Note: Descriptions are shown in the official language in which they were submitted.
~lCG~OUN~ ~l' T!l~ lNV~NTl~N
This invention relates to a detergent composition
especially formulated for the removal of greasy soils.
More particularly, it relates to a detergent composition
containing a semi-polar nonionic detergent and an alkaline
earth metal salt of an anionic detergent.
Detergent compositions containing a wide variety
of water-soluble organic detergents or mixtures thereof
have been formulated. Recognizably, certain water-soluble
105'~ZZ3
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 nonionic detergents are especially use-
ful 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, U.S. Patents 2,691,636, 3,085,982, 3,177,598,
3,179,599, 3,192,166 and 3,223,647 for various orga~ic
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 chloride and magnesium sulfate have been suggested
as detergent composition additives for improving their
detergency (see U.S. Patents 2,908,651 and 2,437,253).
It has now been found that a detergent composition
especially effective in the removal of greasy soil is
formulated using a semi-polar nonionic detergent and an
alkaline earth metal salt of certain anionic detergents.
It is accordingly an object of this invention to
provide a detergent composition useful in the removal of
greasy soils.
It is another object of this invention to provide
a detergent composition containing a semi-polar nonionic
detergent and an anionic detergent.
Still another object of this invention is to provide
a liquid detergent composition containing a semi-polar
nonionic detergent and an alkaline earth metal salt of an
anionic detergent which is especially efficient in removing
~ O~ Z3
greasy soils.
These and other objects will become apparent from the :
description to follow. :
As used herein, all percentages and ratios are by
weight unless otherwise indicated.
SUM~RY OF THE INVENTION
A detergent composition especially effective in
removing greasy soils wherein the organic detergent portion
of said composition consists essentially of a mixture of: ~:
a) a semi-polar organic nonionic detergent selected
from the group consisting of (1) water-soluble amine oxides
having one alkyl or hydroxyalkyl moiety of 8 to 28 carbon
atoms and two alkyl moieties selected from the group con-
sisting of alkyl groups and hydroxyalkyl groups of 1 to 3
carbon atoms, (2) water-soluble phosphine oxides having one
alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms and
two alkyl moieties selected from the group consisting of :
alkyl groups and hydroxyalkyl groups of 1 to 3 carbon atoms,
(3) water-soluble sulfoxides having one alkyl or hydroxy-
alkyl moiety of 8 to 18 carbon atoms and an alkyl moiety
selected from the group consisting of alkyl and hydroxy-
alkyl groups of 1 to 3 carbon atoms, and (4) mixtures
thereof; and
b) an alkaline earth metal salt of an anionic
detergent selected from the group consisting of (1) linear .
alkyl benzene sulfonates having 9 to 15 carbon atoms in
the alkyl group, (2) alkyl 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, (;)
alkyl ether sulfates having 8 to 22 carbon atoms in the
alkyl group and 1 to 30 ethylene oxide units (6) alkyl
-- 3 --
05'~223
glyceryl ether sulfonates having 8 to 22 carbon atoms in
the alkyl group and (7) mixtures thereof in a weight ratio
of semi-polar nonionic detergent to anionic detergent of
from 1:100 to 1:2.
DETAILED DESCRIPTION OF THE INVENTION
.
The detergent compositions of this invention contain
a water-soluble semi-polar nonionic detergent and an
alkaline earth metal salt of an anionic detergent as
essential ingredients. Descriptions of tnese detergents
follow.
Semi-polar nonionic detergents useful herein include
water-soluble amine oxides, phosphine oxides and sulfoxides.
The amine oxide has one alkyl or hydroxyalkyl moiety of
8 to 28 carbon atoms, preferably 8 to 16 carbon atoms and
two alkyl moieties selected from the group consisting of ;
alkyl groups and hydroxyalkyl groups containing 1 to 3
carbon atoms. Examples of such materials include dimethyl-
octylamine oxide, diethyldecylamine oxide, bis-(2-hydroxy-
ethyl) dodecylamine oxide, dimethyldodecylamine oxide,
dipropyltetradecylamine oxide, methylethylhexadecylamine
oxide, and dimethyl-2-hydroxyoctadecylamine oxide.
