Note: Descriptions are shown in the official language in which they were submitted.
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METHOD FOR SANITIZATION OF
SUBSTRATES WITH DETERGENT COMPOSITIONS
RELATED APPLICATIONS
This application claims priority under 35 U.S.C. 119(e) to U.S. Provisional
Application No. 60/053,322, filed on July 21,1997, and to co-pending U. S.
Application
No. 08/961,622, filed October 31, 1997.
TECHNICAL FIELD
The present invention is in the field of detergent compositions, preferably
liquid or
gel detergents. More specifically, the invention relates to a method for
removing soils and
sanitizing (significantly reducing microorganism populations) plastics,
dishware,
countertops, fabric, wood surfaces, and other substrates by applying a light
duty detergent
composition, preferably a liquid, cream, paste, or gel detergent composition,
which
preferably comprises non-quaternary surfactants. This method provides enhanced
cleaning coupled with sanitizing, disinfecting, or antibacterial action on the
treated
surfaces.
BACKGROUND OF THE INVENTION
Detergents used for washing tableware (i.e., glassware, china, silverware,
plastic,
etc.) or kitchenware (i.e. cook ware, cutting boards, counter tops, etc.) in
the home or
institution have long been known. Dishwashing in the seventies is reviewed by
Mizuno in
Vol. 5, Part III of the Surfactant Science Series, Ed. W.G. Cutler and R.C.
Davis, Marcel
Dekker, N.Y., 1973. The particular requirements of cleansing tableware and
leaving it in
a sanitary, essentially soil-free, residue-free state has indeed resulted in
so many particular
compositions that the body of art pertaining thereto is now recognized as
quite distinct
from other cleansing product art.
Furthermore, consumers continue to have a great concern with the sanitary
conditions in their household. There is perceived to be a real problem with
germs in the
household, particularly on dishware, food preparation areas, and on equipment
used with
small children or sick persons.
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2
Consumers continue to experience problems with obtaining adequate
antibacterial
action on various substrates, including typical kitchen surfaces and dishware.
Formulators
have experienced di~culties in formulating detergents which both remove soils
and
reduce the amount of microorganisms on the surface. Typically to accomplish
both jobs, '
consumers have resorted to adding chlorine bleach to the wash water or to
wiping the
already cleaned surface with a bleach-containing solution for added
antibacterial action.
Although chlorine bleach is effective for stain fighting and for antibacterial
action, it
is not compatible with a variety of detergent ingredients and does little to
actually remove
soils from the substrate. Moreover, bleach is consider harsh to many surfaces
and to
consumer's hands and it has an unpleasant odor.
As a consequence to the above-identified problem, there has been a substantial
amount of research to develop detersive systems which are stable with a
variety of
ingredients and which accomplishes both soil removal and sanitization.
Moreover, an important consideration in the development of consumer products
effective on both soils and germ removal or kill is the additional costs
associated with the
inclusion of multiple additives. Accordingly, it is of substantial interest to
the
manufacturers of detergent products to find a less expensive component which
can
perform both duties.
SUMMARY OF THE INVENTION
By the present invention, it has now been discovered that certain surfactants
are
stable, perform very well on removing soils, and sanitize when the surfactant
is applied
without additional water (or with minimum additional water) to a substrate and
allowed
to remain in contact for a period of time.
Accordingly, the present invention solves the long-standing need for an
inexpensive
cleaning system which performs efFlciently and effectively under soil load
conditions and
which provides very good antirnicrobial action. This, in turn, can lead to
healthier family
members which can manifest itself in less sick days, less chance for
transmittance of
disease and fewer trips to a healthcare provider.
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3
The invention herein is a method for sanitizing a microbe containing substrate
comprising the steps of
a) contacting the substrate with a detergent composition comprising an
effective
amount of an antimicrobial agent;
b) allowing the detergent composition to remain in contact with the substrate
for a
sufficient time to significantly reduce the amount of microbes on the
substrate.
In one preferred embodiment of this invention, step b) can be carned out in a
conventional
microwave oven to activate the antimicrobial action of the detergent
composition.
Without intent to limit the types of substrates that may be treated, examples
of
substrates which can be treated by this method include fabrics, ceramic,
porcelain, plastic,
dish cloths, cutting boards, surgicallmedical equipment, baby bottles,
dishware,
dentifiice/dentures, wood, food preparation surfaces, sponges, glass, rubber,
metal,
coated metal (e.g., Teflon~-coated pans) and mixtures thereof.
The method of application can vary significantly. For example, the product can
be
applied directly to the substrate, sprayed onto the substrate, or spread by an
implement
(sponge, roller, paper towel, dish cloth, etc.) onto the surface to be
treated.
The method herein can be employed to kill or reduce the level of viable
microbes
which may include any various microorganisms, such as bacteria (gram + or -),
viruses
(enveloped or unenveloped), parasites, filngi/spores, and other typical
household germs
commonly found on kitchen surfaces.
All percentages and proportions herein are by weight, and all references cited
are
hereby incorporated by reference, unless otherwise specifically indicated.
DETAILED DESCRIPTION OF THE INVENTION
Definitions - The present detergent compositions comprise an "effective
amount" or
a "soil and sanitizing amount" of a particularly defined antimicrobial agent
which is
preferably a surfactant. An "effective amount" or "sanitizing amount" of an
antimicrobial
agent is any amount capable of measurably improving both soil removal from and
sanitization of the substrate, i.e., soiled dishware, when it is washed by the
consumer. In
general, this amount may vary quite widely.
As used herein the terms "disinfecting", "disinfection", "antibacterial",
"germ kill",
and "sarutization" are intended to mean killing microbes commonly found in
household
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kitchens and houses. Examples of various microbes include: germs, bacteria,
viruses,
parasites, and fungi/spores. Preferably the detergent compositions used herein
contact the
substrate for a sufficient time to significantly reduce the amount of microbes
on the
substrate. By "significant reduction" it is meant that at least about 50% of
the microbes
on the substrate are killed or otherwise rendered inactive, preferably the
amount of
microbes on the substrate is reduced by at least about 90%, and most
preferably the
amount of microbes on the substrate is reduced by at least about 99.9%.
Examples of surfactants which are useful antimicrobial agents for use herein
include
anionic, cationic, nonionic, and amphoteric surfactants. Preferred examples
are: alkyl
alkoxy sulfates, including alkyl ethoxy sulfates, linear alkyl benzene
sulfonates, amine
oxides, polyhydroxy fatty acid amides, ethoxylated alcohols, diamines, amides,
alkyl
polyglucosides, betaines, and mixtures thereof. When the antimicrobial agent
is a cationic
surfactant it is preferred that the cationic surfactant is not a quaternary
ammonium
surfactant.
The detergent compositions of the present invention comprise surfactant from
about
1% to about 80%, preferably from about 10% to about 70%, more preferably from
about
20% to about 60%, and most preferably from about 30% to about 50%, by weight
of the
total composition.
Typically the "sufficient time" in step b} is at least about 10 seconds,
preferably from
about I S seconds to about 2 minutes and more preferably from about 30 seconds
to about
1 minute. Longer times, of course, are effective.
