enzymes, then, are selected from the group
consisting of
Alcalase '~ (Novo Industri A/S), HPN', Protease A and Protease B (Genencor),
and mixtures
3i7 thereof. Protease B is most preferred.
Of particular interest for use herein are the proteases described in U.S.
Patent No.
5,470,733.
Also proteases described in W() 9~/1059I . can be
included in the detergent composition of the invention.
CA 02362945 2003-03-06
z1
Another preferred protease, referred to as "Protease T)" is a carbonyl
hydrolase variant
having an amino acid sequence not found in nature, which is derived from a
precursor carbonyl
hydrolase by substituting a~ different amino acid for a plurality of amino
acid residues at a
position in said carbonyl hydrolase equivalent to position +7ti, preferably
also in combination
with one or more amino acid residue positions equivalent to those selected
from the group
consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128,
+135, +156,
+166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or
+274
according to the numbering of Bacillus amyloliquefaciens subtilisin, as
described in WO
95/10615 published April 20, 1995 by Genencor International : lJS 5,679,630
and LJS 6,01.7,871.
~ '
Useful proteases are also described in PCT publications: WO 95/30010 published
November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published
November 9,
1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995
by The
Procter & Gamble Company.
Protease enzyme may be incorporated into the compositions in accordance with
the
invention at a level of from 0.0001% to 2°.~o active enzyme by weight
of the composition.
Amylase - Amylases (a andlor 13) can be included for removal of carbohydrate-
based
stains. Suitable amylases are 'Termamyl~ (Novo Nordisk), >~ungamyl~ and BAN~
(Novo
Nordisk). The enzymes may be of any suitable origin, such as vegetable,
animal, bacterial, fungal
~'0 and yeast origin. Amylase enzymes are normally incorporated in the
detergent composition at
levels from 0.0001% to 2%, preferably from about 0.0001 % to about 0.5%, more
preferably from
about 0.0005% to about O.lp/°, even more preferably from about 0.001%
to about 0.05% of active
enzyme by weight of the detergent composition.
Amylase enzymes also include those described in W095/26397 and WQ 96/23873
~5
One suitable amylase enzyme is NATALASE4~ available from Novo Nordisk.
Other amylases suitable herein include, for example, a-amylases described in
GB
1,296,839 to Novo; RAPII7ASE~', international Bio-Synthetics, Inc. and
TERMAMYL~, Novo.
FUNGAMYL~ from Novo is especially useful.
30 Particularly preferred amylases herein include amylase variants having
additional
modification in the immediate parent as described in WO 9510603 A and are
available from the
assignee, Novo, as DLTRANIYL~. Other particularly preferred oxidative
stability enhanced
amylase include those described in WO 9418314 to Genencor International and WO
9402597 to
Novo. Any other oxidative stability-enhanced amylase can be used, for example
as derived by
CA 02362945 2003-03-06
22
site-directed mutagenesis from lc~own chimeric, hybrid or simple mutant parent
forms of
available amylases. Other preferred enzyme modifications are accessible. See
WO 9509909 A to
Novo.
Various carbohydrase en~rnes which impart antimicrobial activity may also be
included
in the present invention. Such enzymes include endoglycosidase, Type II
endoglycosidase and
glucosidase as disclosed in U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843
and 5,356,803 .
Of course, other enzymes having
antimicrobial activifiy may be employed as well including paroxidases,
oxidases and various other
enzymes.
It is also possible to include an enzyme stabilization system into the
compositions of the
present invention when any enzyme is present in the composition.
Various carbohydrase enzymes which impart antimicrobial activity may also be
included
in the present invention. Such enzymes include endoglycosidase, Type II
endoglycosidase and
glucosidase as disclosed in U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843
and 5,356,803 .
Of course, other enzymes having
antimicrobial activity may be employed as well including peroxidases, oxidases
and various other
enzymes.
It is also possible to include an enzyme stabilization system into the
compositions of the
present invention when any enzyme is present in the composition.
Peroxidase enzymes can be used in combination with oxygen sources, e.g.,
percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are typically used for
"solution bleaching,"
i.e. to prevent transfer of dyes or pigments removed from substrates during
wash operations to
other substrates in the wash solution. Peroxidase enzymes are lmown in the
art, and include, for
example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro-
and bromo-
peroxidase. Peroxidase-containing detergent compositions are disclosed, for
example, in PCT
lntemational Application WO 89/099813, published October 19, 1989, by O. Kirk,
assigned to
Novo Industries A/S. The present invention encompasses peroxidase-free
automatic dishwashing
composition embodiments.
A wide range of enzyme materials and means for their incorporation into
synthetic
detergent compositions are also disclosed in U.S. Patent 3,553,139, issued
January 5, 1971 to
McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place
et al, issued July
18, 1978, and in U,S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzymes
for use in
detergents can be stabilized by various techniques. Enzyme stabilization
techniques are disclosed
and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et
al, and European
CA 02362945 2003-03-06
23
Patent EP 0 199 40.
Enzyme stabilization systems are also described, for example, in IJ.S. Patent
3,519,570.
The enzymes may be incorporated into detergent compositions herein in the form
of
suspensions, "marumes" or "prills". Another suitable type of enzyme comprises
those in the form
of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by
Novo Nordisk under
the tradename "SL" or the microencapsulated enzymes marketed by Novo Nordisk
under the
tradename "LDP."
Enzymes added to the compositions herein in the farm of conventional enzyme
prills are
especially preferred for use herein. Such prills will generally range in size
from about 100 to
1,000 microns, more preferably from about 200 to 800 microns and will be
suspended throughout
the non-aqueous liquid phase of the composition. Prills in the compositions of
the present
invention have been found, in ;,omparison with other enzyme forms, to exhibit
especially
desirable enzyme stability in terms of retention of enzymatic activity over
time. Thus,
1 a compositions which utilize enzyme grills need not contain conventional
enzyme stabilizing such
as must frequently be used when enzymes are incorporated into aqueous liquid
detergents.
If employed, enzymes will normally be incorporated into the non-aqueous liquid
compositions herein at levels sufficient to provide up to about l0 mg by
weight, more typically
from about 0.01 mg to about 5 mg, of active enzyme per gram of the
composition. Stated
2(1 otherwise, the non-aqueous liquid detergent compositions herein will
typically comprise from
about 0.001% to 5%, preferably from about 0.01% to 1°l° by
weight, of a commercial enzyme
preparation, Protease enzymes, for example, are usually present in such
commercial preparations
at levels sufficient to provide from 0.00.5 to 0.1 Anson units (Atl) of
activity per gram of
composition.
~vme Stabilizfne stem - The enzyme-containing compositions herein may
optionally
also comprise from about 0.001% to about 10%, preferably from about 0.005% to
about 8%,
most preferably from about 0.01% to about 6%, by weight of an enzyme
stabilizing system. The
enzyme stabilizing system can be any stabilizing system which is compatible
with the detersive
enzyme. Such a system may be inherently provided by other farrnulation
actives, or be added
30 separately, e.g., by the formulator or by a manufacturer of detergent-ready
enzymes. Such
stabilizing systems can, for example, comprise calcium ion, boric acid,
propylene glycol, short
chain carboxylic acids, boronic acids, and mixritres thereof, and are designed
to address different
stabilization problems depending on the type and physical fc>rrn of the
detergent composition.
CA 02362945 2001-08-13
WO 00/50549 PCT/iJS00/04185
24
Perfumes - Perfumes and perfumery ingredients useful in the present
compositions and
processes comprise a wide variety of natural and synthetic chemical
ingredients, including, but
not limited to, aldehydes, ketones, esters, and the like. Also included are
various natural extracts
and essences which can comprise complex mixtures of ingredients, such as
orange oil, lemon oil,
rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil,
pine oil, cedar, and
the like. Finished perfumes can comprise extremely complex mixtures of such
ingredients.
Finished perfumes typically comprise from about 0.01% to about 2%, by weight,
of the detergent
compositions herein, and individual perfumery ingredients can comprise from
about 0.0001% to
about 90% of a finished perfume composition.
Chelating Agents - The detergent compositions herein may also optionally
contain one or
more iron and/or manganese chelating agents. Such chelating agents can be
selected from the
group consisting of amino carboxylates, amino phosphonates, polyfunctionally-
substituted
aromatic chelating agents and mixtures therein, all as hereinafter defined.
Without intending to
be bound by theory, it is believed that the benefit of these materials is due
in part to their
exceptional ability to remove iron and manganese ions from washing solutions
by formation of
soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
tri-acetates,
ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates,
diethylenetriamine-
pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted
ammonium salts
therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of
the invention when at lease low levels of total phosphorus are permitted in
detergent
compositions, and include ethylenediaminetetrakis (methylenephosphonates) as
DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups
with more than about
6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions
herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
Preferred compounds
of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-
3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November 3, 1987,
to Hartman and Perkins.
CA 02362945 2003-03-06
The compositions herein may also contain water-soluble methyl glycine diacetic
acid
(MGDA) salts {or acid form) as a chelant or co-builder. Similarly, the so
called "weak" builders
such as citrate can also be used as chelating agents.
If utilized, these chelating agents will generally comprise from about 0.1% to
about IS%
5 by weight of the detergent compositions herein. Mare preferably, if
utilized, the chelating agents
will comprise from about 0. I % to about 3.()°!° by weight of
such compositions.
Composition H
The compositions of the invention gill be subjected to acidic stresses created
by food soils
when put to use, i.e., diluted and applied to soiled dishes. If a composition
with a pH greater than
10 7 is to be more effective, it preferably should contain a buffering agent
capable of providing a
generally more alkaline pH in the composition and in dilute solutions, i.e.,
about 0.1% to 0.4% by
weight aqueous solution, of the composition. 'fhe pKa value of this buffering
agent should be
about 0.5 to 1.0 pH units below the desired pH value of the composition
(determined as described
above). Preferably, the pKa of fhe buffering agent should be from about 7 to
about 10. Under
15 these conditions the buffering agent mast effectively controls the pH while
using the least amount
thereof.
The buffering agent may be an active detergent in its own right, or it may be
a low
molecular weight, organic or inorganic material that is used in this
composition solely for
maintaining an alkaline pH. Pre:erred buffering agents f'or compositions of
this invention are
20 nitrogen-containing materials. Some examples are ammo acids such as lysine
or lower alcohol
amines like mono-, dl-, and tri-ethanolamine. Other preferred nitrogen-
containing buffering
agents are Tri(hydroxymethyl)amino methane (HOCH2)3CNH3 (TRIS), 2-amino-2-
ethyl-1,3-
propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol,
disodium glutamate,
N-methyl diethanolamide, 1,3-diamino-propanol N>N'-tetra-methyl-1,3-diarnino-2-
propanol, N,N-
21i bis(2-hydroxyethyl)glycine (bicine) and N-Iris (hydraxymethyl)methyl
glycine (tricine).
Mixtures of any of the above are also acceptable. Useful inorganic
bufftrslalkalinity sources
include the alkali metal carbonates and alkali metal phosphates, e.g., sodium
carbonate, sodium
polyphosphate. For additional buffers see McCutcheon's EMULSIFIERS AND
DETERGENTS,
North American Edition, 1997, MeCutcheon Division, MC Put~lishing Company Kirk
and WO
95/07971.
The buffering agent, if used, is present in the compositions of the invention
herein at a level
of from about 0.1% to 15%, preferably from about 1 % to 10%, most preferably
from about 2% to
8%, by weight of the composition.
Bleaching ~;~pounds
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26
Bleaching Agents and Bleach Activators The granular detergent compositions
herein preferably
further contain a bleach and/or a bleach activators. The granular bleaching
detergent
compositions herein will contain a bleach and a bleach activator. Bleaches
agents will typically,
when present, be at levels of from about 1% to about 30%, more typically from
about 5% to
about 20%, of the detergent composition, especially for fabric laundering. If
present, the amount
of bleach activators will typically be from about 0.1% to about 60%, more
typically from about
0.5% to about 40% of the bleaching composition comprising the bleaching agent-
plus-bleach
acrivator.
The bleaches used herein can be any of the bleaches useful for detergent
compositions in
textile cleaning, hard surface 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 bleaches 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-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such
bleaches are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20,
1984, U.S. Patent
Application 740,446, Burns et al, filed June 3, 1985, European Patent
Application 0,133,354,
Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et
al, issued
November 1, 1983. Highly preferred bleaches also include 6-nonylamino-6-
oxoperoxycaproic
acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums et
al.
Peroxygen bleaches 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 about 500 micrometers to about 1,000 micrometers, not more
than about 10%
by weight of said particles being smaller than about 200 micrometers and not
more than about
10% by weight of said particles being larger than about 1,250 micrometers.
Optionally, the
percarbonate can be coated with silicate, borate or water-soluble surfactants.
Percarbonate is
available from various commercial sources such as FMC, Solway and Tokai Denka.
Mixtures of bleaches can also be used.
Peroxygen bleaches, 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
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27
washing process) of the peroxy acid corresponding to the bleach activator.
Various nonlimiting
examples of activators are disclosed in U.S. Patent 4,915,854, issued April
10, 1990 to Mao et al,
and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) 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.
