Note: Descriptions are shown in the official language in which they were submitted.
3Z4
DETE~CENT COMPOSITION CONTAINING SEMI-POLAR
NON IONIC DETERGENT, ALKALINE EARTH IT'LL ANIONIC
DETERGENT, AND AMIDOALKYLBETAINE DETERCiENT
Lowell W. Bernardino
Edward W. Kuhn
Mark H. K. Mao
Eugene J. Pinker
Background of the Invention
This invention relates to a detergent composition especially
lo formulated for the removal of greasy soils. More particularly, it
relates to a detergent composition containing a semi-polar non ionic
detergent, an alkaline earth metal, preferably magnesium, salt of
an anionic detergent and an amidoalkylbetaine.
Detergent compositions containing a wide variety of
water-soluble organic detergents or mixtures thereof have been
formulated. Recognizably, certain water-soluble organic
detergents are better at removing one type of soil than other
detergents. For example, anionic detergents are noted for their
ability to remove carbohydrate and protein type stains, while
non ionic detergents are especially useful in the removal of grease
and oil stains. Various mixtures of detergents have been tried in
order to find the optimum combination for removing a wide variety
of stains as is normally encountered on soiled articles. (See for
example, US. Patents 2,691,636, 3,085/982, 3,179,599,
3,196,166 and 3,223,647 for various organic detergent
combinations.) However, there is a continuing need for detergent
compositions that are effective in removing soils, especially greasy
soils .
Additionally, various salts such as magnesium and calcium
30 chloride and magnesium sulfate have been suggested as detergent
composition additives for improving their detergency (see US.
Patents 2,908,651~ 2,437,253 and 4,133,779).
It has now been found that a detergent composition
35 especially effective in the removal of greasy soil is formulated
using a semi-polar non ionic detergent, an alkaline earth metal salt
of certain anionic detergents, and an amidoalkylbetaine.
~9324
-- 2 --
As used herein, all percentages, parts and ratios are by
weight unless otherwise indicated.
Summary of the Invention
A detergent composition especially effective in removing
5 greasy soils wherein the organic detergent portion of said
composition consists essentially of a mixture of:
(a) from about I% to about 10%, preferably from about 196 to
about 8%, of a semi-polar organic non ionic detergent selected from
the group consisting of if) water-soluble amine oxides having one
10 alkyd or hydroxyalkyl moiety of 8 to 28 carbon atoms and two
alkyd moieties selected from the group consisting of alkyd groups
and hydroxyalkyl groups of 1 to 3 carbon atoms, (2)
water-soluble phosphine oxides having one alkyd or hydroxyalkyl
moiety of 8 to 28 carbon atoms and two alkyd moieties selected
15 from the group consisting of alkyd groups and hydroxyalkyl
groups a 1 to 3 carbon atoms, (Al water-soluble sulfoxides
having one alkyd or hydroxyalkyl moiety of 8 to 18 carbon atoms
and an alkyd moiety selected from the group consisting of alkyd
and hydroxyalkyl groups of 1 to 3 carbon attires, and (4)
20 mixtures thereof;
(b) from about 10% to about 50%, preferably from about 15%
to about 40%, of an alkaline earth metal, preferably magnesium,
salt of an anionic detergent selected from the group consisting of
(1 ) linear alkyd Bunsen sulfonates having 9 to 15 carbon atoms in
25 the alkyd group, (2) alkyd sulfates having 8 to 22 carbon atoms,
(3) paraffin sulfonates having 8 to 22 carbon atoms, (4) olefin
sulfonates having 8 to 22 carbon atoms, (5) alkyd ether sulfates
having 8 to 22 carbon atoms in the alkyd group and t to 30
ethylene oxide units (6) alkyd glycerol ether sulfonates having 8
30 to 22 carbon atoms in the alkyd group and (7) mixtures thereof;
and
(c) from about to about 15%, preferably from about 196 to
about 10% of an acylamidoalkylbetaine of the formula:
R C - N R2 No R4 C O
_ ..... . ... . .. _. .. . . , . . .. . ., .. ., ., .. .. , , . _ _ _ .. , _
~3~3Z4
-- 3 --
wherein R is an alkyd group, or alkylaryl group
containing from about 7 to about 21 carbon atoms, preferably from
about 9 to about 17 carbon atoms; R1 Jo hydrogen or an alkyd
group containing from 1 to about 6 carbon atoms, preferably from
5 1 to about 3 carbon atoms; R2 is an alkaline group containing
from 1 to about 10 carbon atoms, preferably from about 2 to
about 6 carbon atoms, most preferably 3 carbon atoms; each R3 is
an alkyd or hydroxy alkyd group containing from 1 to about 6
carbon atoms, preferably from 1 to about 3 carbon atoms, most
lo preferably 1 carbon atom or an ethoxylated hydroxy alkyd
containing from about 1 to about 10 ethylene oxide units; and R4
is an alkaline group containing from 1 to about 6 carbon atoms,
preferably one carbon atom.