It has surprisingly been found that placing the substrate, while it is still
in contact
with the detergent composition, in a conventional microwave oven and operating
the oven
for a suffcient time, can enhance the antimicrobial action of the detergent
composition.
While not wanting to be bound by any one theory, it is believed that the
energy imparted
to the detergent composition by the microwave radiation within the oven serves
to
activate and enhance the antimicrobial action of the detergent composition.
Microwave
ovens suitable for use in the present invention are manufactured by companies
such as
Litton, Amana~, Sharp, General Electric, and others, and have become
ubiquitous
in kitchens throughout the industrial world. Microwave ovens can be purchased
at any
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number of department stores, hardware stores and large variety stores, such as
K-Mart~
and Wal-Mart.
By "operating" the microwave oven it is meant that the sufficient time is
selected
and the microwave oven is turned on for the selected length of time; in all
respects, the
manufacturers suggested operating instructions and safety precautions should
be
followed. Depending on the length of time selected for operating the microwave
oven, the
substrate might be warm and require care when removing it from the oven. A
cool down
period for the substrate may also be desirable.
To achieve maximum sanitization action, the detergent compositions are
preferably
applied directly to the substrate with a minimum of water, even more
preferably free of
added water. Moreover, the substrate should remain in contact with the
detergent for a
sufficient time before water is added or before the detergent is rinsed away.
However, the
surface to be treated may be prerinsed or wetted before application of the
detergent
composition herein as long as no standing water remains. In other words, the
surface may
be damp but not submerged in water. It is believed that the detergent
compositions with
the percent surfactant level stated herein have sufficiently high ingredient
concentrations
to allow for some dilution during use. Of course this depends on the
concentration of the
active ingredients in the product. Preferably the detergent composition is
diluted with less
than about 10% water, more preferably less than about 30% water and most
preferably
less than about 50% water.
In contrast and for comparative purposes, in a typical household kitchen, a
sink
filled with water and dishes and dosed by an average amount of liquid
dishwashing
detergent product (4 to 7g, with approximately 10-45% surfactant) will have a
total
product concentration level of less than 1% in the wash water, i.e., diluted
by 99% with
water. If the washing is conducted in a rubber tub or large bowl sitting in
the sink, the
total product concentration is only about 5%, i.e., 95% dilution. Even a
sponge which
has been soaked in water with detergent applied to the sponge's surface will
have a
detergent product concentration of only about 10%, i.e. 90% dilution.
Product/Instructions - This invention also encompasses the inclusion of
instructions
on the use of the detergent composition with the package containing the
detergent
compositions herein or with other forms of advertising associated with the
sale or use of
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6
the detergent compositions. The instructions may be included in any manner
typically
used by consumer product manufacturing or supply companies. Examples include
providing instructions on a label attached to the container holding the
composition; on a
sheet either attached to the container or accompanying it when purchased; or
in
advertisements, demonstrations, andlor other written or oral instructions
which may by
connected to the purchase or use of the detergent compositions.
Specifically the instructions will include a description of the use of the
surfactant
containing detergent composition in connection with allowing the detergent to
remain in
contact with the substrate before the addition of a substantial volume of
water or before
rinsing. The instructions, for instance, may additionally include information
relating to the
length of contact time; the recommended dosage or amount of treating
composition to
apply to the substrate, if soaking or rubbing is appropriate; the recommended
amount of
water, if any, to apply to the substrate before and after treatment; other
recommended
treatment to accompany the detergent application.
Accordingly, the present invention embraces a product comprising a detergent
composition comprising an effective amount of an antimicrobial agent and
instructions for
using the detergent composition, the instructions include the steps of
a) contacting a microbe-containing substrate with the detergent composition;
and
b) allowing the detergent composition to remain in contact with the substrate
for a
sui~icient time to significantly reduce the amount of microbes on the
substrate.
Other Ingredients - Detersive ingredients or adjuncts optionally included in
the
instant compositions can include one or more materials for assisting or
enhancing cleaning
performance, treatment of the substrate to be cleaned, or designed to improve
the
aesthetics, maintain chemical and physical stability, or ease of manufacture
of the
compositions. Other adjuncts which can also be included in compositions of the
invention
at their conventional art-established levels, generally from 0% to about 20%
of the
composition, preferably at from about 0.1% to about 10%, include one or more
processing aids, polymer thickeners, dyes, fillers, enzymes, alkalinity
sources,
hydrotropes, stabilizers, perfumes, solvents, carriers, baking soda,
carbonates,
hydrobenzoic acid, dicarboxylic acid, bleach, divalent ions, dispersant
polymers, chelants,
builders such as citrate and buffers. The composition preferably has a pH of
from about 3
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7
to about 11.5, preferably from about 6 to about 11. The divalent ions, when
present, are
preferably selected from inorganic cations, organic cations and mixtures
thereof, and most
preferably are selected from Mg2+, Ca2+ and mixtures thereof.
Other non-surfactant germicides may be included for additional antimicrobial
action
if they do not adversely interfere with the surfactants used herein. Examples
of
antimicrobials include triclosan, triclocarbon, hydrogen peroxide, other
oxygen bleaches,
para-chloro-meta-xylenol, iodineliodophors, selected alcohols, chlorhexidine,
phenols,
phospholipids, thymol, eugeniol, geraniol, oil of lemon grass, and limonene.
Certain
quaternary surfactants may also show antimicrobial action and may be included
as a
secondary germ kill agent.
Anionic Surfactants - The anionic surfactants useful in the present invention
are
preferably selected from the group consisting of branched alkyl ethoxy
sulfates, Cg-C 1 g
linear alkylbenzene sulfonate, alpha olef n sulfonate, paraffin sulfonates,
methyl ester
sulfonates, primary, branched-chain and random Cg-C20 alkyl sulfates (AS), the
Cg-Clg
secondary (2,3) alkyl sulfates of the formula CH3(CH2)x (CHOS03-M+) CH3 and
CH3
(CH2)y (CHOS03-M+) CH2CH3 where x and (y + 1) are integers of at least about
7,
preferably at least about 9, and M is a water-solubilizing cation, especially
sodium,
unsaturated sulfates such as oleyl sulfate, Cg-Clg alkyl alkoxy sulfates
("AEXS";
especially EO 0.5-7 ethoxy sulfates), Cg-C 1 g alkyl alkoxy carboxylates
(especially the EO
0.5-5 ethoxycarboxylates), the Cg-Clg glycerol ethers, the Cg-Clg alkyl
polyglycosides
and their corresponding sulfated polyglycosides, alkyl sulfonates,
sarcosinates, taurinates,
Cg-C 1 g alpha-sulfonated fatty acid esters and mixtures thereof.
One type of anionic surfactant which can be utilized encompasses alkyl ester
sulfonates. These are desirable because they can be made with renewable, non-
petroleum
resources. Preparation of the alkyl ester sulfonate surfactant component can
be effected
according to known methods disclosed in the technical literature. For
instance, linear
esters of Cg-C20 carboxylic acids can be 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,
and
coconut oils, etc.