Suitable semi-polar nonionic detergents also include
the water-soluble phosphine oxides having one alkyl or
hydroxyalkyl moiety of 8 to 28 carbon atoms, preferably 8
to 16 carbon atoms and two alkyl moieties selected from
the group consisting of alkyl groups and hydroxyalkyl
groups containing 1 to 3 carbon atoms. Examples of suitable
phosphine oxides include dimethyldecylphosphine oxide,
dimethyltetradecylphosphine oxide, methylethyltetradecyl-
phosphine oxide, dimethylhexadecylphosphine oxide, diethyl-
2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)
-- 4 --
lOS'~Z3
dodecylphosphine oxide, and bis(hydroxymethyl)-tetradecyl-
phosphine oxide.
The water-soluble sulfoxide detergents contain one
alkyl or hydroxyalkyl moiety of 8 to 18 carbon atoms, pre-
ferably 12 to 16 carbon atoms and one a~kyl moiety selected
from the group consisting of alkyl and hydroxyalkyl groups
having 1 to 3 carbon atoms. Specific examples of these
sulfoxides include dodecylmethyl sulfoxide, 2-hydroxyethyl-
tridecyl sulfoxide, hexadecylmethyl sulfoxide, 3-hydroxy-
octadecylethyl sulfoxide.
The anionic detergent is an alkaline earth metal salt
of an organic anionic detergent. Especially preferred
salts are the calcium and magnesium salts. The anionic
detergent salt which is useful in the present invention is
selected from the following classes of anionic detergents:
(1) Alkyl benzenes sulfonates in which the alkyl
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 alkyl benzene
sulfonate contains 12 carbon atoms. U.S.
Patents 2,220,099 and 2,477,383 describe
these detergents.
(2) Alkyl sulfates obtained by sulfating an
alcohol having 8 to 22 carbon atoms~, pre-
ferably 12 to 16 carbon atoms. The alkyl
sulfates have the formula (ROSO3)2M where
R is the C8 22 alkyl group and M is the
alkaline earth metal.
(3) Paraffin sulfonates having 8 to 22 carbon
atoms, preferably 12 to 16 carbon atoms in
1052Z23
the alkyl moiety;
(4) Olefin sulfonates having 8 to 22 carbon atoms,
preferably 12 to 16 carbon atoms. U.S. Patent
3,332,880 contains a description of suitable
olefin sulfonates.
(5) Alkyl ether sulfates derived from ethoxylating
an alcohol having 8 to 22 carbon atoms, pre-
ferably 12 to 16 carbon atoms with 1 to 30,
preferably 1 to 12 moles of ethylene oxide.
The alkyl ether sulfates having the formula
[RO(c2H4O)x S3]2
where R is the C8 22 alkyl group, x is 1-30,
and M is an alkaline earth metal.
(6) Alkyl glyceryl ether sulfonates having 8
to 22 carbon atoms, preferably 12 to 16
carbon atoms in the alkyl moiety; and
(7) Mixtures thereof.
The above-described anionic detergents are all available
commercially. The acid form of the anionic detergent may
be converted to the alkaline earth metal salt form either
prior to admixture with the semi-polar nonionic detergent
o~ thereafter. Preferably, a source of magnesium or
calcium is added to the detergent mixture under desirable
reaction conditions to form the desired salts. Calcium -
and magnesium chloride, calcium and magnesium sulfate,
calcium and magnesium acetate or calcium and magnesium ~-
hydroxide are examples of magnesium and calcium sources.
Magnesium sulfate is preferred.
It wil~ be recognized that the alkyl groups for the
above detergents can be derived from either natural or
synthetic sources, e.g., they can be derived from naturally
. _.