Detailed Description of the Invention
The detergent compositions of this invention contain a
water-soluble semi-polar non ionic detergent, an alkaline earth
metal salt of an anionic detergent, and an amidoalkylbetaine as
essential ingredients. Descriptions of these detergents follow.
Semi-polar non ionic detergents useful herein include
20 water-soluble amine oxides, phosphine oxides and sulfoxides.
Amine oxides are preferred. The amine oxide has one alkyd or
hydroxyalkyl moiety of 8 to 26 carbon atoms, preferably 8 to 16
carbon atoms and two alkyd moieties selected from the group
consisting of alkyd groups and hydroxyalkyl groups containing 1
25 to 3 carbon atoms. Examples of such materials include
dimethyloctylamine oxide, diethyldecylamine oxide, Boyce-
droxyethyl)dodecylamine oxide, dimethyldodecylamine oxide,
dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,
and dimethyl-2-hydroxyoctadecylamine oxide.
Suitable semi-polar non ionic detergents also include the
water-soluble phosphine oxides having one alkyd or hydroxyalkyl
moiety of 8 to 28 carbon atoms, preferably 8 to 16 carbon atoms
and two alkyd moieties selected from the group consisting of alkyd
groups and hydroxyalkyl groups containing 1 to 3 carbon atoms.
35 Examples of suitable phosphine oxides include dimethyldecylphos-
pine oxide, dimethyltetradecylphosphine oxide, methylethyltetra-
decylphosphine oxide, dimethylhexadecylphosphine oxide, deathly-
~Z393Z4
-- 4 --
2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl) dodecyl-
phosphine oxide, and bis(hydroxymethyl)tetradecylphosphine
oxide .
The water-soluble sulfoxide detergents contain one alkyd or
hydroxyalkyl moiety of 8 to 18 carbon atoms, preferably 12 to 16
carbon atoms and one alkyd moiety selected from the group
consisting of alkyd and hydroxyalkyl groups having 1 to 3 carbon
atoms. Specific examples of these sulfoxides include
dodecylmethyl sulfoxide, 2-hydroxyethyltridecyl sulfoxide,
hexadecylmethyl sulfoxide, 3-hydroxyoctadecylethyl sulfoxide.
The anionic detergent comprises at least about 109~,
preferably at least about 15% of an alkaline earth metal,
preferably magnesium, salt of an organic anionic detergent. The
remainder are typically sodium, potassium, ammonium and/or
substituted ammonium salts. Especially preferred salts are the
magnesium salts. The anionic detergent salts which are useful in
the present invention are selected from the following classes of
anionic detergents:
I Alkyd Bunsen sulfonates in which the alkyd group
contains from 9 to 15 carbon atoms, preferably 11 to 14
carbon atoms in straight chain or branched chain
configuration. An especially preferred linear alkyd
Bunsen sulfonate contains 12 carbon atoms. U . S.
patents 2,220,099 and 2,477,383 describe these
detergents.
(2) Alkyd sulfates obtained by sulfating an alcohol having 8
to 22 carbon atoms, preferably 12 to 16 carbon atoms.
The alkyd sulfates have the formula (RHIZOME where K
is the C8 22 alkyd group and M is the alkaline earth
metal.
(3) Paraffin sulfonates having 8 to 22 carbon atones,
preferably 12 to 16 carbon atoms in the alkyd moiety;
(43 Olefin sulfonates having 8 to 22 carbon atoms,
preferably 12 to 16 carbon atoms. US. Patent
3,332,880 contains a description of suitable olefin
sulfonates.