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8
The preferred alkyl ester sulfonate surfactant comprises alkyl ester sulfonate
surfactants of the structural formula:
O
R3-CH-C-OR4
S03M
wherein R3 is a Cg-C20 hydrocarbyi, preferably an alkyl, or combination
thereof, R4 is a
C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a
soluble salt-
fonming cation. Suitable salts include metal salts such as sodium, potassium,
and lithium
salts, and substituted or unsubstituted ammonium salts, such as methyl-,
dimethyl, -
trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and
dimethyl
piperdinium, and cations derived from alkanolamines, e.g. monoethanol-amine,
diethanolamine, and triethanolamine. Preferably, R3 is C 1 p-C 16 alkyl, and
R4 is methyl,
ethyl or isopropyl. Especially preferred are the methyl ester sulfonates
wherein R3 is
C 14-C 16 alkyl .
Alkyl sulfate surfactants are another type of surfactant for use herein.
Examples of
alkyl sulfates are water soluble salts or acids of the formula ROS03M wherein
R
preferably is a C 10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C 10-
C20 alkyl component, more preferably a C 12-C 1 g alkyl or hydroxyalkyl, and M
is H or a
cation, e.g., an alkali or alkaline (Group IA or Group IIA) metal cation
(e.g., sodium,
potassium, lithium, magnesium, calcium}, substituted or unsubstituted ammonium
cations
such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium
cations,
e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from
alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and
mixtures
thereof, and the like. Typically, alkyl chains of C12-16 are preferred for
lower wash
temperatures (e.g., below about 50°C) and C16-18 alkyl chains are
preferred for higher
wash temperatures (e.g., above about 50°C).
Alkyl alkoxylated sulfate surfactants are another category of useful anionic
surfactant. These surfactants are water soluble salts or acids typically of
the formula
RO{A)mS03M wherein R is an unsubstituted Clp-C24 alkyl or hydroxyalkyl group
having a C 10-C24 alkyl component, preferably a C 12-C20 alkyl or
hydroxyalkyl, more
preferably C 12-C 1 g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m
is greater
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than zero, typically between about 0.5 and about 6, more preferably between
about 0.5
and about 3, and M is H or a cation which can be, for example, a metal cation
(e.g.,
sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-
ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated
sulfates are
contemplated herein. Exemplary surfactants are C 12-C 1 g alkyl polyethoxylate
( I .0)
sulfate, C I 2-C 1 g alkyl polyethoxylate (2.25) sulfate, C 12-C 1 g alkyl
polyethoxylate (3.0)
sulfate, and C 12-C 1 g alkyl polyethoxylate (4.0) sulfate wherein M is
conveniently
selected from sodium and potassium. Surfactants far use herein can be made
from natural
or synthetic alcohol feedstocks. Chain lengths represent average hydrocarbon
distributions, including branching.
Other anionic surfactants useful for detersive and sanitization 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 soap, Cg-C20 linear alkylbenzene sulphonates, Cg-C22
primary
or secondary alkanesulphonates, Cg-C24 olefin sulphonates, sulphonated
polycarboxylic
acids prepared by sulphonation of the pyrolyzed product of alkaline earth
metal citrates,
e.g., as described in British patent specification No. 1,082,179, alkyl
glycerol sulfonates,
fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol
ethylene oxide
ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as
the acyl
isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinamates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and
unsaturated C 12-
CI g monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6-C 14
diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described below),
branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those
of the
formula RO(CH2CH20)kCH2C00-M+ wherein R is a Cg-C22 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" (VoI. I and II by Schwartz, Perry and
Berch). A
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IO
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 Detergent Surfactants - 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 16, line 6, incorporated herein by
reference.
Exemplary, non-limiting classes of useful nonionic surfactants include: Cg-C 1
g alkyl
ethoxylates ("AE"), with EO about 1-22, including the so-called narrow peaked
alkyl
ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and
mixed
ethoxy/propoxy), alkyl dialkyl amine oxide, alkanoyl glucose amide, and
mixtures thereof.
Other nonionic surfactants for use herein include:
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols. 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 12 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 Igepal~
CO-630, marketed by the GAF Corporation; and Triton~ X-45, X-114, X-100, and X-
102, all marketed by the Rohm & Haas Company. These compounds are commonly
referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
The condensation products of aliphatic alcohols with from about 1 to about 25
moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either
be straight or
branched, primary or secondary, and generally contains from about 8 to about
22 carbon
atoms. Particularly preferred are the condensation products of alcohois having
an alkyl
group containing from about 10 to about 20 carbon atoms with from about 2 to
about 18
moles of ethylene oxide per mole of alcohol. Examples of commercially
available nonionic
surfactants of this type include Tergitol~ 15-S-9 (the condensation product of
Cl I-C15
linear secondary alcohol with 9 moles ethylene oxide), Tergitol~ 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;
Neodol~ 45-9 (the condensation product of C 14-C 15 linear alcohol with 9
moles of
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11
ethylene oxide), Neodol~ 23-6.5 (the condensation product of C 12-C 13 linear
alcohol
with 6.5 moles of ethylene oxide), Neodol~ 45-7 (the condensation product of
C14-C15
linear alcohol with 7 moles of ethylene oxide), Neodol~ 45-4 (the condensation
product
of C 14-C 15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell
Chemical
Company, and Kyro~ EOB (the condensation product of C13-C15 alcohol with 9
moles
ethylene oxide}, marketed by The Procter & Gamble Company. Other commercially
available nonionic surfactants include Dobanol 91-8~ marketed by Shell
Chemical Co.
and Genapol UD-080~ marketed by Hoechst. This category of nonionic surfactant
is
referred to generally as "alkyl ethoxylates."
The condensation products of ethylene oxide with a hydrophobic base formed by
the
condensation of propylene oxide with propylene glycol. 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 to
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
polyoxyethyiene
content is about SO% 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 Pluronic~ surfactants,
marketed by
BASF.
The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of
these
products consists of the reaction product of 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 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 Tetronic~ compounds,
marketed
by BASF.
Semi-polar nonionic surfactants are a special category of nonionic surfactants
which
include water-soluble amine oxides containing one alkyl moiety of from about
10 to about
18 carbon atoms and 2 moieties selected from the group consisting of alkyl
groups and
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hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-
soluble
phosphine oxides containing one alkyl moiety of from about 10 to about 18
carbon atoms
and 2 moieties selected from the group consisting of alkyl groups and
hydroxyalkyl
groups containing from about 1 to about 3 carbon atoms; and water-soluble
sulfoxides
containing one alkyl moiety of from about 10 to about 18 carbon atoms and a
moiety
selected from the group consisting of alkyl and hydroxyalkyl moieties of from
about 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the formula
O
T
R3 ~~R4)xN~RS)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
thereof containing
from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene
group
containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from
0 to about
3; and each RS is an alkyl or hydroxyalkyl group containing from about 1 to
about 3
carbon atoms or a polyethylene oxide group containing from about 1 to about 3
ethylene
oxide groups. The RS groups can be attached to each other, e.g., through an
oxygen or
nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C 10-C 1 g alkyl dimethyl
amine
oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued
7anuary
21, 1986, having a hydrophobic group containing from about 6 to about 30
carbon atoms,
preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g.,
a
polyglycoside, hydrophilic group containing 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,
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13
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 polyalkylene-oxide 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 about 8 to about 18,
preferably
from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a
straight chain
saturated alkyl group. The alkyl group can contain up to about 3 hydroxy
groups and/or
the polyalkyleneoxide chain can contain up to about 10, preferably less than
5,
alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyl,
decyl,
undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and
octadecyl, di-
tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses,
fructosides,
fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-
, tetra-, and
pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about 10
to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2;
t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10,
preferably from
about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The
glycosyl is
preferably derived from glucose. To prepare these compounds, the alcohol or
alkylpolyethoxy alcohol is formed first and 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.