Bleach Activators
Bleach activators useful herein include amides, imides, esters and anhydrides.
Commonly at least one substituted or unsubstituted acyl moiety is present,
covalently
connected to a leaving group as in the structure R-C(O)-L. In one preferred
mode of use,
bleach activators are combined with a source of hydrogen peroxide, such as the
perborates or
percarbonates, in a single product. Conveniently, the single product leads to
in situ production
in aqueous solution (i.e., during the washing process) of the percarboxylic
acid corresponding
to the bleach activator. The product itself can be hydrous, for example a
powder, provided that
water is controlled in amount and mobility such that storage stability is
acceptable.
Alternately, the product can be an anhydrous solid or liquid. In another mode,
the bleach
activator or oxygen bleach is incorporated in a pretreatment product, such as
a stain stick;
soiled, pretreated substrates can then be exposed to further treatments, for
example of a
hydrogen peroxide source. With respect to the above bleach activator structure
RC(O)L, the
atom in' the leaving group connecting to the peracid-forming acyl moiety R(C)O-
is most
typically O or N. Bleach activators can have non-charged, positively or
negatively charged
peracid-forming moieties and/or noncharged, positively or negatively charged
leaving groups.
One or more peracid-forming moieties or leaving-groups can be present. See,
for example,
U.S. 5,595,967, U.S. 5,561,235, U.S. 5,560,862 or the bis-(peroxy-carbonic)
system of U.S.
5,534,179. Mixtures of suitable bleach activators can also be used. Bleach
activators can be
substituted with electron-donating or electron-releasing moieties either in
the leaving-group or
in the peracid-forming moiety or moieties, changing their reactivity and
making them more or
less suited to particular pH or wash conditions. For example, electron-
withdrawing groups
such as N02 improve the efficacy of bleach activators intended for use in mild-
pH (e.g., from
about 7.5- to about 9.5) wash conditions.
An extensive and exhaustive disclosure of suitable bleach activators and
suitable leaving
groups, as well as how to determine suitable activators, can be found in US
Patents 5,686,014
and 5,622,646.
Cationic bleach activators include quaternary carbamate-, quaternary carbonate-
,
quaternary ester- and quaternary amide- types, delivering a range of cationic
peroxyimidic,
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WO 00/50549 PCT/US00/04185
28
peroxycarbonic or peroxycarboxylic acids to the wash. An analogous but non-
cationic palette
of bleach activators is available when quaternary derivatives are not desired.
In more detail,
cationic activators include quaternary ammonium-substituted activators of WO
96-06915, U.S.
4,751,015 and 4,397,757, EP-A-284292, EP-A-331,229 and EP-A-03520. Also useful
are
cationic nitriles as disclosed in EP-A-303,520 and in European Patent
Specification 458,396
and 464,880. Other nitrite types have electron-withdrawing substituents as
described in U.S.
5,591,378.
Other bleach activator disclosures include GB 836,988; 864,798; 907,356;
1,003,310
and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-
0120591; U.S.
Pat. Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393, and the
phenol sulfonate
ester of alkanoyl aminoacids disclosed in U.S. 5,523,434. Suitable bleach
activators include
any acetylated diamine types, whether hydrophilic or hydrophobic in character.
Of the above classes of bleach precursors, preferred classes include the
esters, including
acyl phenol sulfonates, acyl alkyl phenol sulfonates or acyl
oxybenzenesulfonates (0B5 leaving
group); the acyl-amides; and the quaternary ammonium substituted peroxyacid
precursors
including the cationic nitrites.
Preferred bleach activators include N,N,NN'-tetraacetyl ethylene diamine
(TAED) or any
of its close relatives including the triacetyl or other unsymmetrical
derivatives. TAED and the
acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose
are preferred
hydrophilic bleach activators. Depending on the application, acetyl triethyl
citrate, a liquid, also
has some utility, as does phenyl benzoate.
Preferred hydrophobic bleach activators include sodium nonanoyloxybenzene
sulfonate
(HOBS or SNOBS), N-(alkanoyl)aminoalkanoyloxy benzene sulfonates, such as 4-[N-
(nonanoyl)aminohexanoyloxy]-benzene sulfonate or (NACA-OBS) as described in US
Patent
5,534,642 and in EPA 0 355 384 A1, substituted amide types described in detail
hereinafter, such
as activators related to NAPAA, and activators related to certain imidoperacid
bleaches, for
example as described in U.S. Patent 5,061,807, issued October 29, 1991 and
assigned to Hoechst
Aktiengesellschaft of Frankfurt, Germany and Japanese Laid-Open Patent
Application (Kokai)
No. 4-28799.
Another group of peracids and bleach activators herein are those derivable
from acyclic
imidoperoxycarboxylic acids and salts thereof, See US Patent 5415796, and
cyclic
imidoperoxycarboxylic acids and salts thereof, see US patents 5,061,807,
5,132,431, 5,6542,69,
5,246,620, 5,419,864 and 5,438,147.
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WO 00/50549 PCT/US00/04185
29
Other suitable bleach activators include sodium-4-benzoyloxy benzene sulfonate
(SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-
benzoyloxy benzoate (SPCC); trimethyl ammonium toluyloxy-benzene sulfonate; or
sodium
3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS).
Bleach activators may be used in an amount of up to 20%, preferably from 0.1-
10% by
weight, of the composition, though higher levels, 40% or more, are acceptable,
for example in
highly concentrated bleach additive product forms or forms intended for
appliance automated
dosing.
Highly preferred bleach activators useful herein are amide-substituted and an
extensive
and exhaustive disclosure of these activators can be found in US Patents
5,686,014 and
5,622,646.
Other useful activators, disclosed in U.S. 4,966,723, are benzoxazin-type,
such as a
C6H4 ring to which is fused in the 1,2-positions a moiety --C(O)OC(R1)=N-. A
highly
preferred activator of the benzoxazin-type is:
O
II
I
~C
Depending on the activator and precise application, good bleaching results can
be
obtained from bleaching systems having with in-use pH of from about 6 to about
13,
preferably from about 9.0 to about 10.5. Typically, for example, activators
with electron
withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
Alkalis and buffering
agents can be used to secure such pH.
Acyl lactam activators are very useful herein, especially the acyl
caprolactams (see for
example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639). See also
U.S.
4,545,784 which discloses acyl caprolactams, including benzoyl caprolactam
adsorbed into
sodium perborate. In certain preferred embodiments of the invention, NOBS,
lactam activators,
imide activators or amide-functional activators, especially the more
hydrophobic derivatives,
are desirably combined with hydrophilic activators such as TAED, typically at
weight ratios of
hydrophobic activator : TAED in the range of 1:5 to 5:1, preferably about 1:1.
Other suitable
lactam activators are alpha-modified; see WO 96-22350 A1, July 25, 1996.
Lactam activators,
especially the more hydrophobic types, are desirably used in combination with
TAED,
typically at weight ratios of amido-derived or caprolactam activators : TAED
in the range of
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Wb 00/50549 PCT/US00/04185
1:5 to 5:1, preferably about 1:1. See also the bleach activators having cyclic
amidine leaving-
group disclosed in U.S. 5,552,556.
Nonlimiting examples of additional activators useful herein are to be found in
U.S.
4,915,854, U.S. 4,412,934 and 4,634,551. The hydrophobic activator
nonanoyloxybenzene
5 sulfonate (HOBS) and the hydrophilic tetraacetyl ethylene diamine (TAED)
activator are typical,
and mixtures thereof can also be used.
Additional activators useful herein include those of U.S. 5,545,349, which is
also
incorporated herein by reference.
Bleaches other than oxygen bleaching agents are also lrnown in the art and can
be utilized
10 herein. One type of non-oxygen bleaching agent of particular interest
includes photoactivated
bleaches such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.
Patent
4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent
compositions will typically
contain from about 0.025% to about 1.25%, by weight, of such bleaches,
especially sulfonate zinc
phthalocyanine.
15 Bleach Catalysts
The present invention compositions and methods utilize metal-containing bleach
catalysts that are effective for use in ADD compositions. Preferred are
manganese and cobalt-
containing bleach catalysts.
For examples of suitable bleach catalysts see U.S. Pat. Nos. 4,246,612,
5,804542,
20 5,798,326, 5,246,621, 4,430,243, 5,244,594, 5,597,936, 5,705,464,
4,810,410, 4,601,845,
5,194,416, 5,703,030, 4,728,455, 4,711,748, 4,626,373, 4,119,557, 5,114,606,
5,599,781,
5,703,034, 5,114,611, 4,430,243, 4,728,455, and 5,227,084; EP Pat. Nos.
408,131, 549,271,
384,503, 549,272, 224,952, and 306,089; DE Pat. No. 2,054,019; CA Pat No.
866,191.
Preferred are cobalt (III) catalysts having the formula:
25 Co[(NH3)nM'mB'bT'tQqPp) YY
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5
(preferably 4 or 5; most
preferably 5); M' represents a monodentate ligand; m is an integer from 0 to 5
(preferably 1 or 2;
most preferably 1); B' represents a bidentate ligand; b is an integer from 0
to 2; T' represents a
tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or l; P is
a pentadentate ligand; p is
30 0 or 1; and n + m + 2b + 3t + 4q + Sp = 6; Y is one or more appropriately
selected counteranions
present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3;
most preferably 2
when Y is a -1 charged anion), to obtain a charge-balanced salt, preferred Y
are selected from the
group consisting of chloride, iodide, I3-, formate, nitrate, nitrite, sulfate,
sulfite, citrate, acetate,
carbonate, bromide, PF6-, BF4-, B(Ph)4-, phosphate, phosphite, silicate,
tosylate,
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WO 00/50549 PCT/US00/04185
31
methanesulfonate, and combinations thereof [optionally, Y can be protonated if
more than one
anionic group exists in Y, e.g., HP042', HC03', H2P04', etc., and further, Y
may be selected
from the group consisting of non-traditional inorganic anions such as anionic
surfactants, e.g.,
linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS),
alkylethoxysulfonates (AES), etc:,
and/or anionic polymers, e.g., polyacrylates, polymethacrylates, etc.]; and
wherein further at least
one of the coordination sites attached to the cobalt is labile under automatic
dishwashing use
conditions and the remaining coordination sites stabilize the cobalt under
automatic dishwashing
conditions such that the reduction potential for cobalt (IIn to cobalt (In
under alkaline conditions
is less than about 0.4 volts (preferably less than about 0.2 volts) versus a
normal hydrogen
electrode.
Preferred cobalt catalysts of this type have the formula:
[C°~3)n(M~)m] Yy
wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M'
is a labile '
coordinating moiety, preferably selected from the group consisting of
chlorine, bromine,
hydroxide; water, and (when m is greater than 1) combinations thereof; m is an
integer from 1 to
3 (preferably 1 or 2; most preferably 1); m+n = 6; and Y is an appropriately
selected
counteranion present in a number y, which is an integer from 1 to 3
(preferably 2 to 3; most
preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride
salts having the formula [Co(NH3)SCl) Yy, and especially [Co(NH3)SCl]C12.
More preferred are the present invention compositions which utilize cobalt (~
bleach
catalysts having the formula:
[C°~3)n(M)m(B)b] TY
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or more ligands
coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1); B is a
ligand coordinated to the
cobalt by two sites; b is 0 or 1 (preferably 0), and when b=0, then m+n = 6,
and when b=1, then
m=0 and n=4; and T is one or more appropriately selected counteranions present
in a number y,
where y is an integer to obtain a charge-balanced salt (preferably y is 1 to
3; most preferably 2
when T is a -1 charged anion); and wherein further said catalyst has a base
hydrolysis rate
constant of less than 0.23 M'1 s'1 (25°C).
The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate
salts
having the formula [Co(NH3)SOAc] Ty, wherein OAc represents an acetate moiety,
and
especially cobalt pentaamine acetate chloride, [Co(NH3)SOAc)CI2; as well as
CA 02362945 2001-08-13
WO 00/50549 PCT/US00/04185
32
[Co(NH3)50Ac](OAc)2; [Co(NH3)SOAc](PF6)2; [Co(NH3)SOAc](504); [Co-
~3)SOAc](BF4)2; and [Co(NH3)SOAc](N03)2.
As a practical matter, and not by way of limitation, the cleaning compositions
and
cleaning processes herein can be adjusted to provide on the order of at least
one part per hundred
million of the active bleach catalyst species in the aqueous washing medium,
and will preferably
provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05
ppm to about 10
ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach
catalyst species in
the wash liquor. In order to obtain such levels in the wash liquor of an
automatic dishwashing
process, typical automatic dishwashing compositions herein will comprise from
about 0.0005%
to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach
catalyst by weight
of the cleaning compositions.
Builders - Builders can operate via a variety of mechanisms including forming
soluble or insoluble complexes with hardness ions, by ion exchange, and by
offering a surface
more favorable to the precipitation of hardness ions than are the surfaces of
articles to be cleaned.
Builder level can vary widely depending upon end use and physical form of the
composition. For
example, high-surfactant formulations can be unbuilt. The level of builder can
vary widely
depending upon the end use of the composition and its desired physical form.