123~3~24
-- 5 --
(5) Alkyd ether sulfates derived from ethoxylating an
alcohol having 8 to 22 carbon atoms, preferably 12 to 16
carbon atoms with 1 to 30, preferably 1 to 12 moles of
ethylene oxide and then sulfating. The alkyd ether
sulfates having the formula
[RO(C2H40)XS031~M
where R is the C8 22 alkyd group, X is 1-30, and M is
an alkaline earth metal.
(6) Alkyd glycerol ether sulfonates having 8 to 22 carbon
atoms, preferably 12 to 16 carbon atoms in the alkyd
moiety; and
(7) Mixtures thereof.
(2) and/or (5) are preferred.
The above-described anionic detergents are all available
commercially. The acid form of the anionic detergent can be
converted to the alkaline earth metal salt form either prior to
admixture with the semi-polar non ionic detergent or thereafter.
This conversion can be accomplished either by direct neutralize
anion with an alkaline earth metal base or by ion exchange be-
tweet, e.g., an alkali metal, ammonium or alkanolammonium salt of
the anionic detergent and a no n-toxic, water-soluble alkaline
earth metal salt. Preferably, a source of magnesium or calcium
ions is added to the detergent mixture under desirable reaction
conditions to form the desired salts. Calcium and magnesium
chlorides, calcium and magnesium sulfates, calcium and magnesium
acetates or calcium and magnesium hydroxides and oxides are
examples of magnesium and calcium sources. Magnesium chloride
and magnesium sulfate are preferred. Magnesium oxide or
hydroxide is most preferred.
The cation of the anionic detergent is important in that the
alkaline earth metal salts of the herein described anionic
detergent perform better in terms of suds persistence, especially
in the presence of grease, than the alkali metal, ammonium or
alkanolammonium salts of said anionic detergents when in
combination with the semi-polar non ionic detergent and the button
detergent. In some cases, a mixture of cations may be desirable
393~4
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for optimum physical properties or seducing across a range of
conditions and soils, provided sufficient amounts of the anionic
surfactan~ are in the alkaline earth metal form to provide the
desk red g reuse removal . Up to about 25% of the above anionic
5 detergents can be in the form of their sodium, potassium, ammo-
I'm, moo-, dip or triethanolammonium salts, especially ammonium,
monoethanolammonium, or triethanolammonium.
The amidoalkylbetaine surfactant is essential to the improved
performance. The suds persistence (mileage) is less when the
10 amidoalkylbetaine is combined with alkali metal anionic and
semi-polar non ionic detergent mixtures. Overall superior
performance requires all three essential ingredients.
Examples of suitable buttons include coconutacylamidopro-
pyldimethylbetaine; C12_14 acylamidopropylbetaine; C8 acylamido-
15 hexyldiethylbetaine; 4-[C14 16 acylmethylamidodiethylammonio]-1-
carboxybutane; C16_18 acylamidodimethylbetaine; C12 14 acylar!~ido-
pentanediethylbetaine; 2-lC12 16 acylmethylamidodiemethyll-1-
car boxy propane; and C1 2 16 acylmethylamidodimethylbetaine.
Preferred buttons are the C10 18 acylamidopropane (or ethanes
20 dim ethyl (or deathly) buttons.
Suitable amidoalkylbetaines are disclosed in US. Patents
3,950,417; 4,137,191; and 4,375,421 and British Patent GO
2,103,236,
The level of button in the product is preferably more than
25 about I desirably about 4 to us where maximum grease handle
i no i s desk red .
It will be recognized that the alkyd (and azalea) groups for
the above detergents can be derived from either natural or sync
Thetis sources, e.g., they can be derived from naturally occur-
30 ring fatty acids; olefins such as those prepared by Ziegler, or
lZ393:24
Ox processes; or from olefins separated from petroleum either with or without "cracking". Specific examples, e.g., of alkyd
sulfates and alkyd ether sulfates include those derived from
" Nudely 23 "which is a synthetic alcohol prepared by an Ox pro-
5 cuss and containing about I weight percent of dodecanol and
about 54 weight percent of tridecanol.