Fatty acid amide surfactants having the formula:
O
R6-C-N(R7)2
wherein R6 is an alkyl group containing from about 7 to about 21 (preferably
from about
9 to about 17) carbon atoms and each R7 is selected from the group consisting
of
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14
hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H40)xH where x varies from
about
1 to about 3.
Preferred amides are Cg-C20 ammonia amides, monoethanolamides, dietha-
nolamides, and isopropanolamides.
Cationic/amphoteric - Non-quaternary, cationic detersive surfactants can also
be
included in detergent compositions of the present invention. Cationic
surfactants useful
herein are described in U.S. Patent 4,228,044, Cambre, issued October 14,
1980.
Ampholytic surfactants can be incorporated into the detergent compositions
hereof.
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. Preferred
amphoteric
include C12 -Clg alkyl ethoxylates ("AE") including the so-called narrow
peaked alkyl
ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially ethoxylates and
mixed
ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines ("sultaines"), C 10-C 1
g amine
oxides, and mixtures thereof.
Polyhydroxy Fattv Acid Amide Surfactant - The detergent compositions hereof
may
also contain polyhydroxy fatty acid amide surfactant. The polyhydroxy fatty
acid amide
surfactant component comprises compounds of the structural formula:
O R1
R2-C-N-Z
wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture
thereof, preferably C 1-C4 alkyl, more preferably C 1 or C2 alkyl, most
preferably C 1 alkyl
(i.e., methyl); and R2 is a CS-C31 hydrocarbyl, preferably straight chain C7-
C19 alkyl or
alkenyl, more preferably straight chain Cg-C 17 alkyl or alkenyl, most
preferably straight
chain C 11-C 1 S alkyl or alkenyl, or mixtures 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
CA 02297061 2000-O1-19
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preferably will be derived from a reducing sugar in a reductive amination
reaction; more
preferably Z will be 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-CH20H, -CH(CH20H)-(CHOH)n-1-CH20H, -CH2-
(CHOH)2(CHOR')(CHOH}-CH20H, and alkoxylated derivatives thereof, where n is an
integer from 3 to S, inclusive, and R' is H or a cyclic or aliphatic
monosaccharide. Most
preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
R 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-deoxyfiuctityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, I-deoxymannityl, 1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In
general,
they can be made by reacting an alkyl amine with a reducing sugar in a
reductive
amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then
reacting
the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a
condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid
amide
product. Processes for making compositions containing polyhydroxy fatty acid
amides
are disclosed, for example, in G.B. Patent Specification 809,060, published
February 18,
1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20,
1960
to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March
8,
1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of
which is
incorporated herein by reference.
Diamines - Preferred organic diamines are those in which pKl and pK2 are in
the
range of about 8.0 to about 11.5, preferably in the range of about 8.4 to
about 11, even
more preferably from about 8.6 to about 10.75. Preferred materials for
performance and
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16
supply considerations are 1,3 propane diamine (pKl=10.5; pK2=8.8), 1,6 hexane
diamine
(pKl=11; pK2=10), 1,3 pentane diamine (Dytek EP) (pKi=10.5; pK2=8.9), 2-methyl
1,5
pentane diamine (Dytek A) (pKl=11.2; pK2=10.0). Other preferred materials are
the
primary/primary diamines with alkytene spacers ranging from C4 to C8.
Definition ofpKl and pK2 - As used herein, "pKal" and "pKa2" are quantities of
a
type collectively known to those skilled in the art as "pKa" pKa is used
herein in the same
manner as is commonly known to people skilled in the art of chemistry. Values
referenced herein can be obtained from literature, such as from "Critical
Stability
Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London,
1975. Additional information on pKa's can be obtained from relevant company
literature,
such as information supplied by Dupont, a supplier of diamines.
As a working definition herein, the pKa of the diamines is specified in an all-
aqueous
solution at 25oC and for an ionic strength between 0.1 to 0.5 M. The pKa is an
equilibrium constant which can change with temperature and ionic strength;
thus, values
reported in the literature are sometimes not in agreement depending on the
measurement
method and conditions. To eliminate ambiguity, the relevant conditions and/or
references
used for pKa's of this invention are as defined herein or in "Critical
Stability Constants:
Volume 2, Amines". One typical method of measurement is the potentiometric
titration
of the acid with sodium hydroxide and determination of the pKa by suitable
methods as
described and referenced in "The Chemist's Ready Reference Handbook" by Shugar
and
Dean, McGraw Hill, NY, 1990.
It has been determined that substituents and structural modifications that
lower pKl
and pK2 to below about 8.0 are undesirable and cause losses in performance.
This can
include substitutions that lead to ethoxylated diamines, hydroxy ethyl
substituted
diamines, diamines with oxygen in the beta (and less so gamma) position to the
nitrogen
in the spacer group (e.g., Jeffamine EDR 148). In addition, materials based on
ethylene
diamine are unsuitable.
The diamines useful herein can be defined by the following structure:
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17
wherein R1_4 are independently selected from H, methyl, -CH3CH2, and ethylene
oxides;
. Cx and Cy are independently selected from methyiene groups or branched alkyl
groups
where x+y is from about 3 to about 6; and A is optionally present and is
selected from
' electron donating or withdrawing moieties chosen to adjust the diamine pKa's
to the
desired range. If A is present, then x and y must both be 1 or greater.
Examples of preferred diamines include the following:
~N~NH2
Dimethyl aminopropyl amine: ~ ;
HZN
1,6-Hexane Diamine: NHZ ;
1,3 propane diamine - HZN NHZ ;
HzN NH2
2-methyl 1,5 pentane diamine - ;
H2N~
1,3-pentanediamine, available under the tradename Dytek EP NH2 ;
HzN' ~ 'NHz
1-methyl-diaminopropane - ;
~o~o~~z
Jeffamine EDR 148 - ;
and mixturesthereof.
SecondarX, Surfactants - Secondary detersive surfactant can be selected from
quaternary ammonium surfactants as long as the quaternary surfactant does not
adversely
affect the primary surfactant of this invention. Generally, the secondary,
quaternary
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18
surfactant may be added for additional antimicrobial action in the detergent
compositions
herein.