105;~Z;~3
occurring fatty acids; olefins such as those prepared by
Ziegler, or Oxo processes; or from olefins separated from
petroleum either with or without "cracking". Specific
examples, e.g., of alkyl sulfates and alkyl ether sulfates
include those derived from Neodol* 23 which is a syntnetic
alcohol prepared by an Oxo process and containing about 42
weight percent of dodecanol and about 54 weight percent of
tridecanol.
A ratio of semi-polar nonionic detergent to anionic
detergent (salt basis~ of 1:100 to 1:2, preferably 1:15 to
1:3 provides very satisfactory grease removal. The degree
of grease removal obtained from the detergent mixture is
greater than that achieved from either of the individual
detergents alone when used under normal conditions. The
cation of the anionic detergent is also important in that
the alkaline earth metal salts of the hereindescribed
anionic detergent perform better in terms of grease removal
than the alkali metal salts of said anionic detergents when
in combination with the semi-polar nonionic detergent.
The detergent compositions of this invention are
formulated in powder, granular, tablet, paste, or liquid
form. 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 cooking utensils and tableware. The liquid compositions
contain from 1~ to 45%, preferably 10% to 35~ for concentrated
products designed for dilution prior to use and preferably
2% to 15% for products designed for use "as is", of the
* Trade Mark
.
... ,. , . , :
~OSZZZ3
semi-polar nonionic and anionic detergent mixture. The
balance of the formula comprises water. All manner of known
additives may be included in the liquid composition. For
example, suds boosters, organic solvents, e.g., Cl-C5
alkanols (preferably ethanol), perfumes, dyes, and hydro-
tropes may 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 r, potassium hydroxide,
and mono-, di- or trialkanolamines wherein said alkanol
moieties contain from one to five, preferably two to three
carbon atoms, in either a linear or branched configuration
are suitable bases. Normally, the higher chain length
branched alkanolamines are mono- or disubstituted. Common
alkanolamines are mono-, di- and triiospropanolamines and
mono-, di- and triethanolamines. Sufficient base is added
to the composition to raise its pH to above 7.0, but below
9Ø Preferably, the composition has a pH of 8.0 to 8.5.
Such a composition has not only increased greasy soil
removal ability, but also the removal is accelerated. Mono-,
di- and triethanolamines and mixtures thereof are preferred
sources of alkanlinity 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 2% to 6% of a water-soluble amine oxide
having one alkyl moiety of 8 to 16 carbon atoms
and two alkyl moieties of 1 to 3 carbon atoms,
(b) from 15~ to 30% of a calcium or magnesium, pre-
ferably magnesium, alkyl sulfate having 12 to
lOS'~Z3
16 carbon atoms;
(c) from 0% to 9% of a calcium or magnesium, pre-
ferably magnesium, alkyl ether sulfate derived
from an alcohol having 12 to 16 carbon atoms
ethoxylated with 1 to 12 moles of ethylene oxide;
(d) from 0~ to 15% mono-, di- or triethanolammonium,
preferably monoethanolammonium sulfate or mixtures
thereof;
(e) from 0% to 7% mono-, di- or triethanolamine or
mixtures thereof, preferably monoethanolamine;
and
(f) the balance water or water and Cl-C5 alkanol
(preferably ethanol) mixtures.
More concentrated liquids and/or pastes containing from
45~ to about 95% of said mixture of semi-polar nonionic
and anionic detergents are also desirable.
'
~.
:
: - . . .. ,. ~ : : -
1~5~ 3
The granular or ~ableted compositions of this inven-
tion contain from 5% to 50% preferably 10% to 30~ of the semi-
polar nonionic and anionic detergent mixture. The balance of
the composition comprises inert filler salts. A suitable inert
filler salt is sodium sulfate. Various additives, e.g., suds sup-
pressors, dyes, perfume, soil anti-redeposition agents, and water
may also be included in the granular or tableted composition.
The liquid detergent compositions of this invention
are preferably prepared by neutralizing he acid forms of the
anionic detergent with the aforementioned sources of alkalinity,
preferably alkanolamine, most preferably monoethanolamine, and
then adding a soluble alkaline earth metal salt, preferably
magnesium sulfate, to give the finished formula.
The examples which follow are illustrative of this
invention.
lOS'~Z'~3
I I I I I I I, I l I o
I I I I I I I I I o
.
1~ I I I ' I I I I I ~r I I
, , , , , , , o
, ~
I I I I , , I o 1 5 1 ~:
.~, o
3 ~ I I I I I I ~
I I I U I I I I I I ' .
~ ~ ~ .
o
H ~
~ ~ O ~.
~ 0 : '
~ U~ O
,1 I 1 151 1 1 1 1 1 1 1 1 1 .':.' '
U) O
m I ~ lI I I I I I I l I
u
~ ~ ~ I I I I I I I I I I I
a~ a
I
0 ~ 0 o
o 0 ~ o o
3 ~1 ~ O ~ -I 0 0 ~ a~ S
o ~ a) , a) 0 ~ o ~ ~ ~ ~ 0
o ~ ~ ~ X X ~ X ~ ~ ~ -
O N al~1 ~1 U~ 0 0 0 ~ O
N R ~~ 1 U v~
U ~: ~ o 0 ~ tl; C ~ O b~
O ~ ~ ~ O ~ ~ O Ul ~ ^ ~
~ ~v ::1 U ~1 ~ 0 ~I O U G) ~1 U a~ ~ u o
U O ~O O ~ ~ ~ ~1 ~ ~ O ~
~v $ o u ~ t) ~ ~ ~ ~o 0 ~o 8 ~ U _l
~ ~ ''I E3 ''I ~ ' ~ ~ ~ O ~
rl X ~ 0 ,I X
~v~ tJ` u~ ~v tJ~ 'TJ v~ ~v ~ ~v vU 3 o v~ Uv 3 0 ~v u~
o ~ O ~ o ~ o ~ o ~ O ~ ~.
-- 11 --
~ o o ~ OS'ZZZ3
.... ~,
~ ~ C
,,
o n o o 4
~r ~If~In "'
Lr~ :
o n o o
1~ ~r ~ ~ u~
u~
o u~ o o
. . , .
H ~
11~
O Ln O O :'
. , , .
~C ~ n
:
o n o o
In
~.
oIn o o
. . . .
~r ~ o u~ .
~D ' :
o ~ o o
. . . .
er ~ o ul
~ .-
H
OU~ O O
1~:1 . . . .
~ ~ ~r ~ o u~
~D
oU~ o o
~:1 , . . .
U ~ ~ o In
~ ~ ~ .
o n o o
m er
~o a
U
o n o o
. . . , ,_1
~o R
~ .
.,1 u
~C ~
O ~ :
a
.,
U rl
O ~ s~
o
.C ~
u
O
u ~
-- 12 --
-` 10~
Compositions A-L are tested for their ability to
remove grease from a soiled surface. A preweighed 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 1% aqueous solution of the
composition to be tested is added to the cup to completely
fill it. The aqueous solution has a temperature of 45C.
After 15 minutes, the cup is emptied and rinsed with
- distilled water. The cup is dried and then weighed to deter-
mine the amount of grease removal. The results of tests
performed on the above compositions are reported as follows
on a % grease removal basis.
105~''Z3
% Grease Removal
Composition A 10.0%
Composition B 60.0%
Composition C 18.0%
Composition D 64.0%
Composition E 30.0%
Composition F 50.0%
Composition G 33-0%
Composition H 52.0%
10 Composition I 2.0%
Composition J 61.0%
Composition ~ 6.0%
Composition L 64.0%
The above results show that the compositions of
this invention, i.e. compositions B, D, F, H, J and L -
remove more grease than the similar compositions wherein --~
the magnesium cation is not employed.
lOS;~Z~3
d~ o\ o\O o\O o\O d o\
O O O Lrl O O O
n ~ n ~r 0
n
~ :
o\ o\ o~o`, d d d
O O O Ul O O O
~L7 CO ~ ' ~ .