The compositions
will comprise at least about 0.1 %, preferably from about 1 % to about 90%,
more preferably from
about 5% to about 80%, even more preferably from about 10% to about 40% by
weight, of the
detergent builder. Lower or higher levels of builder, however, are not
excluded.
Suitable builders herein can be selected from the group consisting of
phosphates and
polyphosphates, especially the sodium salts; carbonates, bicarbonates,
sesquicarbonates and
carbonate minerals other than sodium carbonate or sesquicarbonate; organic
mono-, di-, tri-, and
tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid,
sodium, potassium
or alkanolammonium salt form, as well as oligomeric or water-soluble low
molecular weight
polymer carboxylates including aliphatic and aromatic types; and phytic acid.
These may be
complemented by borates, e.g., for pH-buffering purposes, or by sulfates,
especially sodium
sulfate and any other fillers or Garners which may be important to the
engineering of stable
surfactant and/or builder-containing detergent compositions.
Builder mixtures, sometimes termed "builder systems" can be used and typically
comprise two or more conventional builders, optionally complemented by
chelants, pH-buffers or
fillers, though these latter materials are generally accounted for separately
when describing
quantities of materials herein. In terms of relative quantities of surfactant
and builder in the
present granular compositions, preferred builder systems are typically
formulated at a weight
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WO 00/50549 PCT/US00/04185
33
ratio of surfactant to builder of from about 60:1 to about 1:80. Certain
preferred granular
detergents have said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably
from 0.95:1.0 to
3.0:1Ø
P-containing detergent builders often preferred where permitted by legislation
include,
but are not limited to, the alkali metal, ammonium and alkanolammonium salts
of polyphosphates
exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-
phosphates; and
phosphonates. Where phosphorus-based builders can be used, 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 3,422,137) can also be used though such materials are more
commonly used in a
low-level mode as chelants or stabilizers.
Phosphate detergent builders for use in granular compositions are well known.
They
include, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts of
polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and
glassy polymeric
meta-phosphates). Phosphate builder sources are described in detail in Kirk
Othmer, 3rd Edition,
Vol. 17, pp. 426-472 and in "Advanced Inorganic Chemistry" by Cotton and
Wilkinson, pp. 394-
400 (John Wiley and Sons, Inc.; 1972).
Preferred levels of phosphate builders herein are from about 10% to about 75%,
preferably from about 15% to about 50%, of phosphate builder.
Phosphate builders can optionally be included in the compositions herein to
assist in
controlling mineral hardness. Builders are typically used in automatic
dishwashing to assist in
the removal of particulate soils.
Suitable carbonate builders include alkaline earth and alkali metal carbonates
as
disclosed in German Patent Application No. 2,321,001 published on November 15,
1973,
although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and
other carbonate
minerals such as trona or any convenient multiple salts of sodium carbonate
and calcium
carbonate such as those having the composition 2Na2C03.CaC03 when anhydrous,
and even
calcium carbonates including calcite, aragonite and vaterite, especially forms
having high surface
areas relative to compact calcite may be useful, for example as seeds. Various
grades and types
of sodium carbonate and sodium sesquicarbonate may be used, certain of which
are particularly
useful as carriers for other ingredients, especially detersive surfactants.
Suitable organic detergent builders include polycarboxylate compounds,
including water-
soluble nonsurfactant dicarboxylates and tricarboxylates. More typically
builder polycarboxylates
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34
have a plurality of carboxylate groups, preferably at least 3 carboxylates.
Carboxylate builders
can be formulated in acid, partially neutral, neutral or overbased form. When
in salt form, alkali
metals, such as sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Polycarboxylate builders include the ether polycarboxylates, such as
oxydisuccinate, see Berg,
U.S. 3,128,287, April 7, 1964, and Lamberti et al, U.S. 3,635,830, January 18,
1972; "TMS/TDS"
builders of U.S. 4,663,071, Bush et al, May 5, 1987; and other ether
carboxylates including
cyclic and alicyclic compounds, such as those described in U.S. Patents
3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other suitable builders are the ether hydroxypolycarboxylates, copolymers of
malefic
anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic
acid; 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 mellitic acid, succinic acid, oxydisuccinic acid, polymaleic
acid, benzene 1,3,5
tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrates, e.g., ciMc acid and soluble salts thereof are important carboxylate
builders due
to availability from renewable resources and biodegradability. Citrates can
also be used in the
present granular compositions, especially in combination with zeolite and/or
layered silicates.
Citrates can also be used in combination with zeolite, the hereafter mentioned
BRITESIL types,
and/or layered silicate builders. Oxydisuccinates are also useful in such
compositions and
combinations. Oxydisuccinates are also especially useful in such compositions
and
combinations.
Where permitted alkali metal phosphates such as sodium tripolyphosphates,
sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such
as ethane-1-
hydroxy-1,1-diphosphonate and other known phosphonates, e.g., those of U.S.
3,159,581;
3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have
desirable
antiscaling properties.
Certain detersive surfactants or their short-chain homologs also have a
builder action.
For unambiguous formula accounting purposes, when they have surfactant
capability, these
materials are summed up as detersive surfactants. Preferred types for builder
functionality are
illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related
compounds disclosed in
U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the CS-
C20 alkyl and
alkenyl succinic acids and salts thereof. Succinate builders also include:
laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate,
and the like. Lauryl-succinates are described in European Patent Application
CA 02362945 2001-08-13
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86200690.5/0,200,263, published November S, 1986. Fatty acids, e.g., C 12-C 1
g monocarboxylic
acids, can also be incorporated into the compositions as surfactant/builder
materials alone or in
combination with the aforementioned builders, especially citrate and/or the
succinate builders, to
provide additional builder activity but are generally not desired. Such use of
fatty acids will
5 generally result in a diminution of sudsing in laundry compositions, which
may need to be taken
into account by the formulator. Fatty acids or their salts are undesirable in
Automatic
Dishwashing (ADD) embodiments in situations wherein soap scums can form and be
deposited
on dishware. . Other suitable polycarboxylates are disclosed in U.S.
4,144,226, Crutchfield et al,
March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl,
U.S. 3,723,322.
10 Other types of inorganic builder materials which can be used have the
formula (Mx)i Cay
(C03)z wherein x and i are integers from 1 to 15, y is an integer from 1 to
10, z is an integer from
2 to 25, Mi are cations, at least one of which is a water-soluble, and the
equation Ei - 1-15(xi
multiplied by the valence of Mi) + 2y = 2z is satisfied such that the formula
has a neutral or
"balanced" charge. These builders are referred to herein as "Mineral
Builders". Waters of
15 hydration or anions other than carbonate may be added provided that the
overall charge is
balanced or neutral. The charge or valence effects of such anions should be
added to the right
side of the above equation. Preferably, there is present a water-soluble
cation selected from the
group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium,
silicon, and
mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium,
ammonium and
20 mixtures thereof, sodium and potassium being highly preferred. Nonlimiting
examples of
noncarbonate anions include those selected from the group consisting of
chloride, sulfate,
fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and
mixtures thereof.
Preferred builders of this type in their simplest forms are selected from the
group consisting of
Na2Ca(C03)2, K2Ca(C03)2, Na2Ca2(C03)3, NaKCa(C03)2, NaKCa2(C03)3, K2Ca2(C03)3,
25 and combinations thereof. An especially preferred material for the builder
described herein is
Na2Ca(C03)2 in any of its crystalline modifications. Suitable builders of the
above-defined type
are further illustrated by, and include, the natural or synthetic forms of any
one or combinations
of the following minerals: Afghanite, Andersonite, AshcroftineY, Beyerite,
Borcarite,
Burbankite, Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne,
DonnayiteY,
30 Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite,
Gregoryite, Jouravskite,
KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY,
Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe,
Sacrofanite,
Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite,
and Zemkorite.
Preferred mineral forms include Nyererite, Fairchildite and Shortite.
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36
Detergent builders can also be selected from aluminosilicates and silicates,
for example
to assist in controlling mineral, especially Ca and/or Mg, hardness in wash
water or to assist in
the removal of particulate soils from surfaces.
Suitable silicate builders include water-soluble and hydrous solid types and
including
those having chain-, layer-, or three-dimensional- structure as well as
amorphous-solid or non
structured-liquid types. Preferred are alkali metal silicates, particularly
those liquids and solids
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1, including, particularly
for automatic
dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp.
under the tradename
BRITESIL~, e.g., BRTTESIL H20; and layered silicates, e.g., those described in
U.S. 4,664,839,
May 12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a
crystalline layered
aluminium-free 8-Na2Si05 morphology silicate marketed by Hoechst and is
preferred especially
in granular laundry compositions. See preparative methods in German DE-A-
3,417,649 and DE-
A-3,742,043. Other 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 also or alternately be
used herein. Layered
silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the a,
(3 and y layer-
silicate forms. Other silicates may also be useful, such as magnesium
silicate, which can serve as
a crispening agent in granules, as a stabilising agent for bleaches, and as a
component of suds
control systems.
Also suitable for use herein are synthesized crystalline ion exchange
materials or
hydrates thereof having chain structure and a composition represented by the
following general
formula in an anhydride form: xM2OySi02.zM'O wherein M is Na and/or K, M' is
Ca andlor
Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,71 l,
Sakaguchi et al, June 27,
1995.
Aluminosilicate builders are especially useful in granular compositions, but
can also be
incorporated in liquids, pastes or gels. Suitable for the present proposes are
those having
empirical formula: [Mz(A102)z(Si02)v]'xH20 wherein z and v are integers of at
least 6, the
molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer
from 1 S to 264.
Aluminosilicates can be crystalline or amorphous, naturally-occurring or
synthetically derived.
An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al,
October 12, 1976.
Preferred synthetic crystalline aluminosilicate ion exchange materials are
available as Zeolite A,
Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P,
the so-called Zeolite
MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the
formula:
Nal2[(A102)12(Si02)12~'~20 wherein x is from 20 to 30, especially 27.
Dehydrated zeolites
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37
(x = 0 - 10) may also be used. Preferably, the aluminosilicate has a particle
size of 0.1-10
microns in diameter.
Detergent builders other than silicates can be used in the compositions herein
to assist in
controlling mineral hardness. They can be used in conjunction with or instead
of
aluminosilicates and silicates. Inorganic as well as organic builders can be
used. Builders are
used in automatic dishwashing to assist in the removal of particulate soils.
Inorganic or non-phosphate-containing detergent builders include, but are not
limited to,
phosphonates, phytic acid, carbonates (including bicarbonates and
sesquicarbonates), sulfates,
citrate, zeolite, and aluminosilicates.
Aluminosilicate builders may be used in the present compositions though are
not
preferred for automatic dishwashing detergents. (See U.S. Pat. 4,605,509 for
examples of
preferred aluminosilicates.) Aluminosilicate builders are of great importance
in most currently
marketed heavy duty granular detergent compositions, and can also be a
significant builder
ingredient in liquid detergent formulations. Aluminosilicate builders include
those having the
empirical formula: Na20~A1203~xSiOz~yH20 wherein z and y are integers of at
least 6, the molar
ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer
from about 15 to about 264.
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. Patent 3,985,669, Krummel, et al, issued
October 12, 1976.
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
another
embodiment, the crystalline aluminosilicate ion exchange material has the
formula:
Nal2[(A102)12(Si02)12j'~20 wherein x is from about 20 to about 30, especially
about 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 about 0.1-10 microns in
diameter. Individual
particles can desirably be even smaller than 0.1 micron to further assist
kinetics of exchange
through maximization of surface area. High surface area also increases utility
of aluminosilicates
as adsorbents for surfactants, especially in granular compositions. Aggregates
of aluminosilicate
particles may be useful, a single aggregate having dimensions tailored to
minimize segregation in
granular compositions, while the aggregate particle remains dispersible to
submicron individual
particles during the wash. As with other builders such as carbonates, it may
be desirable to use
zeolites in any physical or morphological form adapted to promote surfactant
carrier function,
and appropriate particle sizes may be freely selected by the formulator.
CA 02362945 2003-03-06
38
Polyrrteric Soil Release Agent - The compositions according to the present
invention may
optionally comprise one or more soil release agents. Polymeric soil release
agents are
characterized by having both hydrophilic segments, to hydrophilize the surface
of hydrophobic
fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic
;. fibers and remain adhered thereto through completion of the laundry cycle
and , thus, serve as an
anchor for the hydrophilic segments. This can enable stains occuring
subsequent to treatment
with the soil release agent to be mare easily cleaned in later washing
procedures.
If utilized, soil release agents will generally comprise from about 0.01% to
about 10%
preferably from about 0.1% to about 5%, mare preferably from about 0.2% to
about 3% by
weight, of the composition.
The following, all included herein by reference, describe soil release
polymers suitable
far us in the present invention. U.5. 5,691,298 Gosselink et al., issued
November 25, 1997; U.S.
5,599,782 Pan et al., issued February 4, 1997; U.S. 5,~t15,807 (rosselink et
al., issued May 16;
1995; U.S. 5,182,043 Morrall et al., issued January 26, 1993; U.S. 4,956,447
Gosselink et al.,
issued September 11, 1990; U.S. 4,976,879 Maldonado et al. issued December 11,
1990; U.S.