Quaternary surfactants include the ammonium surfactants such as
alkyldimethylammonium halogenides, and those surfactants having the formula:
[R2{OR3 )y~ [R4{OR3 )y~2R5~X-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon
atoms in the alkyl chain, each R3 is selected from the group consisting of -
CH2CH2-,
CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures thereof; each R4 is
selected from the group consisting of Cl-C~ alkyl, CI-C4 hydroxyalkyl, benzyl,
ring
structures formed by joining the two R4 groups, -CH2CHOHCHOHCOR6CHOH-
CH20H wherein R6 is any hexose or hexose polymer having a molecular weight
less than
about 1000, and hydrogen when y is not O; RS is the same as R4 or is an alkyl
chain
wherein the total number of carbon atoms of R2 plus RS is not more than about
I8; each
y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and
X is any
compatible anion.
Builders - Detergent builders can optionally be included in the compositions
herein
to assist in controlling mineral hardness. Inorganic as well as organic
builders can be
used. The level of builder can vary widely depending upon the end use of the
composition
and its desired physical form. Liquid formulations may comprise from about 1 %
to about
50%, more typically about 2% to about 30%, by weight, of detergent builder.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as
disclosed in German Patent Application No. 2,321,001 published on November 15,
1973.
Organic detergent builders suitable for the purposes of the present invention
include,
but are not restricted to, a wide variety of polycarboxylate compounds. As
used herein,
"polycarboxylate" refers to compounds having a plurality of carboxylate
groups,
preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the
composition in acid form, but can also be added in the form of a neutralized
salt. When
utilized in salt form, alkali metals, such as sodium, potassium, and lithium,
or
alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders are. disclosed
in Berg, U.S.
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WO 99103512 PCT/US98/14689
19
Patent 3,128,287, issued April 7, 1964, and Lamberti et a1, U.S. Patent
3,635,830, issued
January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued
to
Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include
cyclic
compounds, particularly alicyclic compounds, such as those described in U.S.
Patents
3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt),
are polycarboxylaie builders of importance for liquid detergent formulations
due to their
availability from renewable resources and their biodegradability. Oxy-
disuccinates are
also especially useful in such compositions and combinations.
Also suitable in the compositions of the present invention are the 3,3-
dicarboxy-4-
oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent
4,566,984,
Bush, issued January 28, 1986. Laurylsuccinates are the preferred builders of
this group,
and are described in European Patent Application 86200690.5/0,200,263,
published
November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,22b,
Crutchfield
et al, issued March I3, 1979 and in U.S. Patent 3,308,067, Diehl, issued March
7, 1967.
See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated into
the
compositions alone, or in combination with the aforesaid builders, especially
citrate and/or
the succinate builders, to provide additional builder activity.
Inorganic or P-containing 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),
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates.
Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other
known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030;
3,422,021;
3,400,148 and 3,422,137) can also be used.
Examples of silicate builders are the alkali metal silicates, such as the
layered sodium
silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P.
Rieck.
NaSKS-6 is the trademark for a crystalline layered silicate marketed by
Hoechst
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(commonly abbreviated herein as "SKS-6"). NaSKS-6 can be prepared by methods
such
as those described in German DE-A-3,417,649 and DE-A-3,742,043. Various other
layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the
alpha,
beta and gamma forms.
Useful aluminosilicate ion exchange materials are commercially available. A
method
for producing aluminosilicate ion exchange materials is disclosed in U. S.
Patent
3,985,669, Krummel, et al, issued October I2, 1976.
Enzymes - Suitable enzymes include proteases, amylases, Iipases, cellulases,
peroxidases, and mixtures thereof of any suitable origin, such as vegetable,
animal,
bacterial, fungal and yeast origin. Preferred selections are influenced by
factors such as
pH-activity and/or stability optima, thermostability, and stability to active
bleach,
detergents, builders and the like. In this respect bacterial or fungal enzymes
are preferred,
such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The term
"cleaning effective amount" refers to any amount capable of producing a
cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness improving effect
on substrates
such as dishware and the like. In practical terms for current commercial
preparations, the
compositions herein may comprise from 0.00/% to 5%, preferably 0.01%-1% by
weight
of a commercial enzyme preparation. Protease enzymes are usually present in
such
commercial preparations at levels sufficient to provide from 0.005 to 0.1
Anson units
(AU) of activity per gram of composition.
The preparation of protease enzyme and analogous enzymes is described in GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from International Bio-Synthetics, Inc., The
Netherlands;
as well as Protease A as disclosed in EP 130,756 A, January 9, /985 and
Protease B as
disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985.
See also
a high pH protease from Bacillus sp. NCIIvVIB 40338 described in WO 9318140 A
to
Novo. Enzymatic detergents comprising protease, one or more other enzymes, and
a
reversible protease inhibitor are described in WO 9203529 A to Novo. Other
preferred
proteases include those of WO 9510591 A to Procter & Gamble . When desired, a
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WO 99/03512 PCTNS98/14689
21
protease having decreased adsorption and increased hydrolysis is available as
described in
WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for
detergents
suitable herein is described in WO 9425583 to Novo.
Amylases suitable herein, especially for, but not limited to automatic
dishwashing
purposes, include, for example, a-amylases described in GB 1,296,839 to Novo;
RAPIDASE~, International Bio-Synthetics, Inc. and TER.~rfAMYL~, Novo.
FUNGAMYL~ from Novo is especially useful. Engineering of enzymes for improved
stability, e.g., oxidative stability, is known. See, for example J. Biological
Chem., Vol.
260, No. 11, June 1985, pp 6S 18-6521 Preferred amylases include (a) an
amylase
according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994.
Other
amylases include variants having additional modification in the immediate
parent as
described in WO 9S 10603 A and are available from the assignee, Novo, as
DURAMYL~
. Other particularly preferred oxidative stability enhanced amylase include
those described
in WO 9418314 to Genencor International and WO 9402597 to Novo.
Cellulases usable herein include those disclosed in U.S. 4,435,307,
Barbesgoard et
al, March 6, 1984. Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-
2.09S.27S and DE-OS-2.247.832. CAREZYME~ {Novo) is especially useful. See also
WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.1 S4,
as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application
53,20487,
laid open Feb. 24, 1978. Other suitable commercial lipases include Amano-CES,
lipases
ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolylicum NRRLB
3673
from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U. S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. LIPOLASE~ enzyme derived from Xumicola lanuginosa and
commercially available from Novo, see also EP 341,947, is a preferred lipase
for use
herein. Lipase and amylase variants stabilized against peroxidase enzymes are
described
in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
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22
Cutinase enzymes suitable for use herein are described in WO 8809367 A to
Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention
of transfer of dyes or pigments removed from substrates during the wash to
other
substrates present in the wash solution. Known peroxidases include horseradish
peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed in WO 89099813 A,
October
19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to
McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al,
July 18,
1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials usefirl
for liquid
detergent formulations, and their incorporation into such formulations, are
disclosed in
U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can
be
stabilised by various techniques. Enzyme stabilization techniques are
disclosed and
exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP
200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also
described,
for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases,
xylanases
and cellulases, is described in WO 9401532 A to Novo.