U~ ~ ~
, '
o\ d o\ dPo\ d o\
O O O O O Ln
C:~ CO CO ~ O ~ It1 ~ .
~1 ~
d o\ d~ d. d o\ tt.
O O O O O ~
C~ ~D 'n ~r o ~ In 1`
~ n
o\ o\ o\ d d~ d~ d
O O O O ~
m ~ O O ~ , ~:
~ ~ ~ .
H . .
H
~ 8
d d d ~ ~P d d
O O O U~ 0 ~,
o o ~r o (`1 In ~ 0
: '
.
0 ~. '
,
O
~1
S~ .
0
O ~ ' : .".'~
.,_1 ~ ', '
,~
.,, ~a 0
O ~ ~ ~ ~ rl
a~ 0 x ~1 ~ x a~
~ O ~ ~ O ~
O ~1 ~ l 0 Q)
o
rl O O O ~ 0
3 ~ ~ 0
o ~ o U~ o ~
-I 0 'I ~1 0 0 E3
o ul 0 ~ ~0 0E~ 3
o ~ s~
0
E~ ~o o ~ ~ u~ O
~: o ,l x ~ 1 0 a~ t)
0 ~ 0
~ -.
-- 15 ~
iO5~
The pH's of Compositions A, B,.C, D, E and F
are 7.0, 7.0, 7.0, 7.0, 8.5, and 8.5, respectively. When
tested for grease removal in the manner described in Example I,
the following results are obtained.
~ Grease Removal
Composition A .9.0%
Composition B 20.0%
Composition C 51.0%
Composition ~ : 36.0%
~10Composition E 49.0%
- Composition F 64.0%
The above results show that Compositions C-F
have better grease removal properties than Compositions A and B.
Additionally, the results show that the inclusion of triethanol-
amine in Compositions E and F provided an increased removalbenefit vers~s similar Compositions D and C, respectively.
105'~2;~3
EXAMPLE III
When Compositions C-F of Example II are formulated
with dimethyldodecylphosphine oxide replacing the amine
oxide, substantially the same grease removal results are
obtained.
EXAMPLE IV
When methyldodecylsulfoxide is used in place of the
amine oxide of Compositions C-F of Example II, substantially
~he same grease removal benefits are obtained.
EXAMPLE V
The use of monoethanolamine, diethanolaminei and
sodium and potassium hydroxide in place of the triethanol-
amine of Compositions E and F of Example II does not change
the grease removal performance of the composition.
EXAMPLE VI
The following granular detergent composition also
shows satisfactory grease removal performance.
Magnesium dodecyl benzene sulfonate 17.0
Diethyltetradecylamlne oxide 3.0~
Sodium sulfate 50-0%
Water 29.0%
Misc. (perfume, dye, etc.) balance
:
1052223
~ ~ o
~ ,1 H I ~ ~1 ~ ~ o
~ ~ ~ ~ .
`,, .,,
o ~
a~
R
,1: $ a~ ~, ,
h
H H ~ co O
~ ~, m
~W X ''
X ~1
~ ~ .
H ~ a U
H O ~ ~ D E3
3 r~
,~: ~ U ~ X
'~ H ~ 3 0 ~
u~ u s
r~
n~ o ~ ~ ~ 3 ~ ~
. ~ O .~ ~ ,, ~ 3
3 Q~ " ~ ~ rq
Q ~ S ~ ~
~1 0 ~ 3
h ~u) ~ u~
rd ~ ~ .~ U ~ ~
rl X ~ ~-r~ O
H O ~ h dP ~ O ~ ~
~ o ~ 3 a~
H ~ ~ ~ 8, u. ~ ~
O ~ ~ ~ ~ ~ ~ ~ ~
~ ~ ~ $~ ~ s ~ ~ ~ o ~ .~
x ~.e ,~ a ~ ~ ~
~1 rl X ~ rl ~ ~ ~ 3 ~ 0
~ ~ ~ ~U~ ~ ~ C ~ ~
~0 ~0 ~ O
- 1 8 -
.
