Note: Descriptions are shown in the official language in which they were submitted.
WO 94/07986 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08874
DETERGENT COMPOSITION COMPRISING A NONALKYLOXYLATED
NONIONIC SURFACTANT
This invention relates to machine dishwashing compositions
comprising a cleaning surfactant system, and preferably a
water-soluble detergent builder system, and a suds
suppressor system. The compositions comprise said
surfactant system at a level which is directly related to
the critical micelle concentration of the surfactant
system, measured in water. Machine dishwashing processes
are also provided.
Conventional machine dishwashing detergent products differ
from commonly available manual dishwashing and laundry
products in one key respect. Whereas surfactants are
traditionally the key active cleaning ingredients of manual
dishwashing detergent products and are also important
components of laundry detergent products, surfactants are
present, if at a11, in conventional machine dishwashing
detergent products at only low levels, of typically less
than 2% by weight.
Commercially available granular machine dishwashing
compositions most often contain certain alkoxylated
nonionic surfactants, especially the low-foaming
ethoxylated or ethoxylated/propoxylated alcohols, which are
usually included at low levels in the formulations as
wetting agents or to provide control of sudsing rather
WO 94/07986 ~ PCT/US93/08874
2
than to provide a primary cleaning function. These
alkoxylated nonionic surfactants commonly also find use as
wetting agents in rinse aid compositions.
Certain other surfactants, which do not fall into the
general class of the low-foaming/suds controlling
alkoxylated nonionics, may act as a source of foaming and
sudsing under the conditions of heat and agitation of a
machine dishwashing process. This sudsing and foaming is
highly undesirable in such a process. The desire to avoid
such sudsing and foaming may explain why these other
surfactants are not currently incorporated into
commercially available machine dishwashing detergent
products as cleaning agents.
It is known that silicone suds suppressor may be
incorporated into machine dishwashing detergent
compositions being disclosed in for example US-A-3933672
and US-A-4136045. The incorporation of such silicone suds
suppressor ameliorates the problem of sudsing and foaming
during the dishwashing process and thus enables the
formulator to include higher levels of surfactant which
need not be inherently low foaming into the detergent
product.
Builder compounds are conventionally used in machine
dishwashing and rinsing detergent products. Their
principal action is to chelate magnesium and calcium ions.
The magnesium and calcium ions may, in the absence of
builder compounds or in underbuilt conditions, form
insoluble salts which deposit as visible spots or films on
the surfaces of the articles being washed. It is desirable
that the builder compounds used in machine dishwashing
detergent products are water-soluble since water insoluble
builder compounds may also deposit on the articles being
washed, remaining as visible spots at the end of the wash
process.
WO 94/07986 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08874
3
The overall performance of a machine dishwashing detergent
product is judged on a combination of its effectiveness in
removing soils, particularly greasy soils, and its ability
to prevent the redepositon of the soils, or the breakdown
products of the soils or of any insoluble salts on the
articles being washed. The insoluble salts may be the
calcium, magnesium or heavy metal ion-containing salts of
the soils, or the breakdown products of the soils, or they
may be purely inorganic in nature. Redeposition effects
result in the articles being coated in an unseemly film,
appearing streaked or being covered in visible spots.
Spotting, filming and streaking effects are usually most
noticeable on glassware and on plastic articles.
For reasons of environmental compatibility it is desirable
that machine dishwashing or rinsing detergent products are
free from chlorine bleaches or phosphate builder compounds.
However, the optimization of cleaning performance and
minimization of spotting and filming effects are known to
be particular challenges for the formulators of machine
dishwashing containing no chlorine bleach and/or no
phosphate builder compound.
The Applicants have now surprisingly found that improved
cleaning performance, particularly improved soil removal
performance, may be achieved in a machine dishwashing
process by the inclusion in the detergent composition used
therein of a cleaning surfactant system, which is distinct
from the more typical wetting and/or suds controlling
alkoxylated nonionic surfactant systems, incorporated at a
level in the composition which is directly related to the
critical micelle concentration of the surfactant system.
The Applicants have also found that enhanced cleaning
performance may be obtained in a machine dishwashing
process where the wash solution employed in the process
..,.
WO 94/07986 PCT/US93/08874
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4
contains surfactant at a level which is directly related to
the critical micelle concentration (CMC) of that
surfactant. In general, where the cleaning surfactant
system has a high CMC value high levels of that surfactant
system will be needed to provide effective cleaning
performance. Where the surfactant system has a low CMC
value lower levels of incorporation are required.
Whilst not wishing to be bound by theory, the Applicants
believe that where certain surfactants for example, amine
oxide surfactants are employed at too low a level in a
machine dishwashing process the surfactant may physically
or chemically interact with any fatty acids present in the
wash solution, in a way which adversely affects the
cleaning performance of the surfactant. For example, it is
believed that with certain surfactants relatively strong
surfactant-fatty acid complexes may be formed which
compromise the availability of the surfactant for
detergency purposes.
Free fatty acids can be present at not insignificant levels
(up to 30% by weight) in "cooked" fat soils, and are also
produced in the enzymatic hydrolysis of protein, and fat
soils. Optimization of surfactant level, with regard to the
critical micelle concentration of the surfactant system, is
hence especially important in the formulation of enzyme-
containing machine dishwashing compositions, particularly
those containing lipolytic enzymes.
The measured CMC value of a surfactant system is to an
extent dependent upon the nature of the solution medium in
which the measurement is made. The ionic strength of the
solution and temperature are relevant factors. The CMC of a
surfactant in the wash solution of a typical machine
dishwashing process, which is formed by dissolving a
multicomponent detergent product in a volume of water at a
certain temperature, will thus be different from, but
y"' WO 94/07986 ~ ~ ~ PCT/US93/08874
related to, the CMC value measured in water under standard
defined conditions CMC. The Applicants believe, and have
found in practice, that the CMC is however an extremely
useful indicator to enable the determination of an
effective "in wash solution" and hence "in product" level
of a surfactant system for use in a machine dishwashing
process.
The critical micelle concentration of a surfactant system
in a solution medium is, as has been noted above, to an
extent dependent on the nature of that solution medium.
Where the ionic strength of the solution medium is
increased, the CMC value will decrease. Thus more effective
cleaning performance is predicted to be obtained in a
machine dishwashing process for wash solutions of high
ionic strength in comparison to those of lower ionic
strength for a fixed concentration of surfactant in the
wash solution.
Preferably, said surfactant systems in accord with the
invention contain at least in part a surfactant which
demonstrates lime soap dispersant capability and hence acts
such as to mitigate spotting and filming effect of articles
in the wash. In addition, the incorporation of a suds
suppressor system, as a preferred optional component, means
that the surfactant system may be of either a low or high
foaming character and may be present at relatively high
levels in the composition.
A lime soap dispersant is a material that prevents the
precipitation of alkali metal, ammonium or amine salts of
fatty acids by calcium or magnesium ions. Traditionally,
lime soap dispersants have found widespread use in fatty
acid soap-containing detergent products such as bar soaps
and soap flakes for use in laundering processes. Lime soap
dispersants are included in such fatty acid soap containing
detergent product, to aid dispersion of the highly
WO 94/07986 PCT/US93/08874
~.~4~~'~7
undesirable lime soap scums or curds which inevitable arise
due to the fatty acid soaps forming insoluble magnesium and
calcium salts with hardness ions present in the wash
solution.
Commercially available machine dishwashing compositions -
typically contain only non-soap surfactants as the
components of any surfactant systems. Many, non-soap
surfactants, typically do not form insoluble magnesium and
calcium salts with hardness ions present in the wash
solution, and therefore the inclusion of lime soap
dispersants in detergent compositions containing only non-
soap surfactants is conventionally seen as unnecessary.
Not a11 surfactants demonstrate lime soap dispersant
capability. However, it is desirable in the detergent
compositions of the invention that any lime soap dispersant
component of the surfactant system is also an effective
surface active agent.
It is therefore an object of the present invention to
provide detergent compositions containing a surfactant
system, and preferably containing water-soluble builder
compound and/or a suds suppressor system which provides for
improved cleaning performance, when used in machine
dishwashing processes.
It. is a further object of the present invention to provide
machine dishwashing detergent compositions which contain a
surfactant system at a level directly related to the
critical micelle concentration, measured in water, of said
surfactant system. Preferably, the surfactant system
contains, at least in part, surfactant which demonstrates
good lime soap dispersant capability.
The machine dishwashing detergent compositions of the
present invention are of particular value when formulated
""'""' WO 94/07986 PCT/US93/08874
~~.~5~ 77
as compositions containing no chlorine bleach and no
phosphate builder compound.
summary of the invention
According to the present invention there is provided a
detergent composition suitable for use in a machine
dishwashing process containing a surfactant system free
from alkoxylated nonionic surfactant at a level, in ppm by
weight, of greater than 1500 times the critical micelle
concentration, in ppm, of said surfactant system, measured
in water.
Preferably, at least 10% by weight of the surfactant system
comprises surfactant having a lime soap dispersant power of
no more than 8 .
Preferably, the composition contains from 1% to 80% by
weight of detergent builder compound.
Preferably the composition contains from 0.01% to 15% by
weight of a suds suppressor system.
Preferably, where present, the detergent builder compound
is a non-phosphate detergent builder compound. Preferably
the composition is free from chlorine bleach.
According to another aspect the present invention there is
also provided a machine dishwashing process comprising
treating soiled articles selected from crockery, glassware,
hollowware and cutlery and mixtures thereof, with a wash
solution having dissolved or dispensed therein an amount of
machine dishwashing composition in accord with the
compositional aspect of the invention, such that the
concentration, in ppm by weight, of said surfactant system
in said wash solution is at least six times, preferably at
WO 94/07986 PCT/US93/08874
~l~a~~'~ ,
s
least ten times, more preferably at least twenty times, and
most preferably at least thirty times the critical micelle
concentration, in ppm, of the surfactant system, measured ,
in water.
Typically, in a machine dishwashing process from 8g to 60g
of product will be employed, the product being dissolved or
dispersed in a wash solution of volume from 3 to 10 litres,
to give a product concentration of from 800 ppm to 20,00
ppm, preferably from 2,000 to 10,000 ppm, more preferably
from 3,000 to 6,000 ppm.
Surfactant system
The machine dishwashing compositions of the invention
contain as an essential component a surfactant system
comprising surfactant which may be selected from anionic,
cationic, nonionic, ampholytic, amphoteric and zwitterionic
surfactants and mixtures thereof. The primary role of said
surfactant system is to aid cleaning, that is soil removal.
The surfactant system of the invention does not contain the
alkoxylated nonionic surfactant compounds described herein.
Such alkoxylated nonionic surfactant compounds may however
be present as optional components of the composition as
wetting agents or as suds controlling components.
The surfactant system is typically present at a level of
from 1.5% to 50% by weight, more preferably 2.5% to 25% by
weight, most preferably from 3% to 20% by weight of the
composition, the components of the surfactant system having
been selected on the basis of their critical micelle
concentration, as measured in water, to allow inclusion at
such levels by weight.
The compositions of the invention preferably contain at
most, only low levels of fatty acid compounds, such as
WO 94/07986 ~ PCT/US93/08874
9
fatty acids, soap surfactants, and other fatty acid salts.
By soap surfactants it is meant herein the sodium and
potassium salts of fatty acids, typically with a carbon,
chain length of from 8 to 18 carbons atom, including for
example, the sodium and potassium salts of stearic,
' palmitic and oleic acids. The compositions of the
invention may however incorporate at levels of no more than
3% by weight, more preferably no more than 1% by weight,
fatty acid compounds, such as for example the C14-C20 fatty
acids, fatty acid-containing compounds such as aluminium
tristearate and soap surfactants which may act as corrosion
inhibitors.
The surfactant system is present in the machine dishwashing
compositions in accord with the invention at a level, in
ppm by weight, of greater than 1500, preferably greater
than 2500, more preferably greater than 5000, most
preferably greater than 10,000 times the critical micelle
concentration of said surfactant system, expressed in ppm,
measured in water.
The surfactant system for inclusion in the compositions in
accord with the invention preferably has a critical micelle
concentration, in water, of not more than 100ppm, more
preferably not more-'than 50gpm, most preferably not more
than 20ppm.
In a process aspect of the invention the compositions are
employed at a product dosage level to provide a
concentration of surfactant system in the wash solution,
expressed in ppm by weight, of at least six times,
preferably at least ten times, more preferably at least
twenty times, most preferably at least thirty times the
critical micelle concentration of the surfactant system, in
ppm, measured in water.
WO 94/07986 PCT/US93/08874
~14~~'~'~
In a preferred aspect of the invention at least 10% by
weight, more preferably 25% by weight, most preferably at
least~50%, and in an exemplary composition in accord with
the invention 100% by weight of the surfactant system
comprises surfactant having good lime soap dispersant
capability, characterized in that said surfactant has a
lime soap dispersant power of no more than 8, preferably no
more than 7, more preferably less than 6.
A lime soap dispersant is a material that prevents the
precipitation of alkali metal, ammonium or amine salts of
fatty acids by calcium or magnesium ions. A numerical
measure of the effectiveness of a lime soap dispersant is
given by the lime soap dispensing power (LSDP) which is
determined using the lime soap dispersion test as described
in an article by H.C. Borghetty and C.A. Bergman, J. Am.
Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime
soap dispersion test method is widely used by practitioners
in this art field being referred to , for example, in the
following review articles; W.N. Linfield, Surfactant
Science Series, Volume 7, p3; W.N. Linfield, Tenside Surf.
Det. , Volume 27, pages159-161, (1990); and M.K. Nagarajan,
W.F. Masler, Cosmetics and Toiletries, Volume 104, pages
71-73, (1989). The LSDP is the % weight ratio of
dispersing agent to sodium oleate required to disperse the
lime soap deposits formed by 0.025g of sodium oleate in
30m1 of water of 333ppm
CaC03 (Ca:Mg=3:2) equivalent hardness.
In the Borghetty/Bergman lime soap dispersion test 5m1 of a
0.5% by weight solution of sodium oleate is added to a test
tube, followed by 10m1 of a hard water solution containing
600ppm Ca2+ and 400ppm Mg2+ (1000ppm as CaC03 equivalent,
70~ Clark Hardness) which will cause formation of a lime
soap deposit (or curd). An arbitrary amount (less than
15m1) of dispersing agent as a 0.25% by weight solution is
then added to the test tube. The total volume of solution
"- WO 94/07986 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08874
11
in the test tube is then made up to 30m1 and the test tube
is stoppered, inverted 20 times and then allowed to stand
for 3-0.-seconds. The contents of the test tube are then
visually inspected to check if the lime soap deposits are
still intact or whether they have been dispersed into the
solution. The test procedure is repeated using different
amounts of dispersing agent solution until the minimum
amount of dispersing agent solution which will cause
dispersion of the lime soap deposits is obtained.
The lime soap dispersing power is then obtained as:
LSDP = (weiQht.of lime soak dispersin~agrent) x 100
(weight of sodium oleate)
Thus in accord with the test method described above a
material with a lower LSDP is a more effective lime soap
dispersant than one with a higher LSDP.
A listing of suitable lime soap dispersants for use in the
surfactant system in accord with the invention is given in
the above mentioned review by M. Linfield to be found in
Tenside. Sust. Det., Volume 27, pages 159-161 (1990).
Surfactants having good lime soap~dispersant capability
will include certain amine oxides, betaines, sulfobetaines,
alkyl ethoxysulfates and ethoxylated alcohols.
Exemplary surfactants having a LSDP of no more than 8 for
incorporation in the surfactant system in accord with the
invention include C16-Clg dimethyl amine oxide, C12-C18
alkyl ethoxysulfates with an average degree of ethoxylation
of from 1-5, particularly C12-C15 alkyl ethoxysulfate
surfactant with a degree of ethoxylation of about 3
(LSDP=4), and the C13-C15 ethoxylated alcohols with an
average degree of ethoxylation of either 12 (LSDP=6) or 30,
WO 94/07986 PCT/US93/08874
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12
sold under the trade names Lutensol A012 and Lutensol A030
respectively, by BASF GmbH.
The surfactant system is preferably formulated to be t
compatible with any enzyme components present in the
composition. In liquid or gel compositions the surfactant
system is most preferably formulated such that it promotes,
or at least does not degrade, the stability of any enzyme
in these compositions.
A typical listing of anionic, nonionic, ampholytic, and
zwitterionic classes, and species of these surfactants, is
given in U.S.P. 3,929,678 issued to Laughlin and Heuring on
December 30, 1975. A list of suitable cationic surfactants
is given in U.S.P. 4,259,217 issued to Murphy on March 31,
1981.
Anionic surfactant
The anionic surfactant may be essentially any anionic
surfactant, including anionic sulfate, and sulfonate
surfactant.
Highly preferred anionic surfactants herein are sodium or
potassium salt-forms for which the corresponding calcium
salt form has a low Krafft temperature of for example 30
deg. C or below, or, even better, 20 deg. C or lower.
Without being limited by theory, including anionic
surfacants, the calcium salts of which have low Krafft
temperatures, into the surfactant systems in accord with
the present invention tends to minimize film formation on
hard surfaces. Examples of such highly preferred anionic
surfactants are the alkyl ethoxy sulfate surfactants.
"~" WO 94/07986 ~ 1 ~ ~ ~ PCT/US93/08874
13
Anionic sulfate surfactant
The anionic sulfate surfactant may be any organic sulfate
surfactant. It is preferably selected from the group
consisting of C6-C20 linear or branched chain alkyl sulfate
which has been ethoxylated with from about 0.5 to about 20
moles of ethylene oxide per molecule, Cg-C1~ acyl-N-(C1-C4
alkyl) glucamine sulfated, -N-(C2-C4 hydroxyalkyl)
glucamine sulfate, and mixtures thereof. More preferably,
the anionic sulfate surfactant is a C6-Clg alkyl sulfate
which has been ethoxylated with from about 0.5 to about 20,
preferably from about 0.5 to about 5, moles of ethylene
oxide per molecule.
Preferred alkyl ethoxy sulfate surfactants comprise a
primary alkyl ethoxy sulfate derived from the condensation
product of a C6-Clg alcohol with an average of from about
0.5 to about 20, preferably from about 0.5 to about 5,
ethylene oxide groups. The C6-Clg alcohol itself is
preferable commercially available. C12-C15 alkyl sulfate
which has been ethoxylated with from about 1 to about 5
moles of ethylene oxide per molecule is preferred alkyl
ethoxy sulfate surfactant. Highly branched C10-Clg alkyl
ethoxy sulfates, with a degree of ethoxylation of from 5 to
20, in combination with linear methyl branched C6-C10 alkyl
ethoxy sulfates with a degree of ethoxylation of from 5 to
20 are also preferred.
Where the compositions of the invention are formulated to
have a pH of between 6 to 9.5, preferably between 7.5 to 9,
wherein the pH is defined herein to be the pH of a 1%
solution of the composition measured at 20~C, surprisingly
robust soil removal, particularly proteolytic soil removal,
is obtained when C10-Clg alkyl ethoxysulfate surfactant,
with an average degree of ethoxylation of from 0.5 to 5 is
incorporated into the composition in combination with a
proteolytic enzyme, such as neutral or alkaline proteases
WO 94/07986 ~ PCT/US93/08874
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14
at a level of active enzyme of from 0.005% to 2%. Preferred
alkyl ethoxysulfate surfactant for inclusion in such
compositions with a pH of between 6 to 9.5 are the C12-C15
alkyl ethoxysulfate surfactants with an average degree of
ethoxylation of from 1 to 5, preferably 2 to 4, most
preferably 3.
Conventional base-catalyzed ethoxylation processes to
produce an average degree of ethoxylation of 12 result in a
distribution of individual ethoxylates ranging from 1 to 15
ethoxy groups per mole of alcohol, so that the desired
average can be obtained in a variety of ways. Blends can
be made of material having different degrees of
ethoxylation and/or different ethoxylate distributions
arising from the specific ethoxylation techniques employed
and subsequent processing steps such as distillation.
Anionic sulfate surfactants include the C5-C17 acyl-N-(C1-
C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates,
preferably those in which the C5-C17 acyl group is derived
from coconut or palm kernel oil. These materials can be
prepared by the method disclosed in U.S. Patent 2,717,894,
Schwartz, issued September 13, 1955.
The counterion for the anionic sulfate surfactant component
is preferably selected from calcium, sodium, potassium,
magnesium, ammonium, or alkanol-ammonium, and mixtures
thereof, more preferably sodium or potassium, or mixtures
thereof.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein
include essentially any sulfonate surfactants including, .
for example, the salts (eg . alkali metal salts) of C5-C20
linear alkylbenzene sulfonates, C6-C22 primary or secondary
alkane sulfonates, C6-C24 olefin sulfonates, sulfonated
WO 94/07986 ~ ;~ ~ ~ ~ PCT/US93/08874
polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfonates,
paraffin sulfonates, and any mixtures thereof. Certain
sulfonate surfactants may form precipitates with hardness
ions making them less preferred for use herein.
Anionic alkyl ethoxy carboxylate surfactant
Alkyl ethoxy carboxylates suitable for use herein include
those with the fomula RO(CH2CH20)x CH2C00-M+ wherein R is
a C6 to Clg alkyl group, x ranges from O to 10, and the
ethoxylate distribution is such that, on a weight basis,
the amount of material where x is 0 is less than about 20
%, preferably less than about 15 %, most preferably less
than about 10 %, and the amount of material where x is
greater than 7, is less than about 25 %, preferably less
than about 15 %, most preferably less than about 10 %, the
average x is from about 2 to 4 when the average R is C13 or
less, and the average x is from about 3 to 6 when the
average R is greater than C13, and M is a cation,
preferably chosen from alkali metal, alkaline earth metal,
ammonium, mono-, di-, and tri-ethanol-ammonium, most
preferably from sodium, potassium, ammonium and mixtures
thereof with magnesium ions. The preferred alkyl ethoxy
carboxylates are those where R is a C12 to Clg alkyl group.
Anionic alkyl oolyethoxy oolycarboxylate surfactant
Alkyl polyethoxy polcarboxylate surfactants suitable for
use herein include those having the formula .
R - O - ( CH - CH - O ) x - R3
R1 R2
wherein R is a C6 to Clg alkyl group, x is from 1 to 25, R1
and R2 are selected from the group consisting of hydrogen,
WO 94/07986 r PCT/US93/08874
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16
methyl acid radical, succinic acid radical, hydroxysuccinic
acid radical, and mixtures thereof, wherein at least one R1
or R2 is a succinic acid radical or hydroxysuccinic acid
radical, and R3 is selected from the group consisting of
hydrogen, substituted or unsubstituted hydrocarbon having
between 1 and 8 carbon atoms, and mixtures thereof.
Alkali metal sarcosinate surfactant
Other anionic surfactants suitable for the purposes of the
invention are the alkali metal sarcosinates of formula
R-CON (R1) CH2 LOOM
wherein R is a C5-C17 linear or branched alkyl or alkenyl
group, R1 is a C1-C4 alkyl group and M is an alkali metal
ion. Preferred examples are the myristyl and oleyl methyl
sarcosinates in the form of their sodium salts.