En~me Stabilizing S, stem - Enzyme-containing, including but not limited to,
liquid
compositions, herein may comprise from about 0.001 % to about 10%, preferably
from
about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by
weight of
an enzyme stabilizing system. Such stabilizing systems can, for example,
comprise
calcium ion, boric acid, propylene glycol, short chain carboxylic acids,
boronic acids, and
mixtures thereof, and are designed to address different stabilization problems
depending
on the type and physical form of the detergent composition. See Severson, U.S.
4,537,706 for a review of Borate stabilizers.
Suitable chlorine scavenger anions are widely known and readily available,
and, if
used, can be salts containing ammonium canons with sulf te, bisulfite,
thiosulfite,
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WO 99/03512 PCT/US98/14689
23
thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc.,
organic amines
such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used. Other
' conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen peroxide
such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium
percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate,
citrate,
formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can
be used if
desired.
Bleaching Agents
Suitable bleaching for possible use herein are listed below:
Diacyl Peroxide Bleaching Species - The composition of the present invention
may
contain diacyl peroxide of the general formula:
RC(O)00(O)CR 1
wherein R and Rl can be the same or different and are hydrocarbyls, preferably
no more
than one is a hydrocarbyl chain of longer than ten carbon atoms, more
preferably at least
one has an aromatic nucleus.
Examples of suitable diacyl peroxides are selected from the group consisting
dibenzoyl peroxide, dianisoyl peroxide, benzoyl gluaryl peroxide, benzoyl
succinyl
peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide, dinaphthoyl
peroxide,
substituted dinaphthoyl peroxide, and mixtures thereof, more preferably
dibenzoyl
peroxide, dicumyl peroxide, diphthaloyl peroxides and mixtures thereof. A
particularly
preferred diacyl peroxide is dibenzoyl peroxide.
Hvdrog-en Peroxide Source - The compositions of the present invention may
comprise a source of oxygen bleach, preferably a source of hydrogen peroxide
with or
without a selected bleach activator. The source of hydrogen peroxide is
typically any
common hydrogen-peroxide releasing salt, such as sodium perborate or sodium
percarbonate. Hydrogen peroxide sources include the various forms of sodium
perborate
and sodium percarbonate and modified forms. An "effective amount" of a source
of
hydrogen peroxide is any amount capable of measurably improving stain removal
(especially of tea and tomato stains) from the soiled substrate compared to a
hydrogen
peroxide source-free composition when the soiled substrate is washed by the
consumer.
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24
The preferred source of hydrogen peroxide used herein can be any convenient
source, including hydrogen peroxide itself. For example, perborate, e.g.,
sodium
perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium
carbonate
peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxy-
hydrate,
urea peroxyhydrate, or sodium peroxide can be used herein. Sodium perborate
monohydrate and sodium percarbonate are particularly preferred. Mixtures of
any
convenient hydrogen peroxide sources can also be used.
Another source of hydrogen peroxide is enzymes. Examples include Lipoxidase,
glucose oxidase, peroxidase, alcohol oxidases, and mixtures thereof.
Bleach Activators - Numerous conventional bleach activators are known. See for
example activators referenced hereinabove in the background as well as U.S.
Patent
4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
Nonanoyloxybenzenesulfonate (HOBS) or acyl lactam activators may be used, and
mixtures thereof with TAED can also be used. See also U.S. 4,634,551 for other
typical
conventional bleach activators. Also known are amido-derived bleach activators
of the
formulae: R1N(RS)C(O)R2C(O)L or RIC(O)N(RS)R2C(O}L wherein R1 is an alkyl
group containing from about 6 to about 12 carbon atoms, R2 is an alkylene
containing
from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or alkaryl containing
from about 1
to about 10 carbon atoms, and L is any suitable leaving group. Further
illustration of
bleach activators of the above formulae include (6-
octanamidocaproyl}oxybenzenesulfonate, (6-nonanamidocaproyl)-
oxybenzenesulfonate,
(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in
U.S.
Patent 4,634,551. Another class of bleach activators comprises the benzoxazin-
type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October
30, 1990.
Still another class of bleach activators includes acyl lactam activators such
as octanoyl
caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,
decanoyl
caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl
valerolactam,
undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethyl-hexanoyl
valerolactam,
t-butylbenzoylcaprolactam, t-butylbenzoylvalerolactam and mixtures thereof.
The present
compositions can optionally comprise aryl benzoates, such as phenyl benzoate,
and acety
triethyl citrate.
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Quaternary Substituted Bleach Activators - The present compositions can also
comprise quaternary substituted bleach activators (QSBA). QSBA's herein
typically have
the formula E-[Z]n-C(O)-L, wherein group E is referred to as the "head", group
Z is
referred to as the "spacer" (n is 0 or I, i.e., this group may be present or
absent, though
its presence is generally preferred) and L is referred to as the "leaving
group". These
compounds generally contain at least one quaternary substituted nitrogen
moiety, which
can be contained in E, Z or L. More preferably, a single quaternary nitrogen
is present
and it is located in group E or group Z. In general, L is a leaving group, the
pKa of the
corresponding carbon acid (HI,) of which can lie in the general range from
about S to
about 30, more preferably, from about 10 to about 20, depending upon the
hydrophilicity
of the QSBA. pKa's of leaving groups are further defined in U.S. Pat. No.
4,283,301.
Leaving groups and solubilizing tendencies of quaternary moieties which can be
present in
the QSBA's are further illustrated in U.S. 4,539,130, Spt. 3, 1985
incorporated by
reference.
British Pat. 1,382,594, published Feb. 5, 1975, discloses a class of QSBA's
found
suitable for use herein. U.S. 4,818,426 issued Apr. 4., 1989 discloses another
class of
QSBA's suitable for use herein. See, for example, U. S. 5,093,022 issued March
3, 1992
and U.S. 4,904,406, issued Feb. 27, 1990. Additionally, QSBA's are described
in EP
552,812 Al published July 28, 1993, and in EP 540,090 A2, published May 5,
1993.
Chlorine Bleach - Any chlorine bleach typically known in the art is suitable
for use
herein. Preferred chlorine bleaches for use herein include sodium
hypochlorite, lithium
hypochlorite, calcium hypochlorite, chlorinated trisodium phosphates, and
mixtures
thereof. For more about chlorine bleaches see Surfactant Science Series, Vol.
5, Part II,
pages 520-26.
Bleach catalysts - If desired, detergent compositions herein may additionally
incorporate a catalyst or accelerator to further improve bleaching or starchy
soil removal.
Any suitable bleach catalyst can be used. The compositions will comprise from
about
0.0001 % to about 0. I % by weight of bleach catalyst.
Typical bleach catalysts those disclosed in U.S. Pat. 4,810,410 to Diakun et
al,
issued March 7, 1989. The active species thereof is believed to be
{Co(NH3)5(OOH)}2+
and is disclosed in J. Chem. Soc. Faraday Trans., 1994, Vol. 90, 1105-1114.
Other
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26
catalysts include manganese-based catalysts disclosed in U.S. Pat. 5,246,621,
U.S.
5,244,594; U.S. 5,194,416; U.S. 5,114,606; and EP Nos. 549,271 A1, 549,272 Al,
544,440 A2, and 544,490 A1. Other metal-based bleach catalysts include those
disclosed
in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with
various
complex ligands to enhance bleaching is also reported in the following United
States
Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280, I I7; 5,274,147;
5,153,161;
and 5,227,084.