4,968,451 Scheibel et al., issued November 6, 1990; U.S. 4,925,577 Borcher,
Sr. et al., issued
May 15, 1990; U.S. 4,861,512 Gasselink, issued August 29, 1989; U.S. 4,877,896
Maldonado et
al., issued October 31, 1989; U.S. 4,702,857 Gosselink et al., issued October
27, 1987; U.S.
4,711,730 Gosselink et al., issued December 8, 1987; L1.S. 4,721,580 Gosselink
issued January
26, 1988; U.S. 4,000,093 Nicol et al., issued December 28, 1976; U.S.
3,959,230 Hayes, issued
May 25, 1976; U.S. 3,893,929 Hssadur, issued Juiy 8, 1975; and European Patent
Application 0
219 048, published April 22, 1987 by Kud et at.
Further suitable soil release agents are described in U.S, 4,201,824 Voilland
et al.; U.S.
4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.; t.l.S. 4,579,681 Ruppert
et al.; U.S.
4,220,918; U.S. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP
457,205 A to
BASF (1991); and DE 2,335,044 to Unilever N.V., 1974.
Clay Soil RemovaUAnti-redeposition Atzents - The conxpositions of the present
invention
can also optionally contain water-soluble ethoxylated amines having clay soil
removal and
antiredeposition properties. Granular compositions which contain these
compounds typically
contain from about 0.01% to about 10.0% by weight of the water-soluble
ethoxylates amines;
liquid detergent compositions typically contain about 0.01% to about 5%.
Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously
be
utilized at levels from about 0.1% to about 7%, by weight, in the compositions
herein, especially
in the presence of zeolite and/or layered silicate builders. Suitable
polymeric dispersing agents
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39
include polymeric polycarboxylates and polyethylene glycols, although others
known in the art
can also be used. It is believed, though it is not intended to be limited by
theory, that polymeric
dispersing agents enhance overall detergent builder performance, when used in
combination with
other builders (including lower molecular weight polycarboxylates) by crystal
growth inhibition,
particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated
monomeric acids that
can be polymerized to form suitable polymeric polycarboxylates include acrylic
acid, malefic acid
(or malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid, citraconic acid
and methylenemalonic acid. The presence in the polymeric polycarboxylates
herein or
monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether, styrene,
ethylene, etc. is suitable provided that such segments do not constitute more
than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such
acrylic acid-based polymers which are useful herein are the water-soluble
salts of polymerized
acrylic acid. The average molecular weight of such polymers in the acid form
preferably ranges
from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most
preferably from
about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can
include, for example,
the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of
this type are
known materials. Use of polyacrylates of this type in detergent compositions
has been disclosed,
for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the
dispersing/anti-redeposition agent. Such materials include the water-soluble
salts of copolymers
of acrylic acid and malefic acid. The average molecular weight of such
copolymers in the acid
form preferably ranges from about 2,000 to 100,000, more preferably from about
5,000 to 75,000,
most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate
segments in such
copolymers will generally range from about 30:1 to about 1:1, more preferably
from about 10:1
to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can
include, for example,
the alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate
copolymers of this type are known materials which are described in European
Patent Application
No. 66915, published December 15, 1982, as well as in EP 193,360, published
September 3,
1986, which also describes such polymers comprising hydroxypropylacrylate.
Still other useful
dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such
materials are also
CA 02362945 2001-08-13
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disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of
acrylic/maleic/vinyl
alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG
can exhibit dispersing agent performance as well as act as a clay soil removal-
antiredeposition
5 agent. Typical molecular weight ranges for these purposes range from about
500 to about
100,000, preferably from about 1,000 to about 50,000, more preferably from
about 1,500 to about
10,000.
Polyaspartate and polyglutamate .dispersing agents may also be used,
especially in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably have a
10 molecular weight (avg.) of about 10,000.
Bri her - Any optical brighteners or other brightening or whitening agents
known in
the art can be incorporated at levels typically from about 0.01 % to about
1.2%, by weight, into
the detergent compositions herein. Commercial optical brighteners which may be
useful in the
present invention can be classified into subgroups, which include, but are not
necessarily limited
15 to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid,
methinecyanines,
dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and
other
miscellaneous agents. Examples of such brighteners are disclosed in "The
Production and
Application of Fluorescent Brightening Agents", M. Zahradnik, Published by
John Wiley &
Sons, New York (1982).
20 Specific examples of optical brighteners which are useful in the present
compositions are
those identified in U.S. Patent 4,790,856, issued to Wixon on December 13,
1988. These
brighteners include the PHORWHTTE series of brighteners from Verona. Other
brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal
SBM; available
from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-phenyl)-
2H-naptho[1,2-
25 d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-
bis(styryl)bisphenyls; and the amino-
coumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-
amino coumarin;
1,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-
bis(benzoxazol-2-yl)thiophene;
2-styryl-naptho[1,2-d]oxazole; and 2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole.
See also U.S.
Patent 3,646,015, issued February 29, 1972 to Hamilton.
30 Dye Transfer InhibitingA~e~ - The compositions of the present invention may
also include one or more materials effective for inhibiting the transfer of
dyes from one fabric to
another during the cleaning process. generally, such dye transfer inhibiting
agents include
polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone
and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures
thereof. If used,
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41
these agents typically comprise from about 0.01% to about 10% by weight of the
composition,
preferably from about 0.01% to about 5%, and more preferably from about 0.05%
to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units
having the following structural formula: R-Ax-P; wherein P is a polymerizable
unit to which an
N-O group can be attached or the N-O group can form part of the polymerizable
unit or the N-O
group can be attached to both units; A is one of the following structures: -
NC(O)-, -C(O)O-, -S-, -
O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics,
heterocyclic or alicyclic
groups or any combination thereof to which the nitrogen of the N-O group can
be attached or the
N-O group is part of these groups. Preferred polyamine N-oxides are those
wherein R is a
heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,
piperidine and derivatives
thereof.
The N-O group can be represented by the following general structures:
O O
~t)X ~ -~2)y~ =N-~Rt)x
(R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or combinations
thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be
attached or form part of
any of the aforementioned groups. 'The amine oxide unit of the polyamine N-
oxides has a pKa
<10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-
soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are
polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and
mixtures thereof. These polymers include random or block copolymers where one
monomer type
is an amine N-oxide and the other monomer type is an N-oxide. The amine N-
oxide polymers
typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the
number of amine oxide groups present in the polyamine oxide polymer can be
varied by
appropriate copolymerization or by an appropriate degree of N-oxidation. The
polyamine oxides
can be obtained in almost any degree of polymerization. Typically, the average
molecular weight
is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most
preferred 5,000 to
100,000. This preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions
herein is
poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000 and an
amine to amine N-oxide ratio of about 1:4.
CA 02362945 2003-03-06
a2
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class
as "PVPVI") are also preferred for use herein.. Preferably the PVPVI has an
average molecular
weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most
preferably from 10,000 to 20,000. ('The average molecular weight range is
determined by light
:i scattering as described in Harth, et al., chemicals, Ana is, ~'oi 113.
"Modern Methods of
Polymer Characterization", the disclosures of which are incorporated herein by
reference.) The
PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from
1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1
to 0.4:1. These
copolymers can be either linear or branched.
1C~ The present invention compositions also may employ a polyvinylpyrrolidone
("PVP")
having an average molecular weight of from about 5,000 to about 400,000,
preferably from about
5,000 to about 200,000, and more preferably frcam about 5,000 to about 50,000.
PVP's are known
to persons skilled in the detergent field; see, for example, EP-A-262,897 and
EP-A-256,696,
Compositions containing PVP can also contain polyethylene
15 glycol ("PEG") having an average molecular weight from about 500 to about
100,000, preferably
from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm
basis delivered
in wash solutions is from about 2:1 to about 50:1, and more preferably from
about 3:1 to about
10:1.
The compositions herein may also optionally contain from about 0.005% to 5% by
weight
20 of certain types of hydrophilic optical brighteners which also provide a
dye transfer inhibition
action. If used, the compositions herein will preferably comprise from about
0.01% to 1% by
weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the
structural formula:
Rt R2
N H H
N O~-N ~ C=C ~ N-~~ N
R~ S03M SO~M Rt
wherein Rl is selected from aniline, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected
from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, rnorphilino, chloro
and amino;
and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is aniline, R2 is N-2-bis-hydroxyethyl and M is
a cation
such as sodium, the brightener is 4,4',-bis[(4-aniline-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-
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43
yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener species is
commercially marketed under the tradename Tinopal-LJNPA-GX by Ciba-Geigy
Corporation.
Tinopal-IJNPA-GX is the preferred hydrophilic optical brightener useful in the
detergent
compositions herein.
When in the above formula, Rl 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-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 SBM-GX
by Ciba-
Geigy Corporation.
When in the above formula, Rl is anilino, R2 is morphilino and M is a canon
such as
sodium, the brightener is 4,4'-bis[(4-anilino-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.
The specific optical brightener species selected for use in the present
invention provide
especially effective dye transfer inhibition performance benefits when used in
combination with
the selected polymeric dye transfer inhibiting agents hereinbefore described.
The combination of
such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected
optical
brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX)
provides
significantly better dye transfer inhibition in aqueous wash solutions than
does either of these two
granular composition components when used alone. Without being bound by
theory, it is
believed that such brighteners work this way because they have high affinity
for fabrics in the
wash solution and therefore deposit relatively quick on these fabrics. The
extent to which
brighteners deposit on fabrics in the wash solution can be defined by a
parameter called the
"exhaustion coefficient". The exhaustion coefficient is in general as the
ratio of a) the brightener
material deposited on fabric to b) the initial brightener concentration in the
wash liquor.
Brighteners with relatively high exhaustion coefficients are the most suitable
for inhibiting dye
transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types of
compounds can optionally be used in the present compositions to provide
conventional fabric
"brightness" benefits, rather than a true dye transfer inhibiting effect. Such
usage is conventional
and well-known to detergent formulations.
Suds Suppressors - Compounds for reducing or suppressing the formation of suds
can be
incorporated into the compositions of the present invention. Suds suppression
can be of
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44
particular importance in the so-called "high concentration cleaning process"
as described in U.S.
4,489,455 and 4,489,574 and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressers, and suds
suppressers are
well known to those skilled in the art. See, for example, Kirk Othmer
Encyclopedia of Chemical
Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc.,
1979). One
category of suds suppresser of particular interest encompasses monocarboxylic
fatty acid and
soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to
Wayne St. John.
The monocarboxylic fatty acids and salts thereof used as suds suppresser
typically have
hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable
salts include the alkali metal salts such as sodium, potassium, and lithium
salts, and ammonium
and alkanolammonium salts.
The compositions herein may also contain non-surfactant suds suppressers.
These
include, for example: high molecular weight hydrocarbons such as paraffin,
fatty acid esters
(e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aliphatic C 1 g-C40 ketones
(e.g., stearone), etc. Other suds inhibitors include N-alkylated amino
triazines such as tri- to
hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as
products of cyanuric
chloride with two or three moles of a primary or secondary amine containing 1
to 24 carbon
atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol
phosphate ester
and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate
esters. The
hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
The liquid
hydrocarbons will be liquid at room temperature and atmospheric pressure, and
will have a pour
point in the range of about -40°C and about 50°C, and a minimum
boiling point not less than
about 110°C (atmospheric pressure). It is also known to utilize waxy
hydrocarbons, preferably
having a melting point below about 100°C. The hydrocarbons constitute a
preferred category of
suds suppresser for detergent compositions. Hydrocarbon suds suppressers are
described, for
example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The
hydrocarbons,
thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or
unsaturated
hydrocarbons having from about 12 to about 70 carbon atoms. The term
"paraffin," as used in
this suds suppresser discussion, is intended to include mixtures of true
paraffins and cyclic
hydrocarbons.
Another preferred category of non-surfactant suds suppressers comprises
silicone suds
suppressers. This category includes the use of polyorganosiloxane oils, such
as polydimethyl-
siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and
combinations of
polyorganosiloxane with silica particles wherein the polyorganosiloxane is
chemisorbed or fused
CA 02362945 2003-03-06
onto the silica. Silicone suds suppressers are well known in the art and are,
for example,
disclosed in 11.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and
EP 0 254 016.
Other silicone suds suppressers are disclosed in U.S. Patent 3,455,839 which
relates to
5 compositions and processes for defoaming aqueous solutions by incorporating
therein small
amounts of polydimethylsiloxane Huids.
Mixtures of silicone and silanated silica are described, for instance, in
German Patent
Application DOS 2,124,526. Silicone defc>amers and suds controlling agents in
granular
detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et
al, and in U.S. Patent
10 4,652,392, Baginsld et al, issued March 24, 1987.
An exemplary silicone based suds suppresser for use herein is a suds
suppressing amount
of a suds controlling agent consisting essentially of:
(l) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,50Q'
cs. at 25°C;
15 {ii) from about 5 to about 50 parts per 100 parts by weight of (l) of
siloxane resin
composed of (CH3)3Si01/2 units of SiO2 units in a ratio of from (CH3)3 Si01/2
units and to Si02 units of from about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 pans per 100 parts by weight of (l) of a solid
silica gel.
In the preferred silicone suds suppresser used herein, the solvent for a
continuous phase
20 is made up of certain polyethylene glycols or polyethylene-polypropylene
glycol copolymers or
mixtures thereof (preferred), or palypropylene glycol. The primary silicone
suds suppresser is
branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with
controlled suds will optionally comprise from about 0.001 to about 1,
preferably from about 0.01
2;i to about 0.7, most preferably from about 0.05 to about 0.5, weight % of
said silicone uds
suppresser, which comprises (1) a nonaqueous emulsion of a primary antifoam
agent which is a
mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone
resin-producing silicone
compound, (c) a finely divided filler material, and (d) a catalyst to promote
the reaction of
nuxture components (a), (b) and (c), to form silanolates; {2) at least one
nonionic silicone
3C1 surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-
polypropylene glycol
having a solubility in water at roam temperature of more than about 2 weight
%; and without
polypropylene glycol. Similar amounts can be used in granular compositions,
gels, etc. See also
U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316,
Starch, issued January
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46
8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents
4,639,489 and
4,749,740, Aizawa et al at column l, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and a
copolymer of polyethylene glycol/polypropylene glycol, all having an average
molecular weight
of less than about 1,000, preferably between about 100 and 800. The
polyethylene glycol and
polyethylene/polypropylene copolymers herein have a solubility in water at
room temperature of
more than about 2 weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular weight
of less than about 1,000, more preferably between about 100 and 800, most
preferably between
200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol,
preferably PPG
200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most
preferably
between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-
polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain
polypropylene glycol,
particularly of 4,000 molecular weight. They also preferably do not contain
block copolymers of
ethylene oxide and propylene oxide, like PLUROhIIC L101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-
alkyl
alkanols) and mixtures of such alcohols with silicone oils, such as the
silicones disclosed in U.S.
4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16
alkyl alcohols
having a C 1-C 16 chain. A preferred alcohol is 2-butyl octanol, which is
available from Condea
under the trademark ISOFOL 12. Mixtures of secondary alcohols are available
under the
trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise
mixtures
of alcohol + silicone at a weight ratio of 1:5 to 5:1.
For any granular compositions to be used in automatic laundry washing
machines, suds
should not form to the extent that they overflow the washing machine. Suds
suppressors, when
utilized, are preferably present in a "suds suppressing amount. By "suds
suppressing amount" is
meant that the formulator of the composition can select an amount of this suds
controlling agent
that will sufficiently control the suds to result in a low-sudsing granular
detergent for use in
automatic laundry washing machines.
The compositions herein may comprise from 0% to about 10% of suds suppressor.
When
utilized as suds suppressors, monocarboxylic fatty acids, and salts therein,
will be present
typically in amounts up to about S%, by weight, of the detergent composition.
Preferably, from
about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds
suppressors are typically utilized in amounts up to about 2.0%, by weight, of
the detergent
composition, although higher amounts may be used. This upper limit is
practical in nature, due
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47
primarily to concein with keeping costs minimized and effectiveness of lower
amounts for
effectively controlling sudsing. Preferably from about 0.01% to about 1% of
silicone suds
suppressor is used, more preferably from about 0.25% to about 0.5%. As used
herein, these
weight percentage values include any silica that may be utilized in
combination with
polyorganosiloxane, as well as any adjunct materials that may be utilized.
Monostearyl
phosphate suds suppressors are generally utilized in amounts ranging from
about 0.1% to about
2%, by weight, of the composition. Hydrocarbon suds suppressors are typically
utilized in
amounts ranging from about 0.01% to about 5.0%, although higher levels can be
used. The
alcohol suds suppressors are typically used at 0.2%-3% by weight of the
finished compositions.
Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates such as those
prepared
from polyacrylates are useful herein to provide additional grease removal
performance. Such
materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq.,
incorporated herein by
reference. Chemically, these materials comprise polyacrylates having one
ethoxy side-chain per
every 7-8 acrylate units. The side-chains are of the formula -
(CH2CH20)m(CH2)nCH3 wherein
m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate
"backbone" to provide
a "comb" polymer type structure. The molecular weight can vary, but is
typically in the range of
about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise
from about 0.05%
to about 10%, by weight, of the compositions herein.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
impalpable
smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December
13, 1977, as well as
other softener clays known in the art, can optionally be used typically at
levels of from about
0.5% to about 10% by weight in the present compositions to provide fabric
softener benefits
concurrently with fabric cleaning. Clay softeners can be used in combination
with amine and
cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp
et al, March 1, 1983
and U.S. Patent 4,291,071, Hams et al, issued September 22, 1981.
NON-AQUEOUS BASED HEAVY DUTY LIQUm DETERGENTS
SURFACTANT-CONTAINING LI(LU~ PHASE
The present invention comprises non-aqueous, liquid, heavy-duty detergent
compositions in
the form of a stable suspension of solid, substantially insoluble particulate
material dispersed
throughout a structured, surfactant-containing liquid phase. The detergent
composition
comprises from about 49% to 99.95% by weight of the composition of a
structured, surfactant-
containing liquid phase formed by combining:
i) from about 1% to 80% by weight of said liquid phase of one or more
nonaqueous
organic diluents; and
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48
ii) from about 20% to 99% by weight of said liquid phase of a surfactant
system
comprising surfactants selected from the group consisting of anionic,
nonionic, cationic
surfactants and combinations thereof.
The surfactant-containing, non-aqueous liquid phase of the present invention
will generally
comprise from about 52% to about 98.9% by weight of the detergent compositions
herein. More
preferably, this liquid phase is surfactant-structured and will comprise from
about 55% to 98% by
weight of the compositions. Most preferably, this non-aqueous liquid phase
will comprise from
about 55% to 70% by weight of the compositions herein. Such a surfactant-
containing liquid
phase will frequently have a density of from about 0.6 to 1.4 g/cc, more
preferably from about 0.9
to 1.3 g/cc. The liquid phase of the detergent compositions herein is
preferably formed from one
or more non-aqueous organic diluents into which is mixed a surfactant
structuring agent which is
preferably a specific type of anionic surfactant-containing powder.
Non-aqueous Organic Diluents
The major component of the liquid phase of the HDL compositions herein
comprises one or
more non-aqueous organic diluents. The non-aqueous organic diluents used in
this invention may
be either surface active, i.e., surfactant, liquids or non-aqueous, non-
surfactant liquids referred to
herein as non-aqueous solvents. The term "solvent" is used herein to connote
the non-surfactant,
non-aqueous liquid portion of the compositions herein. While some of the
essential and/or
optional components of the compositions herein may actually dissolve in the
"solvent"-containing
liquid phase, other components will be present as particulate material
dispersed within the
"solvent"-containing liquid phase. Thus the term "solvent" is not meant to
require that the
solvent material be capable of actually dissolving all of the detergent
composition components
added thereto.
The non-aqueous liquid diluent component will generally comprise from about
50% to
100%, more preferably from about 50% to 80%, most preferably from about 55% to
75%, of a
structured, surfactant-containing liquid phase. Preferably the liquid phase of
the compositions
herein, i.e., the non-aqueous liquid diluent component, will comprise both non-
aqueous liquid
surfactants and non-surfactant non-aqueous solvents.
i) Non-aqueous Surfactant Li~c uids - Suitable types of non-aqueous surfactant
liquids which can
be used to form the liquid phase of the compositions herein include the
alkoxylated alcohols,
ethylene oxide (EO)-propylene oxide (PO) block polymers, polyhydroxy fatty
acid amides,
alkylpolysaccharides, and the like. Such normally liquid surfactants are those
having an HLB
ranging from 10 to 16. Most preferred of the surfactant liquids are the
alcohol alkoxylate
nonionic surfactants.
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WO 00/50549 PCT/US00/04185
49
Alcohol alkoxylates are materials which correspond to the general formula:
R 1 (CmH2m0)nOH
wherein R1 is a Cg - C16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12.
Preferably R1 is an alkyl group, which may be primary or secondary, that
contains from about 9
to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
Preferably also the
alkoxylated fatty alcohols will be ethoxylated materials that contain from
about 2 to 12 ethylene
oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide
moieties per
molecule.
The alkoxylated fatty alcohol materials useful in the liquid phase will
frequently have a
hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More
preferably, the
HLB of this material will range from about 6 to 1 S, most preferably from
about 8 to 15.
Examples of fatty alcohol alkoxylates useful in or as the non-aqueous liquid
phase of the
compositions herein will include those which are made from alcohols of 12 to
15 carbon atoms
and which contain about 7 moles of ethylene oxide. Such materials have been
commercially
marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical
Company.
Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol
averaging 11 carbon atoms
in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an
ethoxylated primary C12
- C13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an
ethoxylated Cg-C11
primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates
of this type have
also been marketed by Shell Chemical Company under the Dobanol tradename.
Dobanol 91-S is
an ethoxylated Cg-C11 fatty alcohol with an average of 5 moles ethylene oxide
and Dobanol 25-7
is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene
oxide per mole of
fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and
Tergitol 15-S-
9 both of which are linear secondary alcohol ethoxylates that have been
commercially marketed
by Union Carbide Corporation. The former is a mixed ethoxylation product of
C11 to C15 linear
secondary alkanol with 7 moles of ethylene oxide and the latter is a similar
product but with 9
moles of ethylene oxide being reacted.
Other types of alcohol ethoxylates useful in the present compositions are
higher molecular
weight nonionics, such as Neodol 45-1 l, which are similar ethylene oxide
condensation products
of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon
atoms and the
number of ethylene oxide groups per mole being about 11. Such products have
also been
commercially marketed by Shell Chemical Company.
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WO 00/50549 PCT/US00/04185 - -
If alcohol alkoxylate nonionic surfactant is utilized as part of the non-
aqueous liquid phase
in the detergent compositions herein, it will preferably be present to the
extent of from about 1%
to 60% of the composition. structured liquid phase. More preferably, the
alcohol alkoxylate
component will comprise about S% to 40% of the structured liquid phase. Most
preferably, an
5 alcohol alkoxylate component will comprise from about 5% to 35% of the
detergent composition
structured liquid phase. Utilization of alcohol alkoxylate in these
concentrations in the liquid
phase corresponds to an alcohol alkoxylate concentration in the total
composition of from about
1% to 60% by weight, more preferably from about 2% to 40% by weight, and most
preferably
from about 5% to 25% by weight, of the composition.
10 Another type of non-aqueous surfactant liquid which may be utilized in this
invention are
the ethylene oxide (E0) - propylene oxide (PO) block polymers. Materials of
this type are well
known nonionic surfactants which have been marketed under the tradename
Pluronic. These
materials are formed by adding blocks of ethylene oxide moieties to the ends
of polypropylene
glycol chains to adjust the surface active properties of the resulting block
polymers. EO-PO
15 block polymer nonionics of this type are described in greater detail in
Davidsohn and Milwidsky
Synthetic Detergents, 7th Ed.; Longman Scientific and Technical (1987) at pp.
34-36 and pp.
189-191 and in U.S. Patents 2,674,619 and 2,677,700. All of these publications
are incorporated
herein by reference. These Pluronic type nonionic surfactants are also
believed to function as
effective suspending agents for the particulate material which is dispersed in
the liquid phase of
20 the detergent compositions herein.
Another possible type of non-aqueous surfactant liquid useful in the
compositions herein
comprises polyhydroxy fatty acid amide surfactants, which have been defined
herein before. If
present, the polyhydroxy fatty acid amide surfactants are preferably present
in a concentration of
from about 0.1 to about 8%.
25 The amount of total liquid surfactant in the preferred surfactant-
structured, non-aqueous
liquid phase herein will be determined by the type and amounts of other
composition components
and by the desired composition properties. Generally, the liquid surfactant
can comprise from
about 35% to 70% of the non-aqueous liquid phase of the compositions herein.
More preferably,
the liquid surfactant will comprise from about 50% to 65% of a non-aqueous
structured liquid
30 phase. This corresponds to a non-aqueous liquid surfactant concentration in
the total composition
of from about 15% to 70% by weight, more preferably from about 20% to 50% by
weight, of the
composition.
ii) Non-surfactant Non-aqueous Organic Solvents - The liquid phase of the HDL
compositions
herein may also comprise one or more non-surfactant, non-aqueous organic
solvents. Such non-
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51
surfactant non-aqueous liquids are preferably those of low polarity. For
purposes of this
invention, "low-polarity" liquids are those which have little, if any,
tendency to dissolve one of
the preferred types of particulate material used in the compositions herein,
i.e., the peroxygen
bleaching agents, sodium perborate or sodium percarbonate. Thus relatively
polar solvents such
as ethanol are preferably not utilized. Suitable types of low-polarity
solvents useful in the non-
aqueous liquid detergent compositions herein do include non-vicinal C4-Cg
alkylene glyeols,
alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene
glycols, lower
molecular weight methyl esters and amides, and the like.
A preferred type of non-aqueous, low-polarity solvent for use in the
compositions herein
comprises the non-vicinal C4-Cg branched or straight chain alkylene glycols.
Materials of this
type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-
butylene glycol and
1,4-butylene glycol. Hexylene glycol is the most preferred.
Another preferred type of non-aqueous, low-polarity solvent for use herein
comprises the
mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6 alkyl ethers. The
specific examples
of such compounds include diethylene glycol monobutyl ether, tetraethylene
glycol monobutyl
ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl
ether. Diethylene
glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-
propanol (BPP)
are especially preferred. Compounds of the type have been commercially
marketed under the
tradenames Dowanol, Carbitol, and Cellosolve.
Another preferred type of non-aqueous, low-polarity organic solvent useful
herein
comprises the lower molecular weight polyethylene glycols (PEGS). Such
materials are those
having molecular weights of at least about 150. PEGs of molecular weight
ranging from about
200 to 600 are most preferred.
Yet another preferred type of non-polar, non-aqueous solvent comprises lower
molecular
weight methyl esters. Such materials are those of the general formula: R1-C(O)-
OCH3 wherein
R1 ranges from 1 to about 18. Examples of suitable lower molecular weight
methyl esters
include methyl acetate, methyl propionate, methyl octanoate, and methyl
dodecanoate.
The non-aqueous, generally low-polarity, non-surfactant organic solvents)
employed
should, of course, be compatible and non-reactive with other composition
components, e.g.,
bleach and/or activators, used in the liquid detergent compositions herein.
Such a solvent
component is preferably utilized in an amount of from about 1 % to 70% by
weight of the liquid
phase. More preferably, a non-aqueous, low-polarity, non-surfactant solvent
will comprise from
about 10% to 60% by weight of a structured liquid phase, most preferably from
about 20% to
50% by weight, of a structured liquid phase of the composition. Utilization of
non-surfactant
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52
solvent in these concentrations in the liquid phase corresponds to a non-
surfactant solvent
concentration in the total composition of from about 1 % to 50% by weight,
more preferably from
about 5% to 40% by weight, and most preferably from about 10% to 30% by
weight, of the
composition.
iii) Blends of Surfactant and Non-surfactant Solvents - In systems which
employ both non-
aqueous surfactant liquids and non-aqueous non-surfactant solvents, the ratio
of surfactant to
non-surfactant liquids, e.g., the ratio of alcohol alkoxylate to low polarity
solvent, within a
structured, surfactant-containing liquid phase can be used to vary the
rheological properties of the
detergent compositions eventually formed. Generally, the weight ratio of
surfactant liquid to
non-surfactant organic solvent will range about 50:1 to 1:50. More preferably,
this ratio will
range from about 3:1 to 1:3, most preferably from about 2:1 to 1:2.
Surfactant Structurant
The non-aqueous liquid phase of the HDL compositions of this invention is
prepared by
combining with the non-aqueous organic liquid diluents hereinbefore described
a surfactant
which is generally, but not necessarily, selected to add structure to the non-
aqueous liquid phase
of the detergent compositions herein. Structuring surfactants can be of the
anionic, nonionic,
cationic, and/or amphoteric types.
Preferred structuring surfactants are the anionic surfactants such as the
alkyl sulfates, linear
alkyl benzene sulfonate (LAS), the alkyl polyalkxylate sulfates and the linear
alkyl benzene
sulfonates. Another common type of anionic surfactant material which may be
optionally added
to the detergent compositions herein as structurant comprises carboxylate-type
anionics.
Carboxylate-type anionics include the C 10-C 1 g alkyl alkoxy carboxylates
(especially the EO 1 to
5 ethoxycarboxylates) and the C 10-C 1 g sarcosinates, especially oleoyl
sarcosinate. Yet another
common type of anionic surfactant material which may be employed as a
structurant comprises
other sulfonated anionic surfactants such as the Cg-C 1 g paraffin sulfonates
and the Cg-C 1 g olefin
sulfonates. Structuring anionic surfactants will generally comprise from about
1% to 30% by
weight of the compositions herein.
As indicated, one preferred type of structuring anionic surfactant comprises
primary or
secondary alkyl sulfate anionic surfactants. Such surfactants are those
produced by the sulfation
of higher Cg-C20 fatty alcohols.
The most preferred type of anionic surfactant for use as a structurant in the
HDL
compositions herein comprises the linear alkyl benzene sulfonate (LAS)
surfactants.
SOLID PARTICULATE MATERIALS
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53
The non-aqueous HDL compositions herein preferably comprise from about 0.01%
to 50%
by weight, more preferably from about 0.2% to 30% by weight, of solid phase
particulate material
which is dispersed and suspended within the liquid phase. Generally such
particulate material
will range in size from about 0.1 to 1500 microns, more preferably from about
0.1 to 900
microns. Most preferably, such material will range in size from about 5 to 200
microns.
The particulate material utilized herein can comprise one or more types of
detergent
composition components which in particulate form are substantially insoluble
in the non-aqueous
liquid phase of the composition. The types of particulate materials which can
be utilized are
described are peroxygen bleaching agent, organic builder, inorganic alkalinity
source (preferably
include water-soluble alkali metal carbonates, bicarbonates, borates,
pyrophosphates,
orthophosphates, polyphosphates phosphonates, silicates and metasilicates),
colored speckles and
mixtures therof.
AQUEOUS BASED HEAVY DUTY LIQUID DETERGENTS
The present invention also comprises aqueous based liquid detergent
compositions. The
aqueous liquid detergent compositions preferably comprise from about 10% to
about 98%,
preferably from about 30% to about 95%, by weight of an aqueous liquid carrier
which is
preferably water. Additionally, the aqueous liquid detergent compositions of
the present
invention comprise a surfactant system which preferably contains one or more
detersive co
surfactants in addition to the branched surfactants disclosed above. The
additional co-surfactants
can be selected from nonionic detersive surfactant, anionic detersive
surfactant, zwitterionic
detersive surfactant, amine oxide detersive surfactant, and mixtures thereof.
The surfactant
system typically comprises from about 5% to about 70%, preferably from about
15% to about
30%, by weight of the detergent composition. These surfactants are
hereinbefore described.
OTHER OPTIONAL HDL COMPOSITION COMPONENTS
In addition to the liquid and solid phase components as hereinbefore
described, the aqueous
and non-aqueous based detergent compositions can, and preferably will, contain
various other
optional components. Such optional components may be in either liquid or solid
form. The
optional components may either dissolve in the liquid phase or may be
dispersed within the liquid
phase in the form of fme particles or droplets. Suitable optional material
includes for example
chelating agents, enzymes, builders, bleach catalysts, bleach activators,
thickeners, viscosity
control agents and/or dispersing agents suds boosters, liquid bleach
activator, dye transfer
inhibitors, solvents, suds suppressors, structure elasticizing agent, anti
redeposition agents, to
exemplify but a few possible optional ingredients. Some of the materials which
may optionally
be utilized in the compositions herein are described in greater detail.
Further details on suitable
CA 02362945 2003-03-06
5Q
adjunct ingredients to HDL compositions, meythods of preparing same and use in
the
compositions can be found in in wQ 99/19451 and V1~'O ~9i19450.
Other Ingredients - T'he detergent compositions wilt further preferably
comprise one
or more detersive adjuncts selected from the following: electrolytes (such as
sodium chloride),
polysaccharides, abrasives, bactericides, tarnish inhibitors, dyes, antifungal
or mildew control
agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids,
suds boosters, anti-
corrosive aids, stabilizers and antioxidants. A wide variety of other
ingredients useful in
detergent compositions can be included in the compositions herein, including
other active
ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or
pigments, solvents for
liquid formulations, etc. If high sudsing is desired, suds boosters such as
the C10-C16
alkanolamides can be incorporated into the compositions, typically at 1%-10%
levels. The C10-
C14 monoethanol and diethanoi amides illustrate a typical class of such suds
boosters. Use of
such suds boosters with high sudsing adjunct surfactants such as the amine
oxides, betaines and
sultaines noted above is also advantageous.
An antioxidant can be optionally added to the detergent compositions of the
present
invention. They can be any conventional antioxidant used in detergent
compositions, such as 2,6-
di-tert-butyl-4-methylphenol (HHT), carbamate, ascorbate, thiosulfate,
monoethanolamine(MEA), diethanolamine, triethanolamine, etc. It is preferred
that the
antioxidant, when present, be present in the composition from about 0.001% to
about 5% by
_ weight.
Various detersive ingredients employed in the present compositions optionally
can be
further stabilized by absorbing said ingredients onto a porous hydrophobic
substrate, then coating
said substrate with a hydrophobic coating. Preferably, the detersive
ingredient is admixed with a
26 surfactant before being absorbed into the porous substrate. In use, the
detersive ingredient is
released from the substrate into the aqueous washing liquor, where it performs
its intended
detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark
SIPERhIAT D10, DeGussa) is admixed with a proteolytic enzyme solution
containing 3%-5% of
Clg-15 ethoxylated alcohol (EO 7) nonionic surfactant. 'typically, the
enzymelsurfactant
solution is 2.5 X the weight of silica. The resulting powder is dispersed with
stirring in silicone
oil (various silicone oil viscosities in the range of 500-12,500 can be used).
'The resulting
silicone oil dispersion is emulsified or otherwise added to the final
detergent matrix. By this
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators, bleach
CA 02362945 2003-03-06
catalysts, photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can
be "protected" for use in detergents, including liquid laundry detergent
compositions.
Further, the compositions rnay optionally comprises a hydrotrope. Suitable
hydrotropes
include sodium, potassium, ammonium or water-soluble substituted ammonium
salts of toluene
5 sulfonic acid, naphthalene sulfonic acid, cumene sulfonic acid, xylene
sulfonic acid.
The manufacture of LDL compositions which comprise a non-aqueous carrier
medium
can be prepared according to the disclosures of LI.S. Patents 4,753,570;
4,767,558; 4,772,413;
4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GI3-A-2,195,649; U.S,
4,988,462; U.S.
5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28r92); EP-A-540,089
(5/5/93); EP-A-
10 540,090 (5/5/93); U.S. 4,615,820; EP-A-565,017 ( 10/ 13193 ); EP-A-030,096
(6/10181 ),
Such compositions can contain various particulate detersive
ingredients stably suspended therein. Such non-aqueous compositions thus
comprise a LIQUID
PHASE and, optionally but preferably, a SOLID PHASE, all as described in more
detail
hereinafter and in the cited references.
1:i The LDL compositions of this invention can be used to form aqueous washing
solutions
for use hand dishwashing. Generally, an effective amount of such LDL
compositions is added to
water to form such aqueous cleaning or soaking solutions. Z'he aqueous
solution so formed is
then contacted with the dishware, tableware, and cooking utensils,
An effective amount of the LDL compositions herein added to water to form
aqueous
20 cleaning solutions can comprise amounts sufficient to dorm from about 500
to 20,000 ppm of
composition in aqueous solution. More preferably, from about 800 to 5,000 ppm
of the detergent
composirions herein will be provided in aqueous cleaning liquor.
The mean particle size of the components of granular compositions in
accordance with
the invention should preferably be such that no more that 5% of particles are
greater than t .7mm
25 in diameter and not more than 5°l° of particles are less than
0.1 Smm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the
composition into a number of fractions (typically 5 fractions) on a series of
Tyler sieves. The
weight fractions thereby obtained are plotted against the aperture size of the
sieves. The mean
particle size is taken to be the aperture size through which SO% by weight of
the sample would
30 pass.
The granular laundry compositions in accordance with the present invention
typically has
a bulk density of from 100 g/litre to 1400 gllitre, more preferably from 300
g/litre to 1200 g/litre,
from 650 g/litre to 1000 g/litre.
Hiah Density Detereent Composition_Processes
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56
Various means and equipment are available to prepare high density (i.e.,
greater than about
550, preferably greater than about 650, grams/liter or "g/1"), high
solubility, free-flowing,
granular detergent compositions according to the present invention. Current
commercial practice
in the field employs spray-drying towers to manufacture granular laundry
detergents which often
have a density less than about 500 g/1. In this procedure, an aqueous slurry
of various heat-stable
ingredients in the final detergent composition are formed into homogeneous
granules by passage
through a spray-drying tower, using conventional techniques, at temperatures
of about 175°C to
about 225°C. However, if spray drying is used as part of the overall
process herein, additional or
alternative process steps as described hereinafter must be used to obtain the
level of density (i.e.,
> 650 g/1) required by modern compact, low dosage detergent products.
For example, spray-dried granules from a tower can be densified further by
loading a
liquid such as water or a nonionic surfactant into the pores of the granules
and/or subjecting them
to one or more high speed mixer/densifiers. A suitable high speed
mixer/densifler for this
process is a device marketed under the tradename "Lodige CB 30" or "Lodige CB
30 Recycler"
which comprises a static cylindrical mixing drum having a central rotating
shaft with
mixing/cutting blades mounted thereon. In use, the ingredients for the
detergent composition are
introduced into the drum and the shaft/blade assembly is rotated at speeds in
the range of 100-
2500 rpm to provide thorough mixing/densification. See Jacobs et al, U.S.
Patent 5,149,455,
issued September 22, 1992, and U.S. Patent 5,565,422, issued October 15, 1996
to Del Greco et
al. Other such apparatus includes the devices marketed under the tradename
"Shugi Granulator"
and under the tradename "Drais K-TTP 80).
Another process step which can be used to densify further spray-dried granules
involves
treating the spray-dried granules in a moderate speed mixer/densifier.
Equipment such as that
marketed under the tradename "Lddige KM" (Series 300 or 600) or "Lodige
Ploughshare"
mixer/densifiers are suitable for this process step. Such equipment is
typically operated at 40-
160 rpm. The residence time of the detergent ingredients in the moderate speed
mixer/densifier
is from about 0.1 to 12 minutes conveniently measured by dividing the steady
state
mixer/densifier weight by the throughput (e.g., Kg/hr). Other useful equipment
includes the
device which is available under the tradename "Drais K-T 160". This process
step which
employs a moderate speed mixer/densifier (e.g. Lodige KM) can be used by
itself or sequentially
with the aforementioned high speed mixer/densifier (e.g. Lodige CB) to achieve
the desired
density. Other types of granules manufacturing apparatus useful herein include
the apparatus
disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942.
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WO 00/50549 PCT/CTS00/04185
57
While it may be more suitable to use the high speed mixer/densifier followed
by the low
speed mixer/densifier, the reverse sequential mixer/densifier configuration
also can be used. One
or a combination of various parameters including residence times in the
mixer/densifiers,
operating temperatures of the equipment, temperature and/or composition of the
granules, the use
of adjunct ingredients such as liquid binders and flow aids, can be used to
optimize densification
of the spray-dried granules in the process of the invention. Byway of example,
see the processes
in Appel et al, U.S. Patent 5,133,924, issued July 28, 1992; Delwel et al,
U.S. Patent 4,637,891,
issued January 20, 1987; Kruse et al, U.S. Patent 4,726,908, issued February
23, 1988; and,
Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992.
In those situations in which particularly heat sensitive or highly volatile
detergent
ingredients are to be incorporated into the final detergent composition,
processes which do not
include spray drying towers are preferred. The formulator can eliminate the
spray-drying step by
feeding, in either a continuous or batch mode, starting detergent ingredients
directly into mixing
equipment that is commercially available. One particularly preferred
embodiment involves
charging a surfactant paste and an anhydrous material into a high speed
mixer/densifier (e.g.
Lodige CB) followed by a moderate speed mixer/densifier (e.g. Lodige KM) to
form high density
detergent agglomerates. See Capeci et al, U.S. Patent 5,366,652, issued
November 22, 1994 and
Capeci et al, U.S. Patent 5,486,303, issued January 23, 1996. Optionally, the
liquid/solids ratio
of the starting detergent ingredients in such a process can be selected to
obtain high density
agglomerates that are more free flowing and crisp. See Capeci et al, U.S.
Patent 5,565,137,
issued October 15, 1996.
Optionally, the process may include one or more recycle streams of undersized
particles
produced by the process which are fed back to the mixerldensifiers for further
agglomeration or
build-up. The oversized particles produced by this process can be sent to
grinding apparatus and
then fed back to the mixing/densifying equipment. These additional recycle
process steps
facilitate build-up agglomeration of the starting detergent ingredients
resulting in a finished
composition having a uniform distribution of the desired particle size (400-
700 microns) and
density (> 550 g/1). See Capeci et al, U.S. Patent 5,516,448, issued May 14,
1996 and Capeci et
al, U.S. Patent 5,489,392, issued February 6, 1996. Other suitable processes
which do not call for
the use of spray-drying towers are described by Bonier et al, U.S. Patent
4,828,721, issued May
9, 1989; Beerse et al, U.S. Patent 5,108,646, issued April 28, 1992; and,
Jolicoeur, U.S. Patent
5,178,798, issued January 12, 1993.
In yet another embodiment, a high density detergent composition using a
fluidized bed
mixer. In this process, the various ingredients of the finished composition
are combined in an
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WO 00/50549 PCT/US00/04185
58
aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed
to provide the
finished detergent granules. Prior to the fluidized bed, this process can
optionally include the
step of mixing the slurry using the aforementioned Lodige CB mixer/densifier
or a "Flexomix
160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of
the type available
under the tradename "Escher Wyss" can be used in such processes.
Another suitable process which can be used herein involves feeding a liquid
acid precursor
of an anionic surfactant, an alkaline inorganic material (e.g. sodium
carbonate) and optionally
other detergent ingredients into a high speed mixer/densifier so as to form
particles containing a
partially or totally neutralized anionic surfactant salt and the other
starting detergent ingredients.
Optionally, the contents in the high speed mixer/densifier can be sent to a
moderate speed
mixer/densifier (e.g. Lodige KM) for further mixing resulting in the finished
high density
detergent composition. See Appel et al, U.S. Patent 5,164,108, issued November
17, 1992.
Optionally, high density detergent compositions according to the invention can
be
produced by blending conventional or densified spray-dried detergent granules
with detergent
agglomerates in various proportions (e.g. a 60:40 weight ratio of granules to
agglomerates)
produced by one or a combination of the processes discussed herein. See U.S.
Patent 5,569,645,
issued October 29, 1996 to Dinniwell et al. Additional adjunct ingredients
such as enzymes,
perfumes, brighteners and the like can be sprayed or admixed with the
agglomerates, granules or
mixtures thereof produced by the processes discussed herein.
Laundry washing method
Machine laundry methods herein typically comprise treating soiled laundry with
an
aqueous wash solution in a washing machine having dissolved or dispensed
therein an effective
amount of a machine laundry detergent composition in accord with the
invention. By an effective
amount of the detergent composition it is here meant from 40g to 300g of
product dissolved or
dispersed in a wash solution of volume from 5 to 65 litres, as are typical
product dosages and
wash solution volumes commonly employed in conventional machine laundry
methods.
As noted, surfactants are used herein in detergent compositions, preferably in
combination with other detersive surfactants, at levels which are effective
for achieving at least a
directional improvement in cleaning performance. In the context of a fabric
laundry composition,
such "usage levels" can vary widely, depending not only on the type and
severity of the soils and
stains, but also on the wash water temperature, the volume of wash water and
the type of washing
machine.
Conventional Surface Cleansing Additive:
CA 02362945 2003-03-06
59
The hard surface cleaner composition of the present invention additionally
contain a
conventional surface cleansing additive. The conventional surface cleansing
additive are present
from about 0.001% to about 99.9°lo by weight. Preferably, conventional
surface cleansing
additive will be present from at least about 0.5%, more preferably, at least
about 1%, even more
a preferably at least about 2%, by weight. Additionally, the conventional
surface cleansing
additives can also be present at least about 5%, at least about 8% and at
least about 10%, by
weight but it is more preferable that the conventional Surface cleansing
additive be present in at
least about 2% by weight. Furthermore, the conventional surface cleansing
additive will be
preferably present in the hard surface composition at preferably at less than
about 45%, more
1(1 preferably less than about 40%, even mare preferably less than about 35%,
even more preferably
less than about 30%, even more preferably less than about 20%, by weight. This
conventional
surface cleansing additive is selected from the group comprising liquid
carrier, co-surfactant
(preferably anionic; nonionic; cationic;ampohteric; zwitterionic; and mixtures
thereof), builder,
co-solvent, polymeric additive (preferably polyalkoxylene glycol; PVP
homopolymers or
15 copolymers thereof; polycarboxylate; sulfonated polystyrene polymer; and
mixtures thereof), pH
adjusting material, hydrotropes; and mixtures thereof. Examples of these
suitable conventional
surface cleansing additives can be found in WU 99119448 arid EP 1 023 431.
20 Packa~,ine for the eor~positions
Commercially marketed executions of the compositions can be packaged in any
suitable
container including those constructed from paper, cardboard, plastic materials
and any suitable
laminates. A preferred packaging execution is described in WO 95/02681.
25 The compositions herein may be packaged in a variety of suitable detergent
packaging
known to those skilled in the art. The liquid compositions are preferably
packaged in
conventional detergent plastic bottles.
The following examples are illustrative of the present invention, but are not
meant to
limit or otherwise define its scope. All parts, percentages and ratios used
herein are expressed as
30 percent weight unless otherwise specified.
EXAMPLE 1
Preparation of Coo ~EO~BOz N,o~ionic Surfactant
Neodol 91-8 (30.00 g, 58.7 mmol) is placed into a 250 ml three-necked round-
bottomed
flask, fitted with a heating mantle, magnetic stirrer, pressure equalizing
dropping funnel, reflux
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WO 00/50549 PCT/US00/04185 --
condenser, internal thermometer and argon inlet, and dried under vacuum at 75
°C. After
releasing the vacuum with argon, sodium metal (0.03 g, 1.2 mmol) is placed
into the flask and the
mixture heated and stirred at 140 °C until all sodium is consumed. 1,2-
Epoxybutane (12.71 g,
176.2 mmol) is then added dropwise at a rate so as to keep the reaction
temperature at >120 °C,
5 with a target of 140 °C. After all of the 1,2-epoxybutane is added
and refluxing has ceased, the
mixture is stirred and heated an additional 3 h at 140°C. The 140
°C mixture is then placed under
vacuum for 15 min to remove any traces of 1,2-epoxybutane. A light brown
liquid is isolated.
NMR is consistent with the desired compound.
EXAMPLE 2
Pr~aration of C9",EOSC(CH,~,CH~CH, Nonionic Surfactant
Neodol 91-8 (30.00 g, 58.7 mmol) is placed into a 250 ml three-necked round-
bottomed
flask, fitted with a heating mantle, magnetic stirrer, internal thermometer
and argon inlet, and
dried under vacuum at 75°C. After cooling to ambient and releasing the
vacuum with argon,
15 methylene chloride (12m1) and 2-methyl-1-butene (4.53 g, 64.6 mmol) are
added. Then boron
trifluoride diethyl etherate (0.83 g, 5.9 mmol) is added all at once. This
mixture is stirred 5 days
at ambient. After adding 200 ml diethyl ether, the mixture is washed once with
saturated sodium
bicarbonate and once with brine. The ether layer is dried under magnesium
sulfate and
concentrated by rotary evaporation to leave a yellow liquid. NMR is consistent
with the desired
20 compound.
EXAMPLE 3
Preparation of C9~~,E0$ CH~4CH, Nonionic Surfactant
Anhydrous tetrahydrofuran (250 ml) and 60% sodium hydride (8.22 g, 205.6 mmol)
are
placed into a 500 ml three-necked round-bottomed flask, fitted with a magnetic
stirrer, pressure
25 equalizing dropping funnel, internal thermometer and argon inlet. After
cooling the mixture to 0
°C, Neodol 91-8 (35.00 g, 68.5 mmol) is added dropwise over 10 minutes.
After warming to
ambient, the mixture is stirred for 2 h. 1-Iodopentane (33.93 g, 171.3 mmol)
is added dropwise
over 10 minutes. After stirring at ambient for 4 days, the mixture is quenched
with alcohol,
neutralized with concentrated HCI, diluted with 500 ml diethyl ether, and then
extracted once
30 with saturated NaHC03 and once with brine. The ether layer is dried under
magnesium sulfate
and concentrated by rotary evaporation. This mixture is purified by flash
chromatography (5:95
MeOH:CHzCIz) to yield a gold liquid. NMR is consistent with the desired
compound.
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61
The following examples are illustrative of the present invention, but are not
meant to
limit or otherwise define its scope. All parts, percentages and ratios used
herein are expressed as
percent weight unless otherwise specified.
In the following Examples, the abbreviations for the various ingredients used
for the
compositions have the following meanings.
LAS Sodium linear C 12 alkyl benzene sulfonate
MBASx Mid-chain branched primary alkyl (average total carbons = x) sulfate
MBAEXSz Mid-chain branched primary alkyl (average total carbons = z)
ethoxylate (average EO = x) sulfate, sodium salt
MBAEx Mid-chain branched primary alkyl (average total carbons = x)
ethoxylate (average EO = 8)
TFAA C16-18 alkyl N-methyl glucamide
CxyEzS Sodium ClX Cly branched alkyl sulfate condensed with z moles of
ethylene oxide
CxyFA C 1 x-C 1 y fatty acid
CxyEz A Clx-ly branched primary alcohol condensed with an average of z
moles of ethylene oxide
C24 N-Me Glucamide C 12-C 14 N-methyl glucamide
CxAPA Alkyl amido propyl amine
Citric acid Anhydrous citric acid
Carbonate Anhydrous sodium carbonate with a particle size between 200pm and
900pm
Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size
distribution between 425pm and 850 pm
Protease Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S
under the tradename Savinase
Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries
A/S under the tradename Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S
under the tradename Termamyl 60T
Lipase Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S
under the tradename Lipolase
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62
Endolase Endoglunase enzyme of activity 3000 CEVU/g sold
by NOVO
Industries A/S
PB 1 Anhydrous sodium perborate bleach of nominal
formula NaB02.H202
NOBS Nonanoyloxybenzene sulfonate in the form of
the sodium salt.
DTPMP Diethylene triamine penta (methylene phosphonate),
marketed by
Monsanto under the Trade name bequest 2060
MEA Monoethanolamine
PG Propanediol
EtOH Ethanol
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-
yl)amino)
stilbene-2:2'-disulfonate.
Silicone antifoamPolydimethylsiloxane 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.
NaOH Solution of sodium hydroxide
DTPA Diethylene triamine pentaacetic acid
NaTS Sodium toluene sulfonic acid
Fatty Acid (C C 12-C 14 fatty acid
12/ 14)
Fatty Acid (TPK)Topped palm kernel fatty acid
Fatty Acid (RPS)Rapeseed fatty acid
Borax Na tetraborate decahydrate
PAA Polyacrylic Acid (mw = 4500)
PEG Polyethylene glycol (mw=4600)
MES Alkyl methyl ester sulfonate
SAS Secondary alkyl sulfate
NaPS Sodium paraffin sulfonate
C45AS Sodium C14-C15 linear alkyl sulfate
CxyAS Sodium ClX Cly alkyl sulfate (or other salt
if specified)
AQA R2.N+(CH3)x((C2H40)yH)z with R2 = Cg - C 1 g
where x +z = 3, x = 0
to3,z=Oto3,y=1 to 15.
STPP Anhydrous sodium tripolyphosphate
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WO 00/50549 PCT/~JS00/04185
63
Zeolite A Hydrated Sodium Aluminosilicate of formula Nal2(A102Si02)12~
27H20 having a primary particle size in the range
from 0.1 to 10
micrometers
NaSKS-6 Crystalline layered silicate of formula 8 -Na2Si205
Bicarbonate Anhydrous sodium bicarbonate with a particle size
distribution between
400pm and 1200~m
Silicate Amorphous Sodium Silicate (Si02:Na20; 2.0 ratio)
Sulfate Anhydrous sodium sulfate
PAE ethoxylated tetraethylene pentamine
PIE ethoxylated polyethylene imine
PAEC methyl quaternized ethoxylated dihexylene triamine
MA/AA Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about
70,000.
CMC Sodium carboxymethyl cellulose
Protease Proteolytic enzyme of activity 4KNPU/g sold by
NOVO
Industries A/S under the tradename Savinase
Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold
by NOVO Industries
A/S under the tradename Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S
under the tradename Termamyl 60T
Lipase Lipolytic enzyme of activity 100kLU/g sold by
NOVO Industries A/S
under the tradename Lipolase
Percarbonate Sodium Percarbonate of nominal formula 2Na2C03.3H202
NaDCC Sodium dichloroisocyanurate
TAED Tetraacetylethylenediamine
DTPMP Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under Tradename bequest 2060
Photoactivated bleach Sulfonated Zinc Phthalocyanine bleach encapsulated in
dextrin soluble
polymer ,
HEDP 1,1-hydroxyethane diphosphonic acid
SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloyl
backbone
SRP 2 sulfonated ethoxylated terephthalate polymer
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64
SRP 3 methyl capped ethoxylated terephthalate polymer
Isofol 16 Condea trademark for C16 (average) Guerbet alcohols
CaCl2 Calcium chloride
MgCl2 Magnesium chloride
DTPA Diethylene triamine pentaacetic acid
EXAMPLES 4 to 8: Nonagueous Liguid Laundry Deterrent compositions
Non-limiting examples of bleach-containing nonaqueous liquid laundry detergent
are
prepared as follows.
Preparation of LAS Powder for Use as a Structurant
Sodium C12 linear alkyl benzene sulfonate (NaLAS) is processed into a powder
containing
two phases. One of these phases is soluble in the non-aqueous liquid detergent
compositions
herein and the other phase is insoluble. It is the insoluble fraction which
serves to add structure
and particle suspending capability to the non-aqueous phase of the
compositions herein.
NaLAS powder is produced by taking a slurry of NaLAS in water (approximately
40-50%
active) combined with dissolved sodium sulfate (3-15%) and hydrotrope, sodium
sulfosuccinate
(1-3%). The hydrotrope and sulfate are used to improve the characteristics of
the dry powder. A
drum dryer is used to dry the slurry into a flake. When the NaLAS is dried
with the sodium
sulfate, two distinct phases are created within the flake. The insoluble phase
creates a network
structure of aggregate small particles (0.4-2 um) which allows the finished
non-aqueous detergent
product to stably suspend solids.
The NaLAS powder prepared according to this example has the following makeup
shown
in Table I.
TABLE I
LAS Powder
Component Wt,
NaLAS 85%
Sulfate 11
Sulfosuccinate 2%
Water 2.5%
Unreacted, etc. balance to
100%
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insoluble LAS 17%
# of phase (via X-ray 2
diffraction)
Non-aqueous based heavy duty liquid laundry detergent compositions which
comprise the
capped nonionic surfactants of the present invention are presented below.
Component 4 5 ~ 6 7 8
LAS, From Example I 15 15 15 15 5
C12,13EOSB01 orC9,11E08B0121.5 15 10 5 25
C12,13E05 - 6.5 11.5 16.5 6.5
BPP 19.5 19 19 19 19
Sodium citrate dihydrate 7 7 7 7 7
Bleach activator 6 6 6 6 6
Sodium carbonate 9 9 9 9 9
Malefic-acrylic copolymer3 3 3 3 3
Colored speckles 0.4 0.4 0.4 0.4 0.4
EDDS 1 1 1 1 1
Cellulase Prills 0.1 0.1 0.1 0.1 0.1
Amylase Prills 0.4 0.4 0.4 0.4 0.4
Ethoxylated diamine quat 1.3 1.3 1.3 1.3 1.3
Sodium Perborate 12 12 12 12 12
Optionals including: brightener,balancebalancebalancebalancebalance
colorant, perfume, thickener,
suds
suppressor, colored speckles
etc.
100% 100% 100% 100% 100%
5
The resulting compositions are stable, anhydrous heavy-duty liquid laundry
detergents
which provide excellent rates of mixing with water as well as good stain and
soil removal
performance when used in normal fabric laundering operations.
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EXAMPLE 9: Hand Dishwashing Liguid compositions
The following Examples further illustrates the invention herein with respect
to a hand
dishwashing liquid.
Example 19:
Ingredient % wt. Ranged% wt.)
C9,11 E08B01 5.0 1 - 20
MBAE2S 15 2.0 0.5-10
Ammonium C12-13 alkyl sulfate7.0 2-35
C 12-C 14 ethoxy ( 1 ) sulfate20.5 5-35
Coconut amine oxide 2.6 2-S
Betaine/Tetronic 704~** 0.87-0.10 0-2 (mix)
Alcohol Ethoxylate C9_1 1E9 1.0 0.5-10
Ammonium xylene sulfonate 4.0 1-6
Ethanol 4,0 0_7
Ammonium citrate 0.06 0-1.0
Magnesium chloride 3.3 0-4.0
Calcium chloride 2.5 0-4.0
Ammonium sulfate 0.08 0-4.0
Perfume 0.18 0-0.5
Maxatase~ protease 0.50 0-1.0
Water and minors ----------Balance--------------------
** Cocoalkyl betaine.
EXAMPLES 10 to 14: Shampoo positions
com
ExamQle
Number
Component 10 11 12 13 14
Ammonium laureth-2 sulfate5 3 2 10 8
Ammonium lauryl sulfate 5 S 4 5 8
C9,11E08B01 2 3 4 5 7
Cocamide MEA 0 0.68 0.68 0.8 0
PEG 14M 0.1 0.35 0.5 0.1 0
Cocoamidopropylbetaine 2.5 2.5 0 0 1.5
Cetylalcohol 0.42 0.42 0.42 0.5 0.5
Stearylalcohol 0.18 0.18 0.18 0.2 0.18
Ethylene glycol distearate1.5 1.5 1.5 1.5 1.5
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Dimethicone 1 1.75 1.75 1.75 1.75 2.0
Perfume solution 0.45 0.45 0.45 0.45 0.45
.
DMDM hydantoin 0.37 0.37 0.37 0.37 0.37
Color solution (ppm) 64 64 64 64 64
Water and minors ------------------to ------------
q. 100%
s. --
1. Dimethicone is a 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone
gum available
from General Electric Silicones Division and a dimethicone fluid having a
viscosity of 350
centistokes.
EXAMPLES 15 to 30: Granular Laundry Deter ents
The following laundry detergent compositions are prepared in accord with the
invention:
15 16 17 18 19 20
MBAS 14.4 8.0 4.0 ~ 4.0 8.0 4.0 4.0
C45AS - 4.0 2.8 - 4.0 2.8
LAS - - 1.2 - - 1.2
C12,13EOSB01 3.4 3.4 3.4 3.4 3.4 3.4
AQA 0.4 0.5 0.6 0.8 0.8 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
DTPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 0.3 0.3 0.3 0.3 0.3 0.3
Protease 0.26 0.26 0.26 0.26 0.26 0.26
Amylase 0.1 0.1 0.1 0.1 0.1 0.1
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm
bleach
Brightener 1 ~ 0.09 0.09 0.09 0.09 0.09 0.09
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Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to
100%
Density in g/litre850 850 850 850 850 850
~'he following laundry detergent compositions are prepared in accord with the
invention:
21 22 23 24 25
MBAS 14.4 22 16.5 11 1 - 10 -
5.5 25
Any Combination 0 1 - 11 16.5 0 - 5
o 5.5
C45 AS
C45E1S
LAS
C16 SAS
C 14-17 NaPS
C14-18 MES
MBAE2S 14.3
AQA 2 2 2 2 0.5 -
4
C12,13E6.SB01 1.5 1.5 1.5 1.5 1 -4
Zeolite A 27.8 27.8 27.8 27.8 20 -
30
PAA 2.3 2.3 2.3 2.3 0 - 5
Carbonate 27.3 27.3 27.3 27.3 20 -
30
Silicate 0.6 0.6 0.6 0.6 0 - 2
PB1 1.0 1.0 1.0 1.0 0 - 3
Protease 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5
Cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.5
Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-1
SRP 1 0.4 0.4 0.4 0.4 0 - 1
.
Brightener 1 0.2 0.2 0.2 0.2 0 - 0.3
or 2
PEG 1.6 1.6 1.6 1.6 0-2
Sulfate 5.5 5.5 5.5 5.5 0 - 6
Silicone Antifoam0.42 0.42 0.42 0.42 0 - 0.5
Moisture & Minors---Balance---
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Density (g/L) ~ 663 ~ 663 ~ 663 ~ 663 ~ 600 - 700
The following laundry detergent compositions are prepared in accord with the
invention:
26 27 28 ~ 29 30
MBAS 14.4 16.5 12.5 8.5 4 1 - 25
Any Combination 0 - 10 14 18.5 0 - 20
of: 6
C45 AS
C45E1S
LAS
C16 SAS
C14-17 NaPS
C14-18 MES
MBAE2S 14.3
AQA 2 2 2 2 1-4
TFAA 1.6 1.6 1.6 1.6 0 - 4
C 12,14E04B01 S 5 5 5 1 - 6
Zeolite A 15 15 15 15 10 - 30
NaSKS-6 11 11 11 11 S - 15
Citrate 3 3 3 3 0 - 8
MA/AA 4.8 4.8 4.8 4.8 0 - 8
HEDP 0.5 0.5 0.5 0.5 0 - 1
Carbonate 8.5 8.5 8.5 8.5 0 - 15
Percarbonate 20.7 20.7 20.7 20.7 0 - 25
or PB 1
TAED 4.8 4.8 4.8 4.8 0 - 8
Protease 0.9 0.9 0.9 0.9 0 - 1
Lipase 0.15 0.15 0.15 0.15 0 - 0.3
Cellulase 0.26 0.26 0.26 0.26 0 - 0.5
Amylase 0.36 0.36 0.36 0.36 0 - 0.5
SRP 1 0.2 0.2 0.2 0.2 0 - 0.5
Brightener 1 0.2 0.2 0.2 0.2 0 - 0.4
or 2
Sulfate ~ 2.3 2.3 2.3 2.3 0 - 25
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Silicone Antifoam 0.4 0.4 0.4 0 - 1
Moisture & Minors---Balance---
Density (g/L) 850 850 850 850
EXAMPLES 31 to 38: Hard Surface Cleaners
The following compositions were made by mixing the listed ingredients in the
listed proportions.
These compositions were used neat to clean marble and dilute to clean
lacquered wooden floors.
5 Excellent cleaning and surface safety performance was observed.
31 32 33 34 35 36 37 38
C 12,13EOSB013.0 3.0 5.0 3.2 3.2 3.2 8.0 8.0
C23E3 1.0 1.0 1.5 1.3 1.3 1.5 3.0 3.5
C24E21 2.0 2.0 2.5 1.9 1.9 2.0 5.0 6.0
NaPS 2.0 1.5 1.2 1.2 1.0 1.7 3.0 2.5
NaTS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0
MgS04 0.20 0.9 0.30 0.50 1.3 2.0 1.0 3.0
Citrate 0.3 1.0 0.5 0.75 1.8 3.0 1.5 6.0
NaHC03 0.06 0.1 - 0.1 - 0.2 - -
Na2HP04 - - 0.1 - 0.3 - - -
Na2H2P2O7 - - - - - - 0.2 0.5
pH 8.0 7.5 7.0 7.25 8.0 7.4 7.5 7.2
Water and q.s. 100%
to
Minors