Alkyl ester sulphonate surfactants
Another class of anionic surfactants useful herein are the
alkyl ester sulfonate surfactants which include linear
esters of Cg-C2p carboxylic acids (i.e., fatty acids) which
are sulfonated with gaseous S03 according to "The Journal
of the American Oil Chemists Society," 52 (1975), pp. 323-
329. Suitable starting materials would include natural
fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactants have the
structural formula:
O
R3 - CH - C ~ OR4
S03M
wherein R3 is a Cg-C2p hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably
an alkyl, or combination thereof, and M is a cation which
WO 94/07986 ~ ~ ~ ~ ~ ~ PCT/US93/08874
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forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as
sodium,_ potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R3 is
C10-Clg alkyl, and R4is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates
wherein R3 is C10-Clg alkyl.
Other anionic surfactants
Other anionic surfactants useful for detersive purposes can
also be included in the compositions hereof. These can
include salts (including, for example, sodium, potassium,
ammonium, and substituted ammonium salts such as mono-, di-
and triethanolamine salts) of fatty.oleyl glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl
phosphates, isethionates such as the acyl isethionates, N-
acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated C12
C18 monoesters) diesters of sulfosuccinate (especially
saturated and unsaturated C6-C14 diesters), N-acyl
sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated
compounds being described herein), branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of
the formula RO(CH2CH20)kCH2C00-M+ wherein R is a C8-CZ2
alkyl, k is an integer from 0 to 10, and M is a soluble
salt-forming cation, and fatty acids esterified with
isethionic acid and neutralized with sodium hydroxide.
Resin acids and hydrogenated resin acids are also suitable,
such as rosin, hydrogenated rosin, and resin acids and
hydrogenated resin acids present in or derived from tall
oil. Further examples are given in "Surface Active Agents
and Detergents" (Vol. I and II by Schwartz, Perry and
18
Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30,
1975 to Laughlin, et al. at Column 23, line 58 through
Column 29, line 23.
Nonionic surfactant
The nonionic surfactant components of the surfactant system
in accord with the invention do not include the nonionic
alkylene oxide condensates (alkyloxylated nonionic
surfactants) described hereinafter, which however may be
present as optional components of compositions in accord
with the invention for their suds controlling and/or
wetting agent properties.
Suitable nonionic detergent surfactants are generally
disclosed in U.S. Patent 3,929,678, Laughlin et al., issued
December 30, 1975, at column 13, line 14 through column l6,
line 6. Exemplary, non-limiting classes of useful nonionic
surfactants are listed below.
Nonionic_polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are
those having the structural formula .
O R1
(I)
R2 - C - N - Z
wherein . R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl, or a mixture thereof; preferable C1-C4
alkyl, more preferably C1 or C2 alkyl, most preferably C1
alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl,
preferably straight-chain C5-Clg alkyl or alkenyl, more
preferably straight-chain Cg-C17 alkyl or alkenyl, most
B
WO 94/07986 ~ ~ ~ ~ ~ PCT/US93/08874
19
preferably straight-chain C11-C1~ alkyl or alkenyl, or
mixture thereof; and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z
preferably will be derived from a reducing sugar in a
reductive amination reaction; more preferably Z is a
glycityl. Suitable reducing sugars include glucose,
fructose, maltose, lactose, galactose, mannose, and xylose.
As raw materials, high dextrose corn syrup, high fructose
corn syrup, and high maltose corn syrup can be utilized as
well as the individual sugars listed above. These corn
syrups may yield a mix of sugar components for Z. It
should be understood that it is by no means intended to
exclude other suitable raw materials. Z preferably will be
selected from the group consisting of -CH2-(CHOH)n-CH2-OH2,
-CH(CH20H)-(CHOH)n-, -CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-
CH20H, where n is an integer from 3 to 5, inclusive, and R'
is H or a cyclic or aliphatic monosaccharide, and
alkoxylate derivative thereof. Most preferred are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
In Formula (I), R1 can be, for example, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-
hydroxy propyl. '
R2-CO-N< can be, for example, cocamide, stearamide,
oleamide, lauramide, myristamide, capricamide, palmitamide,
tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-
deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-
deoxymannityl, 1-deoxymaltotriotityl, etc.
The most preferred polyhydroxy fatty acid amide has the
general formula .
"-"
WO 94/07986 PCT/US93/08874
O CH3
R2 C N - CH2 - (CHOH)4CH20H
wherein R2 is a straight chain C11-C17 alkyl or alkenyl
group.
Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed
in U.S. Patent 4,565,647, Llenado, issued January 21, 1986,
having a hydrophobic group containing from about 6 to about
carbon atoms, preferably from about 10 to about 16
carbon atoms and a polysaccharide, e.g., a polyglycoside,
hydrophilic group containng 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 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used,
e.g., glucose, galactose and galactosyl moieties can be
substituted for the glucosyl moieties. (Optionally the
hydrophobic group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to
a glucoside or galactoside.) The intersaccharide bonds can
be, e.g., between the one position of the additional
saccharide units and the 2-, 3-, 4-, and/or 6- positions on
the preceding saccharide units.
Optionally, and less desirably, there can be a
polyalkyleneoxide chain joining the hydrophobic moiety and
the polysaccharide moiety. The preferred alkyleneoxide is
ethylene oxide. Typical hydrophobic groups include alkyl
groups, either saturated or unsaturated, branched or
unbranched containing from 8 to 18, preferably from 10 to
16, carbon atoms. Preferably, the alkyl group is a
straight-chain saturated alkyl group. The alkyl group can
contain up to about 3 hydroxyl groups and/or the
polyalkyleneoxide chain can contain up to about 10,
WO 94/07986 PCT/US93/08874
21
preferably less than 5, alkyleneoxide moieties. Suitable
alkyl polysaccharides are octyl, nonyldecyl,
undecy.ldodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-,
penta-, and hexaglucosides, galatoses. Suitable mixtures
include coconut alkyl, di-, tri-, tetra-, and
pentaglucosides and tallow alkyl tetra-, penta- and
hexaglucosides.
The 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 10 to 18,
preferably from 12 to 14, carbon atoms; n is 2 or 3,
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 then reacted
with glucose, or a source of glucose, to form the glucoside
(attachment at the 1-position). The additional glycosyl
units can then be attached between their 1-position and the
preceding glycosyl units 2-,3-, 4- and/or 6-position,
preferably predominantly the 2-position.
Nonionic fattv acid amide surfactant
Fatty acid amide surfactants suitable for use herein are
those having the formula:
O
TI
R6- C-N(R7) 2
wherein R6 is an alkyl group containing from 7 to 21,
preferably from 9 to 17 carbon atoms and each R7 is
selected from the group consisting of hydrogen, C1-C4
alkyl, C1-C4 hydroxyalkyl, and
WO 94/07986 PCT/US93/08874
22
-(C2H40)xH, where x is in the range of from 1 to 3.
Ampholytic surfactant
Ampholytic surfactants can be incorporated into the
detergent compositions herein. These surfactants can be
broadly described as aliphatic derivatives of secondary or
tertiary amines, or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic
radical can be straight chain or branched. One of the
aliphatic substituents contains at least about 8 carbon
atoms, typically from about 8 to about 18 carbon atoms, and
at least one contains an anionic water-solubilizing group,
e.g., carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at
column 19, lines 18-35 for examples of ampholytic
surfactants.
Amphoteric surfactant
Alkyl amphocarboxylic acid amohoteric surfactant
Suitable amphoteric surfactants for use herein include the
alkyl amphocarboxylic acids of the formula
0
RC-NHCH2CH2Ri
wherein R is a Cg-Clg alkyl group, and Ri is of the general
formula
(CH2)xC00- (CH2)xC00
N or N(+)-CH2CH20H
R1 R1
WO 94/07986 ~~ ~ ~''~'~ PCT/US93/08874
23
wherein R1 is a (CH2)xCOOM or CH2CH20H, and x is 1 or 2 and
M is preferably chosen from alkali metal, alkaline earth
metal, ammonium, mono-, di-, and tri-ethanolammonium, most
preferably from sodium, potassium, ammonium and mixtures
thereof with magnesium ions. The preferred R alkyl chain
length is a C10 to C14 alkyl group. A preferred
amphocarboxylic acid is produced from fatty imidazolines
wherein the dicarboxylic acid functionality of the
amphodicarboxylic acid is diacetic acid and/or dipropionic
acid. A suitable example of an alkyl aphodicarboxylic acid
for use herein in the amphoteric surfactant Miranol(TM) C2M
Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine Oxide surfactant
Amine oxides useful, as amphoteric surfactants, in the
present invention include those compounds having the
formula .
O
R3 (OR4 ) xN (R5 ) 2
wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures
thereof, containing from 8 to 26 carbon atoms, preferably 8
to 16 carbon atoms; R4 is an alkylene or hydroxyalkylene
group containing from 2 to 3 carbon atoms, preferably 2
carbon atoms, or mixtures thereof; x is from 0 to 5,
preferably from 0 to 3; and each R5 is an alkyl or
hydyroxyalkyl group containing from 1 to 3, preferably from
1 to 2 carbon atoms, or a polyethylene oxide group
containing from 1 to 3, preferable 1, ethylene oxide
groups. The R5 groups can be attached to each other, e.g.,
through an oxygen or nitrogen atom, to form a ring
structure.
.~
24
These amine oxide surfactants in particular include C10-C18
alkyl dimethyl amine oxides and Cg-Clg alkoxy ethyl
dihydroxyethyl amine oxides. Examples of such materials
include dimethyloctylamine oxide, diethyldecylamine oxide,
bis-(2-hydroxyethyl)dodecylamine oxide,
dimethyldodecylamine oxide, dipropyltetradecylamine oxide,
methylethylhexadecylamine oxide, dodecylamidopropyl
dimethylamine oxide, cetyl dimethylamine oxide, stearyl
dimethylamine oxide, tallow dimethylamine oxide and tallow
bis-(2-hydroxy ethyl) amine oxide. Preferred are C10-C1_8
alkyl dimethylamine oxide, and C10-18 acylamido alkyl
dimethylamine oxide.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the
detergent compositions hereof. These surfactants can be
broadly described as derivatives of secondary and tertiary
amines, derivatives of heterocyclic secondary and tertiary
amines, or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S.
Patent No. 3,929,678 to Laughlin et al., issued December
30, 1975 at column 19, line 38 through column 22, line 48
for examples of zwitterionic surfactants.
Betaine surfactant
The betaines useful herein are those compounds having the
formula R(R')2N+R2C00- wherein R is a C6-C18 hydrocarbyl
group, preferably a C10-C16 alkyl group or C10-16 acylamido
alkyl group, each R1 is typically C1-C3 alkyl, preferably
methyl,m and R2 is a C1-C5 hydrocarbyl group, preferably a
C1-C3 alkylene group, more preferably a C1-C2 alkylene
group. Examples of suitable betaines include coconut
acylamidopropyldimethyl betaine; hexadecyl dimethyl
betaine; C12-14 acylamidopropylbetaine; Cg-14
B
~~" WO 94/07986 ~~ ~ ~ ~ ~ PCT/US93/08874
acylamidohexyldiethyl betaine; 4(C14-16
acylmethylamidodiethylammonio]-1-carboxybutane; C16-18
acylamidodimethylbetaine; C12-16 acylamidopentanediethyl-
betaine; [C12-16 acylmethylamidodimethylbetaine. Preferred
betaines are C12-18 dimethyl-ammonio hexanoate and the C10-
ig acylamidopropane (or ethane) dimethyl (or diethyl)
betaines.
Sultaine surfactant
The sultaines useful herein are those compounds having the
formula (R(R1)2N+R2S03- wherein R is a C6-Cig hydrocarbyl
group, preferably a C10-C16 alkyl group, more preferably a
C12-C13 alkyl group, each R1 is typically C1-C3 alkyl,
preferably methyl, and R2 is a C1-C6 hydrocarbyl group,
preferably a C1-Cg alkylene or, less preferably a
hydroxyalkylene group. Examples of suitable sultaines
include C12-C14 dimethylammonio-2-hydroxypropyl sulfonate,
C12-14 amido propyl ammonio-2-hydroxypropyl sultaine, C12-
14 dihydroxyethylammonio propane sulfonate, and C16-18
dimethylammonio hexane sulfonate, with C12-14 amido propyl
ammonio-2-hydroxypropyl sultaine being preferred.
Complex betaine surfactant
The complex betaines for use herein have the formula
R - (A)n - [N - (CHRi)x]y - N - Q (I)
B B
wherein R is a hydrocarbon group having from 7 to 22 carbon
atoms, A is the group (C(O)), n is 0 or 1, R1 is hydrogen
or a lower alkyl group, x is 2 or 3, y is an integer of 0
to 4, Q is the group -R2COOM wherein R2 is an alkylene
group having from 1 to 6 carbon atoms and M is hydrogen or
an ion from the groups alkali metals, alkaline earth
WO 94/07986 , PCT/US93/08874
14 ~ ~.'~
26
metals, ammonium and substituted ammonium and B is hydrogen
or a group Q as defined.
An example in this category is tallowamphopolycarboxy
glycinate, of the formula .
CH2COONa CH2COONa CH2COONa CH2COONa
R - N - CH2CH2CH2 - N - CH2CH2CH2N - CH2CH2CH2N <
CH2COONa
Preferred amides are Cg-C2p alkyl mono- or di-C2-C3
alkanolamides, especially monoethanolamides,
diethanolamides, and isopropanolamides.
Ampholytic, amphoteric and zwitteronic surfactants are
generally used in combination with one or more anionic
and/or nonionic surfactants.
Cationic surfactants
Cationic surfactants can also be used in the detergent
compositions herein and suitable quaternary ammonium
surfactants are selected from mono C6-C16, preferably C6-
Clp N-alkyl or alkenyl ammonium surfactants wherein
remaining N positions are substituted by methyl,
hydroxyethyl or hydroxypropyl groups.
Alkoxylated nonionic surfactant.
Alkoxylated nonionic surfactants (nonionic alkyene oxide
condensate surfactants) are defined herein to include the
nonionic ethoxylated alcohol surfactants , nonionic
condensates of alkyl phenols, the nonionic
ethoxylated/propoxylated fatty alcohols, nonionic EO/PO
condensates with propylene glycol and nonionic EO
WO 94/07986 ~ PCT/US93/08874
27
ethoxylated/propoxylated fatty alcohols, nonionic EO/PO
condensates with propylene glycol and nonionic EO
condensation products with propylene oxide/ethylene diamine
adducts, as described hereinafter.
Such alkoxylated nonionic surfactants may be incorporated
into the machine dishwashing compositions at levels of no
more than 5% by weight, more typically no more than 3% by
weight, preferably from 0.5% to 2.5% by weight of the
composition. These alkyloxylated nonionic surfactants may
act as wetting agents or suds controllers, but typically do
not have a primary cleaning role.
Nonionic condensates of alkyl phenols
The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use herein.
In general, the polyethylene oxide condensates are
preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing
from about 6 to about 18 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 5 to about 25
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, a11 marketed by
the Rohm & Haas Company.
Nonionic ethoxYlated alcohol surfactant
The alkyl ethoxylate condensation products of aliphatic
alcohols with from about 1 to about 25 moles of ethylene
oxide are suitable for use herein. The alkyl chain of the
aliphatic alcohol can either be straight or branched,
primary or secondary, and generally contains from 6 to 22
WO 94/07986 ~ PCT/US93/08874
~1~~1~'~
2$
carbon atoms. Particularly preferred are the condensation
products of alcohols having an alkyl group containing from
8 to 2~0 carbon atoms with from about 2 to about 10 moles of
ethylene oxide per mole of alcohol. Most preferred are the
condensation products of alcohols having an alkyl group
containing from 12 to 18 carbon atoms with from about 6 to
about 10 moles of ethylene oxide per mole of alcohol.
Examples of commercially available nonionic surfactants of
this type include TergitoITM 15-S-9 (the condensation
product of C11-C15 linear alcohol with 9 moles ethylene
oxide), 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 23-6.5 (the condensation product of 012-
C13 linear alcohol with 6.54 moles of ethylene oxide),
NeodoiTM 45-7 (the condensation product of C14-C15 linear
alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the
condensation product of C14-C15 linear alcohol with 4 moles
of ethylene oxide), marketed by Shell Chemical Company, and
KyroTM EOBN (the condensation product of C13-C15 alcohol
with 9 moles ethylene oxide), marketed by The Procter &
Gamble Company.
Nonionic ethoxvlated/propoxvlated fattv alcohol surfactant
The ethoxylated C6-Clg fatty alcohols and C6-Clg mixed
ethoxylated/propoxylated fatty alcohols are suitable
surfactants for use herein, particularly where water
soluble. Preferably the ethoxylated fatty alcohols are the
C10-Clg ethoxylated fatty alcohols with a degree of
ethoxylation of from 3 to 50, most preferably these are the
C12-Clg ethoxylated fatty alcohols with a degree of
ethoxylation from 3 to 40. Preferably the mixed
ethoxylated/propoxylated fatty alcohols have an alkyl chain
"""' WO 94/07986 PCT/US93/08874
29
length of from 10 to 18 carbon atoms, a degree of
ethoxylation of from 3 to 30 and a degree of propoxylation
of from 1 to 10. A highly preferred surfactant of this
type is a C13-C15 mixed ethoxylated/propoxylated fatty
alcohol with an average degree of ethoxylation of 3.8, and
an average degree of propoxylation of 4.5, sold under the
tradename Pluratec LF404 by BASF GmbN.
Nonionic EO/PO condensates with DtOQ,Ylene glycol
The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene
oxide with propylene glycol are suitable for use herein.
The hydrophobic portion of these compounds preferably has a
molecular weight of from about 1500 to about 1800 and
exhibits water insolubility. The addition of
polyoxyethylene moieties of this hydrophobic portion tends
to 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 polyoxyethylene 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 include
certain of the commercially-available PluronicTM
surfactants, marketed by BASF.
Nonionic EO condensation products with propylene
oxide~/ethylene diamine adducts
The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylenediamine are suitable for use herein. The
hydrophobic moiety of these products consists of the
reaction product of ethylenediamine 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
~....
WO 94/07986 PCT/US93/08874
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.
Hydrotropes
A hydrotrope is typically added to the compositions of the
present invention, and may be present at levels of from
0.5% to 10%, preferably from 1% to 5%, by weight.
Useful hydrotropes include sodium, potassium, and ammonium
xylene sulfonates, sodium, potassium, and ammonium toluene
sulfonate, sodium potassium and ammonium cumene sulfonate,
and mixtures thereof.
Other compounds useful as hydrotropes herein include
polycarboxylates. Some polycarboxylates have calcium
chelating properties as well as hydrotropic properties.
Particularly useful hydrotropes are alkylpolyethoxy
polycarboxylate surfactants of the type as previously
described herein.
An example of a commercially available alkylpolyethoxy
polycarboxylate which can be employed herein is POLY-
TERGENT C, Olin Corporation, Cheshire, CT.
Another compound useful as a hydrotrope is alkyl
amphodicarboxylic acid of the generic formula .
(CH2)x COO-
RCNHCH2CH2N<
(CH2)x COOM
wherein R is a Cg to Clg alkyl group, x is from 1 to 2, M
is preferably chosen from alkali metal, alkaline earth
metal, ammonium, mono-, di-, and tri-ethanolammonium, most
preferably from sodium, potassium, ammonium, and mixtures
WO 94/07986 ~ ~ ~ ~ ~ ~'"~ PCT/US93/08874
31
thereof with magnesium ions. The preferred alkyl chain
length (R) is a C10 to C14 alkyl group and the dicarboxylic
acid functionally is diacetic acid and/or dipropionic acid.
A suitable example of an alkyl amphodicarboxylic acid is
the amphoteric surfactant Miranol R 2CM Conc.manufactured
by Miranol, Inc., Dayton, NJ.
Builder compound
The machine dishwashing detergent composition of the
present invention preferably contains water-soluble
detergent builder compound present at a level of from 1% to
80% by weight, preferably from 10% to 70% by weight, most
preferably from 20% to 60% weight of the composition.
Suitable water-soluble detergent builder compounds include,
but are not restricted to monomeric polycarboxylates, of
their acid forms homo or copolymeric polycarboxylic acids
or their salts in which the polycarboxylic acid comprises
at least two carboxylic radicals separated from each other
by not more that two carbon atoms, carbonates,
bicarbonates, borates, phosphates, silicates and mixtures
of any of the foregoing.
Suitable water-soluble monomeric or oligomeric carboxylate
builders can be selected from a wide range of compounds but
such compounds preferably have a first carboxyl logarithmic
acidity/constant (pKl) of less than 9, preferably of
between 2 and 8.5, more preferably of between 4 and 7.5.
The logarithmic acidity constant is defined by reference to
the equilibrium
H+ + A- ~ HA
where A is the fully ionized carboxylate anion of the
builder salt.
WO 94/07986 PCT/US93/08874
y 14 ~ 1'~ '~
32
The equilibrium constant for dilute solutions is therefore
given by the expression
K1 _ [HA)
CH+) ~A_)
and pKl = loglpK.
For the purposes of this specification, acidity constants
are defined at 25~C and at zero ionic strength. Literature
values are taken where possible (see Stability Constants of
Metal-Ion Complexes, Special Publication No. 25, The
Chemical Society, London): where doubt arises they are
determined by potentiometric titration using a glass
electrode.
The carboxylate or polycarboxylate builder can be momomeric
or oligomeric in type although monomeric polycarboxylates
are generally preferred for reasons of cost and
performance.
Monomeric and oligomeric builders can be selected from
acyclic, alicyclic, heterocyclic and aromatic carboxylates
having the general formulae
(a) Y
R1 X ~ R2
1
Z m
(b)
X
Z
n
or
(c) YP ~ zq
33
wherein R1 represents H,C1_30 alkyl or alkenyl optionally
substituted by hydroxy, carboxy, sulfo or phosphono groups
or attached to a polyethylenoxy moiety containing up to 20
ethyleneoxy groups; R2 represents H, C1_4 alkyl, alkenyl or
hydroxy alkyl, or alkaryl, sulfo, or phosphono groups;
X represents a single bond; O; S; SO; S02; or NR1;
Y represents H; carboxy;hydroxy; carboxymethyloxy; or
C1-30 alkyl or alkenyl optionally substituted by hydroxy or
carboxy groups;
Z represents H; or carboxy;
m is an integer from 1 to 10;
n is an integer from 3 to 6;
p, q are integers from 0 to 6, p + q being from 1 to 6; and
wherein, X, Y, and Z each have the same or different
representations when repeated in a given molecular formula,
and wherein at least one Y or Z in a molecule contain a
carboxyl group.
Suitable carboxylates containing one carboxy group include
the water soluble salts of lactic acid, glycolic acid and
ether derivatives thereof as disclosed in Belgian Patent
Nos. 831,368, 821,369 and 821,370. Polycarboxylates
containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy)
diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid and fumaric acid, as well as the ether
carboxylates described in German Offenlegenschrift
2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and
the sulfinyl carboxylates described in Belgian Patent No.
840,623. Polycarboxylates containing three carboxy groups
include, in particular, water-soluble citrates, aconitrates
and citraconates as well as succinate derivatives such as
the carboxymethyloxysuccinates described in British Patent
No. 1,379,241, lactoxysuccinates described in British
Patent No. 1,389,732, and aminosuccinates described in
Canadian Patent No. 973,771 issued September 2, 1975, and
the oxypolycarboxylate
B
WO 94/07986 ~ ~ ~ ~ - PCT/US93/08874
34
materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448,
and the sulfonated pyrolysed citrates described in British
Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include
cyclopentane-cis,cis,cis-tetracarboxylates,
cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-
tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-
tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane -
hexacarboxylates and carboxymethyl derivatives of
polyhydric alcohols such as sorbitol, mannitol and xylitol.
Aromatic polycarboxylates include mellitic acid,
pyromellitic acid and the phthalic acid derivatives
disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups
per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric
polycarboxylate chelating agents or mixtures thereof with
their salts, e.g. citric acid or citrate/citric acid
mixtures are also contemplated as components of builder
systems of detergent compositions in accordance with the
present invention.
WO 94/07986 PCT/US93/08874
Other suitable water soluble organic salts are the homo- or
co-polymeric polycarboxylic acids or their salts in which
the polycarboxylic acid comprises at least two carboxyl
radicals separated from each other by not more than two
carbon atoms. Polymers of the latter type are disclosed in
GB-A-1,596,756. Examples of such salts are polyacrylates
of MWt 2000-50o0 and their copolymers with malefic
anhydride, such copolymers having a molecular weight of
from 20,000 to 70,000, especially about 40,000. These
materials are normally used at levels of from 0.5% to 10%
by weight more preferably from 0.75% to 8%, most preferably
from 1% to 6% by weight of the composition.
Water-soluble detergent builders 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), phytic acid, silicates, carbonates
(including bicarbonates and sesquicarbonates), and
sulfates. Borate builders, as well as builders containing
borate-forming materials that can produce borate under
detergent storage or wash conditions can also be used but
are not preferred at wash conditions less that about 50~C,
especially less than about 40~C.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates, including sodium carbonate and
sesqui-carbonate and mixtures thereof with ultra-fine
calcium carbonate as disclosed in German Patent Application
No. 2,321,001 published on November 15, 1973.
Specific examples of phosphate builders are the alkali
metal tripolyphosphates, sodium, potassium and ammonium
pyrophosphate, sodium and potassium and ammonium
pyrophosphate, sodium and potassium orthophosphate, sodium
polymeta/phosphate in which the degree of polymerization
ranges from about 6 to 21, and salts of phytic acid.
WO 94/07986 ~- PCT/US93/08874
36
Suitable silicates include the water soluble sodium
silicates with an Si02: Na20 ratio of from 1.0 to 2.8, with
ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio
being most preferred. The silicates may be in the form of
either the anhydrous salt or a hydrated salt. Sodium
silicate with an Si02: Na20 ratio of 2.0 is the most
preferred silicate.
Silicates are preferably present in the machine dishwashing
detergent compositions at the invention at a level of from
5% to 50% by weight of the composition, more preferably
from 10% to 40% by weight.
Whilst water-soluble detergent builders are preferable
components of the detergent compositions of the invention
the compositions may also include less water soluble
builders although preferably their levels of incorporation
are minimized. Examples of such less water soluble
builders include the crystalline layered silicates and the
largely water insoluble sodium aluminosilicates.
Crystalline layered sodium silicates have the general
f ormu 1 a
NaMSixOx+l.yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to
4 and y is a number from o to 20. Crystalline layered
sodium silicates of this type are disclosed in EP-A-0164514
and methods for their preparation are disclosed in DE-A-
3417649 and DE-A-3742043. For the purpose of the present
invention, x in the general formula above has a value of 2,
3 or 4 and is preferably 2. More preferably M is sodium
and y is 0 and preferred examples of this formula comprise
the of -, !3 -, ~' - and ~'- forms of Na2Si205. These
materials are available from Hoechst AG FRG as respectively
37
NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred
material is ~ -Na2Si205, NaSKS-6.
The crystalline layered sodium silicate material is
preferably present in granular detergent compositions as a
particulate in intimate admixture with a solid, water-
soluble ionisable material. The solid, water-soluble
ionisable material is selected from organic acids, organic
and inorganic acid salts and mixtures thereof. The primary
requirement is that the material should contain at least on
functional acidic group of which the pKa should be less.
than 9, providing a capability for at least partial
neutralisation of the hydroxyl ions released by the
crystalline layered silicate.
The incorporation in the particulate of other ingredients
additional to the crystalline layered silicate and
ionisable water soluble compound can be advantageous
particularly in the processing of the particulate and also
in enhancing the stability of detergent compositions in
which the particulates are included. In particular,
certain types of agglomerates may require the addition of
one or more binder agents in order to assist in binding the
silicate and ionisable water soluble material so as to '
produce particulates with acceptable physical
characteristics.
The crystalline layered sodium silicate containing
particulates can take a variety of physical forms such as
extrudates, marumes, agglomerates, flakes or compacted
granules. A preferred process for preparing compacted
granules comprising crystalline layered silicate and a
solid, water-soluble ionisable material has been disclosed
in the commonly assigned WO 92/18594 published October 29,
1992.
WO 94/07986 PCT/US93/08874
38
Suitable aluminosilicate zeolites have the unit cell
formula Naz[(A102)z(Si02)y]. XH20 wherein z and y are at
least.6; the molar ratio of z to y is from 1.0 to 0.5 and x
is at least 5, preferably from 7.5 to 276, more preferably
from 10 to 264. The aluminosilicate material are in
hydrated form and are preferably crystalline, containing
from 10% to 28%, more preferably from 18% to 22% water in
bound form.
The above aluminosilicate ion exchange materials are
further characterised by a particle size diameter of from
0.1 to 10 micrometers, preferably from 0.2 to 4
micrometers. The term "particle size diameter" herein
represents the average particle size diameter of a given
ion exchange material as determined by conventional
analytical techniques such as, for example, microscopic
determination utilizing a scanning electron microscope or
by means of a laser granulometer. The aluminosilicate ion
exchange materials are further characterised by their
calcium ion exchange capacity, which is at least 200 mg
equivalent of CaC03 water hardness/g of aluminosilicate,
calculated on an anhydrous basis, and which generally is in
the range of from 300 mg eq./g to 352 mg eq./g. The
aluminosilicate ion exchange materials herein are still
further characterised by their calcium ion exchange rate
which is at least 130 mg equivalent of CaC03/ litre /
minute / (g/litre) [2 grains Ca + +/ gallon/ minute/ gram/
gallon)] of aluminosilicate (anhydrous basis), and which
generally lies within the range of from 130 mg equivalent
of CaC03/ litre/ minute/ (gram/litre) [2 grains/ gallon/
minute/ (gram/ gallon)] to 390 mg equivalent of CaC03/
litre/ minute/ (gram/litre) [4 grains/ gallon/ minute/
(gram/ gallon)], based on calcium ion hardness.
Optimum aluminosilicates for builder purpose exhibit a
calcium ion exchange rate of at least 260 mg equivalent of
~' WO 94/07986 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08874
39
CaC03/litre/ minute/ (gram/litre) [4 grains/gallon/minute/
(gram/ gallon)].
The aluminosilicate ion exchange materials can be naturally
occurring materials, but are preferably synthetically
derived. A method for producing aluminosilicate ion
exchange materials is discussed in US Patent No. 3,985,669.
Synthetic crystalline aluminosilicate ion exchange
materials are available under the designations Zeolite A,
Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures
thereof. Zeolite A has the formula
Na 12 [A102) 12 (Si02)12J~ xH20
wherein x is from 20 to 30, especially 27. Zeolite X has
the formula Nag6 [(A102)g6(Si02)106]~ 2~6 H20 has the
formula Na6 [(A102)6(Si02)6] 7.5 H20).
The machine dishwashing or rinsing detergent compositions
of the invention preferably comprise a suds suppressing
system present at a level of from 0.01% to 15%, preferably
from 0.05% to 10%, most preferably from 0.1% to 5% by
weight of the composition.
Suitable suds suppressing systems for use herein may
comprise essentially any known antifoam compound,
including, for example silicone antifoam compounds, 2-alkyl
alcanol antifoam compounds, and paraffin antifoam
compounds.
By antifoam compound it is meant herein any compound or
mixtures of compounds which act such as to depress the
foaming or sudsing produced by a solution of a detergent
composition, particularly in the presence of agitation of
that solution.
,. r~
WO 94/07986 ~ 1 ~ ~ ~ PCT/US93/08874
The suds suppressing system may be incorporated into the
detergent compositions by essentially any process route.
One preferred suds suppressing system comprises in
combination a spray-on component and a particulate
component.
Preferred spray-on components comprise in combination an
antifoam compound and a carrier fluid and optionally a
dispersant compound. The antifoam compound is dissolved,
dispersed, suspended or emulsified in said carrier fluid.
The carrier fluid should be inert in nature, that is it
should not undergo undesirable chemical reaction with the
antifoam compound, and also preferably be storage stable
under normal atmospheric conditions and in the environment
of a granular detergent matrix.
Any spray-on component is incorporated into the granular
detergent compositions of the invention by a spray-on
process, that is a process whereby the fluid is sprayed on
to some or a11 of the individual granular components of the
composition. Highly preferably the spray-on process will
be such as to provide a uniform and sufficient application
of the suds suppressing component to any granular
components of the composition which comprise a high sudsing
surfactant.
A preferred composition for a spray-on component comprises
(a) antifoam compound, preferably silicone antifoam
compound, most preferably a silicone antifoam compound
comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to
99%, preferably 75% to 95% by weight of the silicone
antifoam compound; and
(ii)silica, at a level of from 1% to 50%, preferably
5% to 25% by weight of the silicone/silica antifoam
compound;
"""'~ WO 94/07986 ~ ~ ~ ~ ~ ~ PCT/US93/08874
41
wherein said silica/silicone antifoam compound is
incorporated at a level of from 5% to 50%, preferably 10%
to 40% by weight of the spray-on component;
(b) a dispersant compound, most preferably comprising a
silicone glycol rake copolymer with a polyoxyalkylene
content of 72-78% and an ethylene oxide to propylene oxide
ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to
l0%, preferably 1% tol0% by weight of the spray-on
component; a particularly preferred silicone glycol rake
copolymer of this type is DC0544, commercially available
from DOW Corning;
(c) an inert carrier fluid compound, most preferably
comprising a C16-Clg ethoxylated alcohol with a degree of
ethoxylation of from 5 to 50, preferably 8 to 15, at a
level of from 5% to 80%, preferably 10% to 70%, by weight
of the spray-on component;
Any spray on component of the suds suppressing system may
be incorporated as such, or in a,preferred execution may be
mixed with other components such as liquid nonionic
surfactants, and perfume, and this mixture sprayed on as a
whole.
Particulate components of the suds suppressing system are
particulate in form and incorporated into the compositions
of the invention in this form.
By particulate form it is meant essentially any of the
particulate forms which may be typically adapted by a
component of a granular detergent composition. The
particulate component can therefore be, for example, in the
form of granules, flakes, prills, marumes or noodles. In a
preferred execution the particulate is granular in nature.
Granules themselves may be agglomerates formed by pan or
drum agglomeration or by an in-line mixer, and also may be
WO 94/07986 PCT/US93/08874
~~45~'~'~
42
spray-dried particles produced by atomising an aqueous
slurry of the ingredients in a hot air stream which removes
most of_the water. The spray dried granules are then
subjected to densification steps, eg . by high speed cutter
mixers and/or compacting mills, to increase density before
being reagglomerated.
Any particulate component of the suds suppressing system
may comprise in combination antifoam compound, and a
carrier material which is highly preferably water-soluble
or water-dispersible in nature.
A suitable particulate antifoam component useful in the
compositions herein comprises a mixture of an alkylated
siloxane of the type hereinabove disclosed and solid
silica.
The solid silica can be a fumed silica, a precipitated
silica or a silica, made by the gel formation technique.
The silica particles suitable have an average particle size
of from 0.1 to 50 micrometers, preferably from 1 to 20
micrometers and a surface area of at least 50m2/g. These
silica particles can be rendered hydrophobic by treating
them with dialkylsilyl groups and/or trialkylsilyl groups
either bonded directly onto the silica or by means of a
silicone resin. It is preferred to employ a silica the
particles of which have been rendered hydrophobic with
dimethyl and/or trimethyl silyl groups. A preferred
particulate antifoam compound for inclusion in the
detergent compositions in accordance with the invention
suitably contain an amount of silica such that the weight
ratio of silica to silicone lies in the range from 1:100 to
3:10, preferably from 1:50 to 1:7.
Another suitable particulate antifoam component is
represented by a hydrophobic silanated (most preferably
trimethyl-silanated) silica having a particle size in the
43
range from 10 nanometers to 20 nanometers and a specific
surface area above 5om2/g, intimately admixed with dimethyl
silicone fluid having a molecular weight in the range from
about 500 to about 200,000 at a weight ratio of silicone to
silanated silica of from about 1:1 to about 1:2.
Suitable particulate antifoam components are disclosed in
Bartollota et al. US Patent 3,933,672.
A highly preferred particulate antifoam component is -
described in EP-A-0210731 and comprises a silicone antifoam
compound and an organic carrier material having a melting
point in the range 50~C to 85~C, wherein the organic
carrier material comprises a monoester of glycerol and a
fatty acid having a carbon chain containing from 12 to 20
carbon atoms. EP-A-0210721 discloses other preferred
particulate antifoam components wherein the organic carrier
material is a fatty acid or alcohol having a carbon chain
containing from 12 to 20 carbon atoms, or a mixture
thereof, with a melting point of from 45~C to 80~C.
Other highly preferred particulate antifoam components are
described in copending Canadian Application 2,099,129 in
the name of the Procter and Gamble Company which components
comprise silicone antifoam compound, a carrier material, an
organic coating material and glycerol at a weight ratio of
glycerol . silicone antifoam compound of 1:2 to 3:1.
Copending EP 461,699 published December 18, 1991 also discloses
highly preferred particulate antifoam components comprising
silicone antifoam compound, a carrier material, an organic
coating material and crystalline or amorphous
aluminosilicate at a weight ratio of aluminosilicate .
silicone antifoam compound of 1:3 to 3:1. The preferred
carrrier material in both of the above described highly
preferred granular suds controlling agents is starch.
B
WO 94/07986 PCT/US93/08874
""
44
An exemplary particulate antifoam component for use herein
is a particulate agglomerate component, made by an
agglomeration process, comprising in combination
(i) from 5% to 30%, preferably from 8% to 15% by weight of
the component of silicone antifoam compound, preferably
comprising in combination polydimethyl siloxane and silica;
(ii) from 50% to 90%, preferably from 60% to 80% by weight
of the component, of carrier material, preferably starch;
(iii)from 5% to 30%, preferably from 10% to 20% by weight
of the component of agglomerate binder compound, where
herein such compound can be any compound, or mixtures
thereof typically employed as binders for agglomerates,
most preferably said agglomerate binder compound comprises
a C16-Cig ethoxylated alcohol with a degree of ethoxylation
of from 50 to 100; and
(iv)from 2%~to 15%, preferably from 3% to 10%, by weight of
C12-C22 hydrogenated fatty acid.
The incorporation of silicone antifoam compounds as
components of seperate particulate components also permits
the inclusion therein of C20-C24 fatty acids,
microcrystalline waxes and high MWt copolymers of ethylene
oxide and propylene oxide which would otherwise adversely
affect the despersibility of the matrix. Techniques for
forming such particulates are disclosed in US Patent No.
3,933,672.
A preferred suds suppressing system has the weight ratio of
antifoam compound comprised in the spray-on component to
antifoam compound comprised in the particulate component of
from 5:1 to 1:1, most preferably from 4:1 to 2:1.
Particularly preferred antifoam compounds for use herein
are silicone antifoam compounds defined herein as any
antifoam compound including a silicone component. Such
WO 94/07986 ~ ~ (~ ~ ~ ~'~ PCT/US93/08874
silicone antifoam compounds also typically contain a silica
component. The term "silicone" as used herein, and in
general throughout the industry, encompasses a variety of
relatively high molecular weight polymers containing
siloxane units and hydrocarbyl group of various types.
Preferred silicone antifoam compounds are the siloxanes
having the general structure .
R R
R Si0 Si R
R R
n
where each R independently can be an alkyl or an aryl
radical. Examples of such substituents are methyl, ethyl,
propyl, isobutyl, and phenyl. Preferred
polydiorganosiloxanes are polydimethylsiloxanes having
trimethylsilyl endblocking units and having a viscosity at
25~C of from 5 x 10-5m2/s to O.lm2/s i.e. a value on n in
the range 40 to 1500. These are preferred because of their
ready availability and their relatively low cost.
Other suitable antifoam compounds include the
monocarboxylic fatty acids and soluble salts thereof.
These materials are described in US Patent 2,954,347,
issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids, and salts thereof, for use as
suds suppressor 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.
WO 94/07986 ~ . PCT/US93/08874
46
Other suitable antifoam compounds include, for example,
high molecular weight hydrocarbons such as paraffin, fatty
esters._(e.g. fatty acid triglycerides), fatty acid esters
of monovalent alcohols, aliphatic Clg-C40 ketones (e. g.
stearone) 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, bis stearic acid amide and
monostearyl di-alkali metal (e. g. sodium, potassium,
lithium) 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 5~C, and a minimum boiling point not less than 110~C
(atmospheric pressure). It is also known to utilize waxy
hydrocarbons, preferably having a melting point below about
100~C. Hydrocarbon suds suppressors 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
supressor dicussion, is intended to include mixtures of
true paraffins and cyclic hydrocarbons.
2-alkyl alcanol antifoam compounds.
Suitable 2-alky-alcanols antifoam compounds for use herein
have been described in DE 40 21 265. The 2-alkyl-alcanols
suitable for use herein consist of a C6 to C16 alkyl chain
carrying a terminal hydroxy group, and said alkyl chain is
substituted in the a position by a C1 to C10 alkyl chain.
Preferably, the alkyl chain carrying the hydroxy group is a
Cg to C12 alkyl chain, and the alkyl chain in the a
position is a C2 to Cg alkyl chain, most preferably C3 to
""~ WO 94/07986 ~ ~ PCT/US93/08874
47
C6. Preferably a11 alkyl chains herein are straight. It
has been found that 2-hexyl-decanol and 2-butyl-octanol are
particularly suitable for use herein. 2-hexyl-decanol and
2-butyl- octanol are commercially available fron Condea
under the trade names ISOFOL 16 and ISOFOL 12. The suds
suppressing system for use herein comprises from 0.01% to
15% by weight of the total composition of said 2-alkyl-
alcanols, preferably from 0.05% to 10%, most preferably
from 0.1% to 5%. Mixtures of 2-alkyl-alcanols can be used
in the compositions according to the present invention.
Such mixtures are comprised in commercially available
materials, for instance ISALCHEM 123 R from Enichem.
The machine dishwashing detergent compositions of the
invention will preferably included bleaching agent selected
from chlorine bleaches, inorganic perhydrate salts,
peroxyacid bleach precursors and organic peryoxacids.
Chlorine bleaches include the alkali metal hypochlorites
and chlorinated cyanuric acid salts.
The machine dishwashing detergent compositions in accord
with the invention will generally include an inorganic
perhydrate salt, normally in the form of the sodium salt at
a level of from 1% to 40% by weight, more preferably from
2% to 30% by weight and most preferably from 5% to 25% by
weight of the detergent compositions.
The machine dishwashing detergent compositions of the
present invention will. also generally include peroxyacid
bleach precursors (bleach activators). The peroxyacid
bleach precursors are normally incorporated at a level of
from 1% to 20% by weight, more preferably from 1% to 10% by
weight, most preferably from 1% to 7% by weight of the
compositions.
WO 94/07986 ~ ~ ~'~ ~~ ~ ' PCT/US93/08874 "'"
48
The machine dishwashing detergent compositions may also
contain organic peroxyacids at a level of from 1% to 15% by
weight; more preferably from 1% to 10% by weight of the
composition.
Examples of inorganic perhydrate salts include perborate,
percarbonate, perphosphate, persulfate and persilicate
salts. The inorganic perhydrate salts are normally the
alkali metal salts. The inorganic perhydrate salt may be
included as the crystalline solid without additional
protection. For certain perhydrate salts however, the
preferred executions of such granular compositions utilize
a coated form of the material which provides better storage
stability for the perhydrate salt in the granular product.
Sodium perborate, which is the most preferred perhydrate
for inclusion in the machine dishwashing detergent
compositions in accordance with the invention, can be in
the form of the monohydrate of nominal formula NaB02H202 or
the tetrahydrate NaB02H202.3H20.
Sodium percarbonate, which is another preferred perhydrate
for inclusion in detergent compositions in accordance with
the invention, is an addition compound having a formula
corresponding to 2Na2C03.3H202, and is available
commercially as a crystalline solid. The percarbonate is
most preferably incorporated into such compositions in
coated form. The most preferred coating material comprises
mixed salt of an alkali metal sulphate and
carbonate. Such coatings together with coating processes
have previously been described in GB-1,466,799, granted to
Interox on 9th March 1977. The weight ratio of the mixed
salt coating material to percarbonate lies in the range
from 1 . 200 to 1 . 4, more preferably from 1 . 99 to 1 .
9, and most preferably from 1 . 49 to 1 . 19. Preferably,
the mixed salt is of sodium sulphate and sodium carbonate
which has the general formula Na2S04.n.Na2C03 wherein n is
""' WO 94/07986 PCT/US93/08874
49
form 0.1 to 3, preferably n is from 0.3 to 1.0 and most
preferably n is from 0.2 to 0.5.
Another suitable coating material is sodium silicate of
Si02 . Na20 ratio from 1.6 . 1 to 3.4 . 1, preferably 2.8 .
1, applied as an aqueous solution to give a level of from
2% to 10%, (normally from 3% to 5%) of silicate solids by
weight of the percarbonate. Magnesium silicate can also be
included in the coating. Other suitable coating materials
include the alkali and alkaline earth metal sulphates and
carbonates.
Potassium peroxymonopersulfate is another inorganic
perhydrate salt of particular usefulness in the machine
dishwashing detergent compositions.
Peroxyacid bleach precursors for inclusion in the machine
dishwashing detergent compositions in accordance with the
invention probably contain one or more N- or O- acyl
groups, which precursors can be selected from a wide range
of classes. Suitable classes include anhydrides, esters,
imides and acylated derivatives of imidazoles and oximes,
and examples of useful materials within these classes are
disclosed in GB-A-1586789. The most preferred classes are
esters such as are disclosed in GB-A-836988, 864798,
1147871 and 2143231 and imides such as are disclosed in GB-
A-855735 & 1246338.
Particularly preferred precursor compounds are the
N,N,N1,N1 tetra acetylated compounds of formula
O O
\\ I1
CH3 - C C - CH3
N - (CH2)x - N
CH3 - C C CH3
0 0
WO 94/07986 ~ ~ ~ ('~ ~'''~ ~ " PCT/US93/08874
wherein x can be O or an integer between 1 & 6.
Examples include tetra acetyl methylene diamine (TAMD) in
which ~x=1, tetra acetyl ethylene diamine (TAED) in which
x=2 and tetraacetyl hexylene diamine (TAHD) in which x=6.
These and analogous compounds are described in GB-A-907356.
The most preferred peroxyacid bleach precursor is TAED.
Another preferred class of peroxyacid bleach activator
compounds are the amide substituted compounds of the
following general formulae:
R1 - C - N-R2 - C - L or R1 - N - C- R2 - C - L
O R5 O R5 O O
wherein R1 is an aryl or alkaryl group with from about 1 to
about 14 carbon atoms, R2 is an alkylene, arylene, and
alkarylene group containing from about 1 to 14 carbon
atoms, and R5 is H or an alkyl, aryl, or alkaryl group
containing 1 to 10 carbon atoms and L can be essentially
any leaving group. R1 preferably contains from about 6 to
12 carbon atoms. R2 preferably contains from about 4 to 8
carbon atoms. R1 may be straight chain or branched alkyl,
substituted aryl or alkylaryl containing branching,
substitution, or both and may be sourced from either
synthetic sources or natural sources including for example,
tallow fat. Analogous structural variations are
permissible for R2. The substitution can include alkyl,
aryl, halogen, nitrogen, sulphur and other typical
substituent groups or organic compounds. R5 is preferably
H or methyl. R1 and R5 should not contain more than 18
carbon atoms total. Amide substituted bleach activator
compounds of this type are described in EP-A-0170386.
Other peroxyacid bleach precursor compounds include sodium
nonanoyloxy benzene sulfonate, sodium trimethyl hexanoyloxy
benzene sulfonate, sodium acetoxy benzene sulfonate and
51
sodium benzoyloxy benzene sulfonate as disclosed in, for
example, EP-A-0341947.
The machine dishwashing detergent compositions of the
invention may also contain organic peroxyacids of which a
particularly preferred class are the amide substituted
peroxyacids of general formulae:
R1 -C - N-R2 - C - OOH or R1 - N -C-R2 -C - OOH
~ O R5 O R5 O 'O
where R1, R2 and R5 are as defined previously for the
corresponding amide substituted peroxyacid bleach activator
compounds.
Other organic peroxyacids include diperoxy dodecanedioc
acid, diperoxy tetra decanedioc acid,
diperoxyhexadecanedioc acid, mono- and diperazelaic acid,
mono- and diperbrassylic acid, monoperoxy phthalic acid,
perbenzoic acid, and their salts as disclosed in, for
example, EP-A-0341 947.
Detergent compositions in which solid peroxybleach
precursors are protected via an acid coating are disclosed
in the Applicant's copending Canadian Application No.
2,10l,448.
Anti-redeposition and soil-suspension agents suitable
herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, homo-or co-polymeric polycarboxylic
acids or their salts and polyamino compounds. Polymers of
this type include the polyacrylates and copolymers of
malefic anhydride with ethylene; methylvinyl ether or
methacrylic acid, the malefic anhydride constituting at
least 20 mole percent of the copolymer disclosed in detail
in EP-A-137669. Polyamino compounds such as those derived
WO 94/07986 ~, ~" ~ ~ ~~~ ~..
PCT/US93/08874
52
from aspartic acid are disclosed in EP-A-305282, EP-A-
305283 and EP-A-351629. These materials are normally used
at levels of from 0.5% to 10% by weight, more preferably;
from 0.75% to 9%, most preferably from 1% to 8% by weight
of the composition.
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about
4000. These are used at levels of from 0.2% to 5% by
weight, more preferably from 0.25% to 2.5% by weight.
These polymers and the previously mentioned homo- co-
polymeric polycarboxylate salts are valuable for reducing
ash deposition, and improving cleaning performance on~clay,
proteinaceous and oxidizable soils in the presence of
transition metal impurities.
Another optional ingredient useful in detergent
compositions is one or more enzymes.
Preferred enzymatic materials include the commercially
available amylases, neutral and alkaline proteases,
lipases, esterases and cellulases conventionally
incorporated into detergent compositions. Suitable enzymes
are discussed in US Patents 3,519,570 and 3,533,139.
For granular detergents, the enzymes are preferably coated
or prilled with additives inert toward the enzymes to
minimize dust formation and improve storage stability.
Techniques for accomplishing this are well known in the
art. In liquid formulations, an enzyme stabilization
system is preferably utilized. Enzyme stabilization
techniques for aqueous detergent compositions are also well
known in the art.
Preferred commercially available protease enzymes include
those sold under the tradenames Alcalase and Savinase by
'""' WO 94/07986 ~ ~ ~ ~ ~ ~ PCT/US93/08874
53
Novo Industries A/S (Denmark) and Maxatase by International
Bio-Synthetics, Inc. (The Netherlands). Protease enzyme
may be incorporated into the compositions in accordance
with'the invention at a level of from 0.005% to 2% active
enzyme by weight of the composition.
Preferred amylases include, for example, &-amylases
obtained from a special strain of B licheniforms, described
in more detail in GB-1,269,839 (Novo). Preferred
commercially available amylases include for example,
Rapidase, sold by International Bio-Synthetics Inc, and
Termamyl, sold by Novo Industries A/S. Amylase enzyme may
be incorporated into the composition in accordance with the
invention at a level of from 0.005% to 2% active enzyme by
weight of the composition.
An especially preferred lipase enzyme is manufactured and
sold by Novo Industries A/S (Denmark) under the trade name
Lipolase (Biotechnology Newswatch, 7 March 1988, page 6)
and mentioned along with other suitable lipases in EP-A-
0258068 (Novo). Another especially preferred lipcise is
described in EP-A-0218272 in the name of Gist-Brocades NV.
Lipase enzyme may be incorporated into the compositions in
accordance with the invention at a level of from 0.005% to
2% active enzyme by weight of the composition.
Other optional ingredients suitable for inclusion in the
compositions of the invention include perfumes, colours and
filler salts, with sodium sulfate being a preferred filler
salt.
Corrosion inhibitor
The present compositions may also contain corrosion
inhibitor, preferably incorporated at a level of from
0.05% to 10%, preferably from 0.1% to 5% by weight of
the total composition.
,....
WO 94/07986 PCT/US93/08874
- 1~14~1'~7
54
Suitable corrosion inhibitors include paraffin oil
typically a predominantly branched aliphatic
hydrocarbon having a number of carbon atoms in the
range of from 20 to 50; preferred paraffin oil
selected from predominantly branched C25-45 species
with a ratio of cyclic to noncyclic hydrocarbons of
about 32:68; a paraffin oil meeting these
characteristics is sold by Wintershall, Salzbergen,
Germany, under the trade name WINOG 70.
Other suitable corrosion inhibitor compounds include
benzotriazole and any derivatives thereof, mercaptans
and diols, especially mercaptans with 4 to 20 carbon
atoms including lauryl mercaptan, thiophenol,
thionapthol, thionalide and thioanthranol. Also
suitable are the C12-C20 fatty acids, or their salts,
especially aluminium tristearate. The C12-C20 hydroxy
fatty acids, or their salts, are also suitable.
Phosphonated octa-decane and other anti-oxidants such
as betahydroxytoluene (BHT) are also suitable.
Heavy metal ion sequestrant
The detergent compositions of the invention may be
formulated to contain as a non-essential component
heavy metal ion sequestrant, incorporated at a level
of from 0.005% to 3%, preferably 0.05 to 1%, most
preferably 0.07% to 0.4%, by weight of the total
composition.
Suitable heavy metal ion sequestrant for use herein
include organic phosphonates, such as amino alkylene
poly (alkylene phosphonate), alkali metal ethane 1-
hydroxy disphosphonates, nitrilo trimethylene
phosphonates.
"'"' WO 94/07986 ~ PCT/US93/08874
Preferred among above species are diethylene triamine
penta (methylene phosphonate), hexamethylene diamine
tetra.(-methylene phosphonate) and hydroxy-ethylene 1,1
diphosphonate.
The phosphonate compounds may be present either in
their acid form or as a complex of either an alkali or
alkaline metal ion, the molar ratio of said metal ion
to said phosphonate compound being at least 1:1. Such
complexes are described in US-A-4,259,200.
Preferably, the organic phosphonate compounds are in
the form of their magnesium salt.
Other suitable heavy metal ion sequestrant for use
herein include nitrilotriacetic acid and
polyaminocarboxylic acids such as
ethylenediaminotetracetic acid, ethylenetriamine
pentacetic acid, ethylenediamine disuccinic acid or
the water soluble alkali metal salts thereof.
Especially preferred is ethylenediamine-N,N'-
disuccinic acid (EDDS) or the alkali metal, alkaline
earth metal, ammonium, or substituted ammonium salts
thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or
magnesium salt or complex thereof. Examples of such
preferred sodium salts of EDDS include Na2EDDS and
Na3EDDS. Examples of such preferred magnesium
complexes of EDDS include MgEDDS and Mg2EDDS. The
magnesium complexes are the most preferred for
inclusion in compositions in accordance with the
invention.
Still other suitable heavy metal ion sequestrants for
use herein are iminodiacetic acid derivatives such as
2-hydroxyethyl diacetic acid or glyceryl imino
diacetic acid, described in EPA 317 542 and EPA 399
133.
WO 94/07986 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08874
56
The heavy metal ion sequestrant herein can consist of
a mixture of the above described species.
The machine dishwashing compositions of the invention can
be formulated in any desirable form such as powders,
granulates, pastes, liquids, gels and tablets but are
preferably granular.
In general, granular machine dishwashing detergent
compositions in accordance with the present invention can
be made via a variety of methods including dry mixing,
spray drying, agglomeration and granulation. A preferred
method of making the granular machine dishwashing
compositions involves a combination of dry mixing and
agglomeration techniques.
The bulk density of the granular detergent compositions in
accordance with the present invention typically have a bulk
density of at least 650 g/litre, more usually at least 700
g/litre and more preferably from 800 g/litre to 1200
g/litre.
Bulk density is measured by means of a simple funnel and
cup device consisting of a conical funnel moulded rigidly
on a base and provided with a flap valve at its lower
extremity to allow the contents of the funnel to be emptied
into an axially aligned cylindrial cup disposed below the
funnel. The funnel is 130 mm and 40 mm at its respective
upper and lower extremities. It is mounted so that the
lower extremity is 140 mm above the upper surface of the
base. The cup has an overall height of 90 mm, an internal
height of 87 mm and an internal diameter of 84 mm. Its
nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with
powder by hand pouring, the flap valve is opened and powder
WO 94/07986 ~ PCT/US93/08874
57
allowed to overfill the cup. The filled cup is removed
from the frame and excess powder removed from the cup by
passing a straight edged implement e.g. a knife, across its
upper edge. The filled cup is then weighed and the value
obtained for the weight of powder doubled to provide~the
bulk density in g/litre. Replicate measurements are made as
required.
The particle size of the components of granular
compositions in accordance with the invention should
preferably be such that no more than 5% of particles are
greater than l.4mm in diameter and not more than 5% of
particles are less than 0.15mm in diameter.
Generally, if the machine dishwashing detergent
compositions are in liquid form the liquid should be
thixotropic (ie; exhibit high viscosity when subjected to
low stress and lower viscosity when subjected to high
stress), or at least have very high viscosity, for example,
of from 1,000 to 10,000,000 centipoise. In many cases it
is desirable to include a viscosity control agent or a
thixotropic agent~to provide a suitable liquid product
form. Suitable thixotropic or viscosity control agents
include methyl cellulose, carboxymethylcellulose, starch,
polyvinyl, pyrrolidone, gelatin, cplloidal silica, and
natural or synthetic clay minerals.
Pasty compositions in accordance with the invention
generally have viscosities of about 5,000 centipoise and up
to several hundred million centipoise. In order to provide
satisfaction pasty compositions a small amount of a solvent
or solubilizing agent or of a gel-forming agent can be
included. Most commonly, water is used in this context and
forms the continuous phase of a concentrated dispersion.
Certain nonionic surfactants at high levels form a gel in
the presence of small amount of water and other solvents.
WO 94/07986 PCT/US93/08874
z ~ ~ ~~~ ~1 ~ -~ i
58
Such gelled compositions also envisaged in the present
invention.
Measurement of Critical Micelle Concentration
The surfactant system of the compositions/processes of the
invention is incorporated at a level which is directly
related to the critical micelle concentration of that
surfactant system measured in water at a temperature of
20~C. The critical micelle concentration is expressed in
units of ppm. Many methods are known for the determination
of critical micelle concentrations. Any reliable method is
suitable for use in the determination of these values
therein. Suitable methods are described in "Critical
Micelle Concentrations of Aqueous Surfactant Systems" by P.
Mukerjee and K.J. Mysels, NSRDS-NBS 36, pages 8 to 19.
Greasy soil removal test method.
A test method for assessing the greasy soil removal
(cleaning) ability of a detergent composition in a machine
dishwashing process is the "lipstick removal test method".
In this method, lipstick soiled plastic beakers are
prepared by taking clean plastic beakers and applying three
lipstick lines, of surface area approx lcm x 4cm to each
beaker. Thirty-two of such soiled beakers are prepared.
The lipstick commonly employed is No. 539, "Raspberry Rage"
from the Cover Girl Remarkable range as sold by Noxell.
Two soiled beakers are then placed in each of four
automatic dishwashing machines together with a ballast load
of clean glasses. The test plastic beakers are distributed
such that one is in the front right hand position, and the
other in the front left hand position in the upper wash
basket. The 50~C wash cycle, with no prewash, is selected
and 20 g. of product employed, with a wash volume of
typically 5 litres. The water has a Clark hardness of
13~C. Different comparative detergent products are used in
WO 94/07986 ~ ~ ~ ~ ~: ~ ~ PCT/US93/08874
59
each of the four machines, and the test procudure repeated
four times, such that each product is used once in each
machine. Lipstick removal is comparatively graded using a
Scheffe scale by three expert graders. Statistical
analysis is used to identify statistically significant (95%
confidence level) performance benefits.
Foaming power
The foaming power of a surfactant system, within a
detergent composition, may be measured using the DIN 53902
parts 1 and 2 test methods.
Wetting power
The wetting power of a surfactant system may be measured
using the DIN 53901 test method.
m
WO 94/07986
PCT/US93/08874
Examples
In Examples 1 and 2 the abbreviated component
identifications have the following meanings:
Citrate: Tri-Sodium citrate dihydrate
Phosphate . Sodium tripolyphosphate
MA/AA: Copolymers of 1:4 maleic/acrylic acid,
average molecular weight about 80,000
Silicate: Amorphous Sodium Silicate (Si02:Na20 ratio
normally follows)
Carbonate: Anhydrous sodium carbonate
Protease: Proteolytic enzyme sold under the tradename
Savinase by Novo Industries A/S
Amylase: Amylolytic enzyme sold under the tradename
Termamyl by Novo Industries A/S
Lipase: Lipolytic enzyme sold under the tradename
Lipolase by Novo Industries A/S
Nonionic: C13-015 mixed ethoxylated/propoxylated fatty
alcohol with an average degree of
ethoxylation of 3.8 and an average degree of
propoxylation of 4.5 sold under the
tradename Plurafac LF404 by BASF Gmbh
(alkoxylated nonionic surfactant).
Sulphate: Anhydrous Sodium Sulphate
Perborate: anhydrous sodium parborate monohydrate
bleach, empirical formula NaB02.H20
TAED: Tetraacetyl ethylene diamine
SCS: Sodium cumene sulphonate
Dobanol: A blend of C12-C15 ethoxylated alcohols with
an average degree of ethoxylation of 9, sold
under the tradename Dobanol 25.9 by Shell
Chemicals (UK) Ltd
C18DMA0.2M20 Octadecyldimethylamine N-oxide dihydrate,
ADMOX 18, Ethyl corp.
35AE3S: C13-015 alkyl ethoxysulfate with an average
degree of ethoxylation of 3
""" WO 94/07986 PCT/US93/08874
61
25AE3S . C12-C15 alkyl ethoxysulfate with an average
degree of ethoxylation of 3.
Suds Suppressor:l2% silicone/silica,l8% stearyl alcohol,
70% starch, in granular form.
WO 94/07986 ~~ PCT/US93/08874
62
Example 1
The following machine dishwashing detergent compositions
were prepared (parts by weight) in accord with the
invention.
A B C D E
Citrate 24.0 - - 24.0 24.0
Phosphate - 46.0 46.0 - -
MA/AA 6.0 - - 6.0 6.0
Silicate (2.0 ratio) 27.5 33.0 33.0 27.5 27.5
Carbonate 12.5 - - 12.5 12.5
Perborate 10.4 10.4 10.4 10.4 10.4
TAED 3.0 3.0 3.0 3.0 3.0
Protease 2.2 2.2 2.2 2.2 2.2
Amylase 2.0 1.5 1.5 1.5 1.5
Lipase - 2.65 2.65 2.65 2.65
Nonionic - 1.5 1.5 1.5 1.5
Sulphate 1.4 2.4 2.4 12.1 l2.1
Dobanol 6.5 - - - -
SCS 3.5 - - - -
35AE3S 10.0 5.0 - 5.0
C18DMA0.2H20 - - 5.0 - 5.0
Suds suppressor 1.0 - - - -
(NB: formulations do not always add up to 100)
35AE3S has a critical micelle concentration, measured in
water, of about 30ppm. C18DMA0.2H20 has a critical micelle
concentration, measured in water, of about lppm.
The composition was used in a process in accord with the
process aspect of the invention as follows . the 50~C wash
setting of a mini dishwasher was selected, the wash process
comprising main wash and rinse cycles. The volume of wash
'~"" WO 94/07986 PCT/US93/08874
~14~i.?'
63
solution in the main wash was about 2.5 litres. 10 grams of
each of products A to E was employed in each case to give a
surfactant level in the main wash solution of LSD1 of 400
ppm for product A and 200 ppm for products B to E
respectively. The water hardness was 10~ Clark Hardness
(142.9 ppm CaCO3 equivalent). Plastic beakers and a ballast
load of clean crockery comprised the wash load. Improved
cleaning, and in particular spotting/filming prevention,
was obtained when the performance of products A to E was
compared to products related to A to E, being identical
other than in not containing the (non-alkoxylated nonionic)
surfactant.
WO 94/07986 ,. , PCT/US93/08874
~~.4~17'~
64
Example 2
The following granular machine dishwashing detergent
compositions were prepared (parts by weight). Product D is
a prior art composition and product E is a composition in
accordance with the invention. The pH of both compositions
D and E, as a 1% solution measured at 20oC, was 8.7.
D E
Citrate 28.0 28.0
MA/AA 7.5 7.5
Bicarbonate 30.0 30.0
PB4 8.0 8.0
TAED 3.8 3.8
Protease 2.2 2.2
Amylase 1.5 1.5
Nonionic 1.5 1.5
25AE3S - 5.0
Paraffin 0.5 0.5
Water, miscellaneous to balance.
Product E gave good spotting/filming performance when
employed in a machine dishwashing process at a product
dosage of 4,000 ppm in the wash solution (i.e.
concentration of 25AE3S of 200 ppm in the wash solution).
Product E also gave improved soil removal, over product D
which contains no 25AE3S. 25AE3S has a critical micelle
concentration measured in water of about 30ppm.
WO 94/07986 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08874
In Example 3 hereinafter, the abbreviated component
identifications have the following meanings:
Amine Oxides
1. C18DMA0.2H20: Octadecyldimethylamine N-Oxide
dihydrate, ADMOX 18, Ethyl Corp.
2. BLEND DMAO: 80:20 wt. C18/C16 blend of
Octadecyldimethylamine N-Oxide
dihydrate and Hexadecyldimethylamine
N-Oxide dihydrate
3. BHEAO Blend 70:30 wt C18/C16 blend of octadecyl
bis(hydroxyethyl) amine N-Oxide
anhydrous and
Hexadecylbis(hydroxyethyl)
amine N-Oxide anhydrous
pH-Adjustinc Agents
1. Citrate: trisodium citrate dihydrate
2. Citric Acid: citric acid anhydrous granular
3. Carbonate: sodium carbonate anhydrous granular
4. Silicate: Hydrous Sodium Silicate, Si02:Na20 =
2:1, PQ Corp. , sold as BRITESIL H20
Alkoxylated Nonionic
Surfactant
1. LF404: C13-C15 mixed ethoxylated/propoxylated
fatty alcohol with average degree of
ethoxylation 3.8 and average degree
of
propoxylation 4.5 sold under the
tradename PLURAFAC LF404 by BASF Gmbh.
suds suporessors
1. ISOFOL 16 Branched Alcohol from Condea Chemie
Detersive Enzymes / Enayme Stabilizers
1. Savinase 6T protease from Novo Industri
2. Alcalase 3T protease from Novo Industri
3. Termamyl 60T amylase from Novo Industri
4. L2: lipase from pseudomonas
pseudoalcaligenes, activity 100,000
LU/g
Disoersant Polymers
WO 94/07986 ~ 1 ~ ~ ~ ~ ~ PCT/US93/08874
66
1. MA/AA-1 Dispersant polymer from BASF sold as
SOKOLAN CPS, dry form (92% active)
2. 480 Dispersant polmyer from Rohm & Haas
sold as ACCUSOL 480 ND
Bleaches
1. PC: Sodium Percarbonate granular
2. PB: Sodium Perborate (Monohydrate or
Tetrahydrate) granular
4. TAED: tetra-acetylethylenediamine, 92%
active prill with
carboxymethylcellulose
Other Optional Adiuncts
1. Sulfate: Sodium sulfate anhydrous
2. Paraffin: WINOG 70
In Example 3 hereinafter, the quantities of ingredients are
percentages by weight of ingredients on an anhydrous basis
unless otherwise indicated, regardless of the forms of the
ingredients actually mixed to form the compositions.
WO 94/07986 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08874
67
EXAMPLE 3
Granular automatic dishwashing detergents of the invention
are as follows:
I II III
C18DMA0.2H20 0 0 2
Blend DMAO 0 4 0
BHEAO Blend 5 0 0
Citric Acid 29 0 19
Citrate 0 19 0
Silicate (As Si02) 26 19 8.5
MA/AA-1 4 0 0
Carbonate 0 20 9.5
LF404 1.5 0 0
480 0 6 6
PB (as Av0) 0.8 1.8 0
PC 0 0 11.4
TAED 4.0 0 3.8
Alcalase 3T 0 0 2.4
Savinase 6T 2.0 2.4 0
Termamyl 60T ~ 1.0 1.1 1.1
L2 0.1 0 0
ISOFOL 16 1.0 0 0
Paraffin 0.5 0 0
Balance to 100% -----------------sulphate, perfume,
water
The compositions are used at a concentration of about 0.28%
by weight in North American GE Potscrubber dishwashers; or
at a concentration of about 0.4% by weight in European
Miele Dishwashers, to remove eg: lipstick from plastic
beakers in the lipstick removal test method. The
compositions I - III provide statistically significant
performance benefits in the lipstick removal test method
over related formulations identical, other than that they
WO 94/07986 , PCT/US93/08874
~ 4 ~ ~.'~'~
68
do not contain amine oxide surfactants. The critical
micelle concentrations, measured in water, of
C18DMA0.2I~i2o, Blend DHAO and BEHEAD Blend, are about 1
ppm, 2ppm and 4ppm respectively.