Ratios of semi-polar non ionic detergent and button to anionic
detergent salt basis) of from about 1: 20 to about 1: 2, preferably
from about 1:15 to about 1: 3 provide very satisfactory grease
10 removal. The degree of grease removal obtained from the
detergent mixture is greater than that achieved by the individual
detergents atone when used under normal conditions.
The detergent compositions of this invention are formulated
in powder, granular, tablet, paste, or, preferably, liquid form.
15 Regardless of the form of the composition, it is especially
effective in the removal of greasy soils.
A preferred detergent composition containing the
above-described detergents is in a liquid form. Such liquid
compositions are especially useful for the hand washing of soiled
20 cooking utensils and tableware. The liquid compositions contain
from about 5% to about 60%, preferably from about 10% to about
50~ for concentrated products designed for dilution prior to use
and preferably from about 1% to about 40% for products designed
for use "as is", of the semi-polar non ionic, anionic, and button
25 detergent mixture. The balance of the formula comprises water.
All manner of known additives can be included in the liquid
composition. For example, suds boosters, organic solvents, e.g.,
C1-C5 alkanols (preferably ethanol), perfumes, dyes, and hydra-
troves can be added for their known functions.
An especially preferred liquid detergent composition also
contains a source of alkalinity for increased greasy soil removal.
Sodium hydroxide, potassium hydroxide, ammonium hydroxide,
and moo-, dip or trialkanolamines wherein said alkanol moieties
contain from one to five, preferably two to three carbon atoms, in
35 either a linear or branched configuration are suitable bases.
Jo * Trademark
1~35~32i~
-- 8 --
Normally, the higher chain length branched alkanolamines are
moo- or di-substituted. Common alkanolamines are moo- and
diisopropanolamines and moo-, dip and triethanolamines.
Sufficient base is added to the composition to raise its pi to
above 7.0, but below about 9Ø Such a composition has not only
increased greasy soil removal ability, but also the removal is
accelerated. Ammonia, dip and triethanolamines and mixtures
thereof are preferred sources of alkalinity because of the
resultant compositions physical characteristics, i.e., the
compositions have good fluidity and viscosity.
A liquid detergent composition having the following
formulation is most preferred: -
(a) from about 2% to about 6% of a water-soluble amine
oxide having one alkyd moiety of from about 8 to about
16 carbon atoms and two alkyd moieties of from 1 to
about 3 carbon atoms;
by from about 10% to about 309~ of magnesium alkyd sulfate
having from about 12 to about 16 carbon atoms;
(c) from 09~ to 30% of a calcium or magnesium, preferably
magnesium, alkyd ether sulfate derived from an alcohol
having from about 12 to about 16 carbon atoms
ethoxylated with from about 1 to about 12 moles of
ethylene oxide
(d) from 0% to about 20~ of ammonium, moo-, do-, or
triethanolammonium alkyd ether sulfate derived from an
alcohol having from about 12 to about 16 carbon attunes
ethoxylated with from about 1 to about 12 moles of
ethylene oxide;
(e) From about 196 to about 8% of a C12 16
acylamidopropyldimethylbetaine;
(f) from I to 15g6 moo-, do-, or triethanolammonium, or
ammonium, preferably ammonium sulfate, or chloride,
hydroxide or mixtures thereof; and
(g) the balance comprises water or water and C1-C5 alkanol
I; 35 (preferably ethanol) mixtures.
_ .. . _ .. _ .. ._. _ . . . , ... . .. . . ... . . _ .. . _ .. _ . ..... . . . _ _
~23~33Z4
g
More concentrated liquids and/or pastes containing from
about 45% to about 95% of said mixture of semi-polar non ionic,
anionic, and button detergents are also desirable.
The granular or tabulated compositions of this invention
contain from about 5% to about 50%, preferably from about 1096 to
about 3596 of the semi-polar non ionic, anionic, and button
detergent mixture. The balance of the composition comprises
inert filler salts. A suitable inert filler salt is sodium sulfate.
Various additives, e.g., suds suppressors, dyes, perfume, soil
lo anti-redeposition agents, and water can also be included in the
granular or tabulated composition.