Transition metals may be precomplexed or complexed in-situ with suitable donor
ligands selected in function of the choice of metal, its oxidation state and
the denticity of
the ligands. Other complexes which may be included herein are those of U.S.
Application Ser. No. 08/210,186, filed March 17, 1994.
Perfumes - Perfumes and perfizmery ingredients useful in the present
compositions
and processes comprise a wide variety of natural and synthetic chemical
ingredients,
including, but not limited to, aldehydes, ketones, esters, and the like. Also
included are
various natural extracts and essences which can comprise complex mixtures of
ingredients, such as orange oil, lemon oil, rose extract, lavender, musk,
patchouli,
balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished
perfumes can
comprise extremely complex mixtures of such ingredients. Finished perfumes
typically
comprise from about 0.01% to about 4%, by weight, of the detergent
compositions
herein, and individual perfumery ingredients can comprise from about 0.0001%
to about
90% of a finished perfume composition.
Material Care Agents - The present compositions may optionally contain as
corrosion inhibitors and/or anti-tarnish aids one or more material care agents
such as
silicates. Material care agents include bismuth salts, transition metal salts
such as those of
manganese, certain types of paraffin, triazoles, pyrazoles, thiols,
mercaptans, aluminium
fatty acid salts, and mixtures thereof and are preferably incorporated at low
levels, e.g.,
from about 0.01 % to about 5% of the composition. A preferred paraffin oil is
a
predominantly branched aliphatic hydrocarbon comprising from about 20 to about
50
carbon atoms with a ratio of cyclic to noncyclic hydrocarbons of about 32 to
68 sold by
Wintershall, Salzbergen, Germany as WINOG 70~. Bi(N03)3 may be added. Other
corrosion inhibitors are illustrated by benzotriazole, thiols including
thionaphtol and
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27
thioanthranol, and finely divided aluminium fatty acid salts. All such
materials will
- generally be used judiciously so as to avoid producing spots or films on
glassware or
compromising the bleaching action of the compositions. For this reason, it may
be
' preferred to formulate without mercaptan anti-tarnishes which are quite
strongly bleach
reactive or common fatty carboxylic acids which precipitate with calcium.
Chelating Agents - The detergent compositions herein may also optionally
contain
one or more iron and/or manganese chelating agents. Such chelating agents can
be
selected from the group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures therein,
all as
hereinafter defined. Without intending to be bound by theory, it is believed
that the
benefit of these materials is due in part to their exceptional ability to
remove iron and
manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates usefial as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates,
ethylenediamine tetraproprionates, triethylenetetra-amine-hexacetates,
diethylene-
triaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and
substituted
ammonium salts therein and mixtures therein.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use
herein is
ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described
in U.S.
Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1 %
to about
10% by weight of the detergent compositions herein. More preferably, if
utilized, the
chelating agents will comprise from about 0.1% to about 3.0% by weight of such
compositions.
Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously
be
utilized at levels from about 0.1% to about 7%, by weight, in the compositions
herein,
especially in the presence of zeolite and/or layered silicate builders.
Suitable polymeric
dispersing agents include polymeric polycarboxylates and polyethylene glycols,
although
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28
others known in the art can also be used. It is believed, though it is not
intended to be
limited by theory, that polymeric dispersing agents enhance overall detergent
builder
performance, when used in combination with other builders (including lower
molecular
weight polycarboxylates) by crystal growth inhibition, particulate soil
release peptization,
and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric segments,
containing no carboxylate radicals such as vinylmethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble
salts of
polymerized acrylic acid. The average molecular weight of such polymers in the
acid
form preferably ranges from about 2,000 to 10,000, more preferably from about
4,000 to
7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of
such acrylic
acid polymers can include, for example, the alkali metal, ammonium and
substituted
ammonium salts. Soluble polymers of this type are known materials. Use of
polyacrylates of this type in detergent compositions has been disclosed, for
example, in
Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the
dispersing/anti-redeposition agent. Such materials include the water-soluble
salts of
copolymers of acrylic acid and malefic acid. The average molecular weight of
such
copolymers in the acid form preferably ranges from about 2,000 to 100,000,
more
preferably from about 5,000 to 75,000, most preferably from about 7,000 to
65,000. The
ratio of acrylate to maleate segments in such copolymers will generally range
from about
30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts
of such
acrylic acid/maleic acid copolymers can include, for example, the alkali
metal, ammonium
and substituted ammonium salts. Soluble acrylate/maleate copolymers of this
type are
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29
known materials which are described in European Patent Application No. 66915,
published December 15, 1982, as well as in EP 193,360, published September 3,
1986,
which also describes such polymers comprising hydroxypropylacrylate. Still
other useful
dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such
materials are
also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer
of
acrylic/maleic/vinyl alcohol.
Other polymeric materials which can be included are polypropylene glycol
(PPG),
propylene glycol (PG), and polyethylene glycol (PEG). PEG can exhibit
dispersing agent
performance as well as act as a clay soil removal-antiredeposition agent.
Typical
molecular weight ranges for these purposes range from about 500 to about
100,000,
preferably from about 1,000 to about 50,000, more preferably from about 1,500
to about
10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably have
a molecular weight (avg.) of about 10,000.
Alkoxylated polycarboxylates such as those prepared from polyacrylates are
useful
herein to provide additional grease removal performance. Such materials are
described in
WO 91/08281 and PCT 90/01815 at p. 4 et seq. Chemically, these materials
comprise
polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The
side-chains
are of the formula -(CH2CH20)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The
side-
chains are ester-linked to the polyacrylate "backbone" to provide a "comb"
polymer type
structure. The molecular weight can vary, but is typically in the range of
about 2000 to
about 50,000. Such alkoxylated polycarboxylates can comprise from about 0..05%
to
about 10%, by weight, of the compositions herein.
Another polymer dispersant form use herein includes polyethoxyated-polyamine
polymers (PPP). The preferred polyethoxylated-polyamines useful herein are
generally
polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably
polyethyleneamine
(PEA's), polyethyleneimines (PEI's). A common polyalkyleneamine (PAA) is
tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and
ethylene
dichloride, followed by fractional distillation. The common PEA's obtained are
triethylenetetramine (TETA) and teraethylenepentamine (TEPA). Above the
pentamines,
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i.e., the hexamines, heptamines, octamines and possibly nonamines, the
cogenericaily
derived mixture does not appear to separate by distillation and can include
other materials
such as cyclic amines and particularly piperazines. There can also be present
cyclic
amines with side chains in which nitrogen atoms appear. See U.S. Patent
2,792,372,
Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
Polyamines can be prepared, for example, by polymerizing ethyleneimine in the
presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric
acid, hydrogen
peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing
these
polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al.,
issued
December S, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962;
U.S. Patent
2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839,
Crowther,
issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21,
1951; all
herein incorporated by reference.
Additionally, certain alkoxylated (especially ethoxylated) quaternary
polyamine
dispersants are useful herein as dispersants. The alkoxylated quaternary
polyamine
dispersants which can be used in the present invention are of the general
formula:
A A A
RI-N~ R N~ R N~ R~ (m + 2) X~
R~ m
where R is selected from linear or branched C2-C 12 alkylene, C3-C 12
hydroxyalkylene,
C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, [(CH2CH20)qCH2CH2]- and -
CH2CH(OH)CH20-(CH2CH20)qCH2CH(OH)CH2]- where q is from about 1 to about
100. If present, Each R1 is independently selected from C1-C4 alkyl, C7-C12
aikylaryl,
or A. R1 may be absent on some nitrogens; however, at least three nitrogens
must be
quaternized.
A is of the formula:
(CH-CH2-O)nB
R3
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31
where R3 is selected from H or CI-C3 alkyl, n is from about 5 to about 100 and
B is
- selected from H, CI-C4 alkyl, acetyl, or benzoyl; m is from about 0 to about
4, and X is a
water soluble anion.
In preferred embodiments, R is selected from C4 to Cg alkylene, R1 is selected
from C1-C2 alkyl or C2-C3 hydroxyalkyi, and A is:
(CH-CH2-0)nH
R3
where R3 is selected from H or methyl, and n is from about 10 to about 50; and
m is 1.
In another preferred embodiment R is linear or branched C6, R1 is methyl, R3
is
H, and n is from about 20 to about S0, and m is I.
The levels of these dispersants used can range from about 0.1% to about IO%,
typically from about 0.4% to about 5%, by weight. These dispersants can be
synthesized
following the methods outline in US. Patent No. 4,664,848, or other ways known
to
those skilled in the art.
Hydrotropes - Hydrotropes suitable for use in the compositions herein include
CI-
C3 alkyl aryl sulfonates, C6-C12 alkanols, C1-C6 carboxylic sulfates and
sulfonates, urea,
hydrocarboxylates, CI-C4 carboxylates, organic diacids, and mixtures thereof.
Suitable C1-C3 alkyl aryl sulfonates include sodium, potassium, calcium, and
ammonium xylene sulfonates, toluene sulfonates, cumene sulfonates, and
naphthalene
sulfonates.
Divalent Ions - Compositions of this invention herein optionally, but
preferably,
contain magnesium and or calcium ions to aid in good grease removal and
improved
storage stability. These ions can be present in the compositions herein at an
active level
of from about 0.1 % to about 4%, by weight.
Thickeners - Thickeners for use herein can be selected from clay,
polycarboxylates,
such as Polygel~, gums, carboxymethyl cellulose, polyacrylates,
polyvinylpyrrolidone,
polyamide resins, titanium dioxide, fumed silica, and mixtures thereof.
One preferred clay type herein has a double-layer structure. The clay may be
naturally occurring, e.g., Bentonites, or artificially made, e.g., Laponite~.
Laponite~ is
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32
supplied by Southern Clay Products, Inc. See The Chemistry and Physics of
Clays,
Grimshaw, 4th ed., 1971, pages 138-155, Wiley-Interscience.
Another preferred thickener for use in the present invention is hydroxypropyl
methylcellulose.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid, malefic anhydride,
fumaric acid,
itaconic, acid, aconitic acid, mesaconic acid, citraconic acid, and
methylenemalonic acid.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. See for
example, Diehl, U.S. Pat. 3,308,067, March 7, 1967.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol,
propanol, and isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing surfactant, but polyols such as those containing from 2 to about
6 carbon
atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene
glycol,
glycerine, and 1,2-propanediol) can also be used. The compositions may contain
from 5%
to 90%, typically 10% to 50% of such carriers.
Non-Aqueous Liquid Detergents - The manufacture of liquid detergent
compositions which comprise a non-aqueous carrier medium can be prepared
according
to the disclosures of U.S. Patents 4,753,570; 4,767,558; 4,772,413; 4,889,652;
4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S. 4,988,462;
U.S.
5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089
(5/5/93);
EP-A-540,090 (515/93); U.S. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096
(6/10/81), incorporated herein by reference. Such compositions can contain
various
particulate detersive ingredients (e.g., bleaching agents, as disclosed
hereinabove) stablely
suspended therein. Such non-aqueous compositions thus comprise a LIQUID PHASE
and, optionally but preferably, a SOLID PHASE, all as described in more detail
hereinafter and in the cited references.
Aside from sanitizing as discussed above, the compositions of this invention
can be
used to form aqueous washing solutions for use in hand dishwashing. Generally,
an
effective amount of such compositions is added to water to form such aqueous
cleaning
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33
or soaking solutions. The aqueous solution so formed is then contacted with
the
.. dishware, tableware, and cooking utensils.
An effective amount of the detergent compositions herein added to water to
form
aqueous cleaning solutions can comprise amounts sufficient to form from about
500 to
20,000 ppm of composition in aqueous solution. More preferably, from about 500
to
5,000 ppm of the detergent compositions herein will be provided in aqueous
cleaning
liquor.
The following examples are illustrative of the present invention, but are not
meant to
limit or otherwise define its scope. All parts, percentages and ratios used
herein are
expressed as percent weight unless otherwise specified.
In the following Examples all levels are quoted as % by weight of the
composition.
EXAMPLE I
Ingredient A B C D E F
Na AExS {x is 33 30 33 36 26 31
0.5)
Amine Oxide 5 6 5 5 2 4.5
Polyhydroxy fatty4 4 4 2 1 4
acid amide
C11E9 nonionic 1 1 1 1 5 1
Betaine 2
Ethanol 5 5 5 5 6 5
DTPA 0.1 0.1 0.1 0.1 - 0.1
MgCl2 3 3 3 3 - -
Hydrotrope 5 S 5 5 2 5
Na2SO4 0.2 0.15 0.2 0.2 0.2 0.15
Hydrogen peroxide0.05 0.05 0.05 0.05 - 0.05
Thickener - - 0.5 0.5 - 1.4
Potassium Carbonate- - - - - 3
Potassium Chloride- - - - - 3
Balance (water, to to to to to to
unreacted, filler,100% 100% 100% 100% 100% 100%
etc.
pH (10%) 7.5 7.5 7.4 7.5 8 10.5
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34
Ingredient G H
Na AExS 33 22
Amine Oxide 6 -
Pentane/Hexane Diamine7 -
Linear Alkyl Benzene- 13
Sulfonate
Methyl ethanolamine- 1.5
Alkyl polyglucoside- 11
C11E9 nonionic 5 -
Ethanol S 4.5
DTPA 0.1 -
Hydrotrope - 2.5
Hydrogen peroxide 0.03 -
Na2S04 0.2 -
Thickener 0.5 -
Balance (water, to to
unreacted, filler, 100% 100%
etc.)
DTPA is ethylenediaminetetracetate.
Hydrotropes can be selected from calcium, sulfate or sodium xylene sulfonates
and
toluene sulfonates.
Thickeners include Tetronic~"" and AccusotT""
The formulas provide significant germ kill (Escherichia coli and Staphococcus
aureus) when applied to a surface and allowed to remain in contact with the
surface for at
least 1 S seconds before rinsing.