The liquid detergent compositions of this invention are
preferably prepared by neutralizing the acid forms of the anionic
detergent with the aforementioned sources of alkalinity,
magnesium hydroxide, magnesium oxide, and/or adding a soluble
alkaline earth metal source, preferably magnesium sulfate or
magnesium chloride, to give the finished formula.
The examples which follow are illustrative of this invention.
EXAMPLE I
The following detergent compositions are formulated on a
weight percent basis.
B C D E F_ _ _
Sodium dodecyl Bunsen sulfonate22 . 0
Magnesium dodecyl Bunsen
sulfonate - 22.0
Sodium coconut sulfate - - 25.0
Magnesium coconut sulfate - - - 25.0 - -
Sodium C14 olefin sulfonate - - - - 25.0
Magnesium Ct4 olefin sulfonate - - - - - 25.0
30 Dimethyldodecylamine oxide 4.0 4.0 4.0 4.0 4.0 4.0
C1 2-1 4 a~ylamidopropYldimethyl
button - 5.0 - So - So
Triethanolamine 3.5 3.5 3.5 3.5 3.5 3.5
Water 63.0 63.0 60.0 60.0 60.0 60.0
Ethanol 5.0 5.0 5.0 5.0 5.0 5.0
Misc. perfume, dye, et. Balinese----------
.. . .. . . . . , ... . . .
~.Z3~3324
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G H I J K L
Sodium C14 paraffin sulfonate 26.0
Magnesium C14 paraffin sulfonate - 26 . o - - - -
Sodium salt of a sulfated cocos
nut alcohol ethoxylated with
3 moles of ethoxylated oxide - - 34.0
Magnesium salt of a sulfated cocos
nut alcohol ethoxylated with
3 moles of ethylene oxide - - - 34.0
Sodium coconut glycerol ether
sulfonate - - - - 30. 0
Magnesium coconut glycerol ether
sulfonate - - - - - 30.0
Dimethyldodecylamine oxide 4.0 4.0 4.0 4.04.0 4.0
C12-1 4 acylamidopropyldimethYI
button _ 5 . 0 - 5 . 0- 5 0
Triethanolamine 3 . 5 3 . 5 3 . 53 . 53 . 5 3 . 5
Water 59.0 59.0 51.0 51.0 55.0 55.0
Ethanol 5.0 5.0 5.0 5.0 5.0 5.0 .
Misc. (perfume, dye, et. ) ---------balance-------------
When compositions A-L are tested for their ability to remove
grease from a soiled surface, the results will show that the
compositions of this invention, i.e. compositions B, D, F, H, J
and L will remove more grease and have better suds mileage than
25 the similar compositions wherein the magnesium cation and button
are not employed.
EXAMPLE H
%
My Clue alkyd sulfate 5 0
My C12_13 alkyd polyethoxylate ~1.0) sulfate 15.1
NH4 C12_13 alkyd polyethoxylate (sulfite 8.1
C12-13 alkyldimethylamine oxide 2.7
NH4 zillion sulfonate 3.0
Ethanol 5 . 0
Water and minor ingredients balance
~g3Z4
This base formula was compared to compositions A, B and C
in which 5% C12 14 acylamidopropyl button was added. In
addition, in A the My salts were replaced by ammonium salts and
in B the amine oxide was removed. Water was removed or added
S to maintain the given percentages.
A reweighed 250 cc. polypropylene cup has 3 cc. of a
melted beef grease applied to its inner bottom surface. After the
grease has solidified, the cup is reweighed. Then a 0.4% aqueous
solution of the composition to be tested is added to the cup to
10 completely fill it. The aqueous solution has a ten portray of
45C. After 15 minutes, the cup is emptied and rinsed with
distilled water. The cup is dried and then weighed to determine
the amount of grease removal. The results of tests performed on
the above compositions are reported as follows on a % grease
removal basis.
Formula % Grease Removal
Base 67
Composition A 72
Composition B 56
Composition C 71 . 5
As can be seen from the above, the amine oxide and the
magnesium anionic detergent and/or button are essential for
optimum grease removal. In soft water, both the magnesium
anionic detergent and the button are required for both improved
25 suds mileage and improved grease removal.
WHAT IS CLAIMED IS:
