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Патент USA US3085992

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United States Patent O?ce
3,085,982
Patented Apr. 16, 1963
1
2
3,085,982
the need for solvent and/ or special surface active agents
(alkylolamide or alkylglyceryl ether sulfonate) in a ho
LIQUID DETERGENT COMPOSITION
David C. Steer and Norman R. Smith, Cincinnati, Ohio,
assiguors to The Procter & Gamble Company, Cin
cinnati, Ohio, a corporation of Ohio
No Drawing. Filed Apr. 22, 1959, Ser. No. 808,022
8 Claims. (Cl. 252-437)
mogeneous built liquid detergent; the object of an aspect
of the invention is to do so when silicate is present.
These and other objects are accomplished by a deter
gent formulation containing: (I) from about 3% to about
10% of an aliphatic tertiary amine oxide; (2) from about
3% to about 15% of a non~soap synthetic detergent of
the sulfated or sulfonated type; (.3) from about 3% to
about 10% of a soluble hydrotrope; and (4) from about
10% to about 30% of a soluble pyrophosphate salt.
This invention relates to liquid detergents of medium
duty and heavy-duty, sudsing type. More particularly, it
relates to improved liquid detergents which contain a
tertiary amine oxide surface active agent.
In recent years built liquid detergents have been gaining
favor for washing soiled clothing, for washing dishes and
for other purposes requiring an effective detergent. A
built detergent is one which contains, in addition to the
surface active agent, a soluble salt capable of sequester
ing calcium and magnesium ions of hard water and also
These ingredients are dissolved in an aqueous vehicle.
When the use of the formulation makes a corrosion in
hibitor desirable, ‘from about 3.5% to about 6% of alkali
metal silicate solids are dissolved in the same solution.
In the following more complete disclosure of the inven
tion, percentages refer to weight percent of the total for
mula unless otherwise indicated. It will be appreciated
capable of increasing the level of detergent effectiveness
that in an aqueous system it is for the most part immaterial
of the surface active agent. Built liquid detergents have, 20 by which ionic salts a particular ion is introduced; for
to some extent, replaced granular built detergents for
in the aqueous product there will be substantially com
various reasons. These reasons include: complete free
plete and continuous exchange of ions.
dom from dustiness, compact package, convenience in
Amine oxides are compounds of the general formula
pouring and measuring, and simpli?cation of manufacture.
R1R2R3N->O. The arrow is a conventional representa
The problems which have to be overcome in formulat 25 tion of a semipolar bond. They are generally prepared
ing built detergents in clear homogeneous liquid form are
by the direct oxidation of the appropriate tertiary amine.
mainly the problems of incorporating suf?cient surface
When R1 is a much longer chain than R2 and R3, amine
active agent and builder into the same solution. In cur
oxides have surface activity. For the purpose of this
rent practice an anionic sulfated or sulfonated compound
invention R1 is an alkyl radical of from about 10 to about
is ordinarily used as surface active agent, and potassium 30 16 carbon atoms. Desirable surface active properties
pyrophosphate is used as builder. Various surface active
are lost if R1 is substantially less ‘than 10 carbon atoms,
agents, hydrotropes and solvents are employed to increase
and solubility in the present formulation is too low if R1
their compatibility. The fact that the builder may cor
is greater than 16 carbon atoms. R2 and R3 are each
rode non-ferrous metals such as aluminum, may, depend
selected from the group consisting of methyl and ethyl
ing on the use for which the product is intended, lead to 35 radicals. ‘Preferably R1 is a dodecyl radical or a mixture
the inclusion of sodium silicate as a corrosion inhibitor.
of dodecyl with de-cyl, tetradecyl and hexadecyl radicals,
Its presence requires that special provisions be made to
keep the ingredients compatible. Limitations on the pH
of the formulation or the presence of agents designed to
such that at least 50% of the radicals are dodecyl radicals.
A convenient source of a preferred mixture is the middle
cut of coconut fatty alcohol which has the approxi
achieve compatibility is usually required.
40
mate chain length composition: 2%—Cm, 66%—C12,
In U.S. Patent 2,859,182 a combination of alkali metal
aryl sulfonate and at least one alkylolamide is disclosed
23%——C,4, and 9%——C1?. R2 and R3 are preferably
solubilizing agent, for example triamylphosphate or potas
invention. They complex the calcium and magnesium ions
methyl radicals. The amine oxide is used at from about
for making certain detergent compositions homogeneous.
3% to about 10% of the total formula. Too little amine
In these compositions the pH must be adjusted to about
oxide adversely affects the performance of the formula
11.4 or above to keep silicate in solution.
45 tions and too much amine oxide interferes with achieving
Different agents for solving the problem of making
builder and detergent in sufficient amount in a homoge
neous liquid.
detergent, builder and silicate compatible, which are dis
Soluble pyrophosphate salts are suitable builders in this
closed in US. Patents 2,877,185 and 2,877,186, are: a
sium benzene sulfonate; and an “assistant solubilizer," 50 of hard water; and, when the calcium ions of hard Water
for example ethyl alcohol or diethyleneglycol monobutyl
are present in excess, have an additional water softening
ether; and a particular detergent, alkyl glyceryl ether sul
fonate. The alkyl glyceryl ether sulfonate and the
solubilizing agent are used together, and the assistant
solubilizer is preferably included.
55
‘
effect by precipitating calcium pyrophosphate. They also
serve to increase the level of detergency obtainable with
synthetic surface active agents. Potassium, sodium, eth
anolammonium, diethanolammonium, and triethanolam
Liquid detergents generally contain one or more agents,
monium are suitable salts of the pyrophosphate anion in
called suds builders, to increase their sudsing. Typical
the practice of this invention; potassium pyrophosphate is
especially preferred. The soluble salt of pyrophosphate is
suds builders are coconut ethanolamide and lauryl al
In addition to being one more ingredient to be
cohol.
employed at a level of from about 10% to about 30%.
The pyrophosphate salts, like other sequestering agents,
‘ added to an already complicated formula, these suds 60
are corrosive towards aluminum. If the detergent solution
‘ builders may require, in certain formulations, a partic
is to contact this metal for prolonged periods of time, es
pecially at elevated temperatures, a corrosion inhibitor
should be desirably included. In a product designed for
colored for use in liquid products. They are not con
65 hand laundry of fine fabrics, it is unnecessary. Soluble
sidered to serve the cleaning function of a detergent.
silicates are highly effective inhibitors and can be added
An object of this invention is to provide a homoge
to the formulas of this invention without difficulty at levels
neous built liquid detergent of improved sudsing charac
of from about 3.5% to about 6%. Potassium, or prefer
ular perfume to cover their odor.
Amide-type suds
builders, unless puri?ed, are often undesirably highly
teristics and good detergent effectiveness.
ably sodium silicates haviug a weight ratio of Slog/M20
A further object of this invention is to eliminate suds 70 of from about 1.0 to about 2.16 and preferably from about
builders from a high sudsing liquid detergent formulation.
1.6 to about 2.6 can be used. “M” in this ratio refers to
An additional object of this invention is to eliminate
sodium or potassium. Less than about 3.5% sodium sili
3,085,982
3
4
cate solids, although useable in the present compositions,
does not provide protection against corrosion at typical
fonate and alkyl sulfate are therefore especially preferred
anionic detergents. Preferred formulas of this invention
use conditions, and more than about 6% sodium silicate
include those in which two anionic detergents are used in
solids is difficult to incorporate into a homogeneous liquid.
combination with the amine oxide. For example, C12
alkyl benzene sulfonate, coconut alkyl sulfate and dimeth
Suitable hydrotropes to increase the compatibility of the
ingredients of the formulations of this invention are the
aryl sulfonates disclosed in the hercinbefore cited patents.
More speci?cally they are soluble salts of the hydrotrope
anions. Preferred hydrotrope anions are benzene sulfon
ate, xylene sulfonate and toluene sulfonate. They are used 10
yldodecylarnine oxide in approximately equal quantities
in a detergent combination which gives superior sudsing.
good mildness to the skin and relatively low cost and is
especially preferred in the practice of this invention. Slight
variations from equal quantities of the amine oxide and
the anionic detergents permits ?ne adjustment of the prop
erties of the formulas. If more of one detergent is used,
ammonium, and triethanolammonium and especially as
preferably less of another is used. To maintain the ho
the alkali metal, potassium, or sodium, salts. Sodium or
mogeneous character of the product, the sum of anionic
potassium toluene sulfonate is especially preferred. The
hydrotrope salt is added at levels of from about 3% to 15 detergent and amine oxide is preferably kept in the range
of from about 10% to about 25%.
about 10%. Levels of from about 4% to about 6% are
The inorganic builder content is preferably raised as
preferred. The upper limit of about 10% is set by in
the total synthetic detergent content is lowered; so that
creasing dilution of the product by an ingredient substan
the sum of builder and detergent is kept from about 25%
tially inert so far as sudsing and detergency are concerned.
The lower limit is the amount required to achieve a 20 to about 40%. In this range of composition the product
has particularly good performance and homogeneous
homogeneous solution. It will be appreciated that it is
character. As a rough generalization, when the total de
necessary that the formulations of this invention should
tcrgent is greater than the builder the product is of me
be liquid at somewhat higher and at somewhat lower tem»
dium-duty type and can be recommended for hand laun
peratures than usual room temperature. The amount of
hydrotrope salt used is preferably the minimum amount 25 dering of ?ne fabrics and dishwashing. When the deter
gent level is lowcr or equal to the builder, the product is
which will hold the ingredients in solution at the temper
as the soluble salts such as: ethanolammonium, diethanol
ature to which it is desired that the formula can be cooled
of heavy-duty type especially adapted for laundry and gen
without phase separation.
eral purpose use.
Silicate is particularly desirable in the
Amine oxide is an effective detergent; however, in order
to achieve the objects of this invention, a supplemental
heavy-duty product.
non-soap anionic synthetic detergent is added. From
about 3% to about 15% anionic detergent is employed.
be added in minor amounts materials which make the
product more effective or more attractive. The following
are mentioned by way of example. A soluble sodium
carboxymethylcellulose may be added in amounts up to
Preferred anionic detergents which can be included are:
alkyl benzene sulfonate, alkyl ethylene oxide ether sulfate
In a ?nished detergent formulation there will preferably
wherein there are from 1 to 5 ethylene oxide residues per 35 about 2% to inhibit soil redeposition. A tarnish inhibitor
such as benzotriazole or ethylenethiourea may be added
alkyl and the mixtures formed when 1 to 5 ethylene oxides
in amounts up to about
Fluorescers, perfume, and
are reacted with one mole of alcohol, and alkyl sulfate.
color, while not essential in the compositions of the in
These may be represented, respectively, as:
vention, may be added in amounts less than about 1%.
40
All the constituents of these liquid detergent formula
where x is an integer from 1 to 5, and R804. In these
tions are dissolved in water with the possible exception
of certain of the minor nonessential ingredients which are
compounds the alkyl chain (R) will contain from about
at least ?nely and homogeneously dispersed to give the
9 to about 16 carbon atoms and preferably about 12 car
bon atoms. Mixtures of alkyl radicals of different chain
lengths are preferably used since they are soluble and
effect of a one—phase composition. A maximum water
level of about 70% is set by the need to get enough active
ingredient in the solution to hold the volume required per
usage to an acceptable level. The minimum water level
readily available from synthetic or natural sources, e.g.,
coconut alcohol and a mixture containing tri-, tetra-, and
pentapolypropylene polymers and averaging about 12 car
of about 45% is set by the requirement of having su?i
cient water to dissolve the ingredients.
bon atoms. These detergents are used as soluble salts; 50
The mole ratio of potassium (and any alkanolammo~
speci?cally, they are used as sodium, potassium, ethanol
nium ions) to sodium is maintained above about 3:1 to
ammonium, diethanolammonium and triethanolammo
nium salts.
Sodium and triethanolamine salts are pre
ferred. Other non-soap anionic synthetic detergents, with
alkyl radicals as speci?ed above, can be usefully employed
if they have the following characteristics: their salts, as
speci?ed above, are soluble to the extent of at least 3% in
an aqueous solution of 3% dimethyldodecylamine oxide,
3% potassium toluene sulfonate and 10% potassium pyro
phosphate; and they are stable against hydrolysis in alka
line solution. An example is the potassium salt of the
sulfated condensation product of four moles of ethylene
oxide with a mole of nonyl phenol.
The formulas of this invention, containing amine oxide,
maintain the one-phase nature of the product and prefer
ably is maintained above about 3.511.
Example I
The following compositions were prepared and exam
ined. All were clear homogeneous pourable liquids at
room temperature.
Formulas B and C were cooled to
lower temperatures and remained clear at 50° F.
Dimethyldodccyl amino oxide
percent _____________________ ..
4
Sodium polypropylene benzene
suds so well in the laundry and dishpan that no suds build
sulfonate (a mixture. of tri-,
er is required. Among the anionics, the alkyl sulfate
tetrm, and peutapropylenit
averaging about C12} percent"
makes a particular contribution to sudsing in the formulas
Sodium coconut 1sulfate._ .do_.
Potassiutntoluencsulfunate _ , do. _
of this invention. Alkyl benzene sulfonate is particularly
l’otassiumpyrophosphate_._ . ' lo. _
favored for this purpose because in most circumstances it
Sodium silicate solids S5102:
'
r
"at,"
reduces the cost of the formula. A supplemental anionic 70
detergent can tend to improve the mildness of the formu
Water ____________________ “do”
6
15
_,do _
lations, alkyl benzene sulfonate being particularly note
worthy in this respect. The supplemental anionic deter
gents also permit the achieving of higher levels of active
ingredients in a homogeneous liquid. Alkyl benzene sul 75
_
K/Nu,approx_1nole rutio_._llo_.
5
7
5
8
6
4
ti
3
5
4
‘2
3
4
4
8
7
G
t‘,
6
(I
18
18
ltt
18
____ -_; ____ __
‘
as
. _
_
_
__
(1)
4.1
as}
as
0.1’)
(1.15
til
4.2
(2?
l o
as
_ _ _
_
_
as
_
_ _
(5)
i
.
_
_
l?)
5.0
is
_ _
.
.
__
(“I
d ‘J
1 Coconut refers to the alkyls of lllltltllt? cut coconut ult-ohul containing
about 292-010. [iti‘lk-On, ?lmy-Cu ul1tl9‘;T;,.—~C1s.
2 Balance.
3,085,982
5
6
for the purposes for which medium-built liquid products
An additional composition, G, was prepared as a dupli
are intended.
cate of F except the 8% sodium coconut sulfate was re
In these compositions, methylethylcoconutamine oxide
placed by 6% potassium salt of a sulfated condensation
or diethylcoconutamine oxide can be substituted for di
product of one mole coconut 1 alcohol with 3 moles of
methylcoconutamine oxide without substantially adversely
1 Coconut refers to the alkyls of middle out coconut alcohol
affecting the physical characteristics or performance of the
containing about 2%——Cio, 66%—Ci2, 23%—'C14. and 9%—Cld.
compositions.
ethylene oxide. The K/ Na mole ratio in this product was
What is claimed is:
about 7.4.
1. A substantially clear, high-sudsing, concentrated
Products A, C, D, and F proved to be superior in main
liquid detergent composition consisting essentially of:
taining suds during the washing of soiled dishes to com- 10
(a) from about 3% to about 10% of an aliphatic ter
mercially available built liquid detergents tested under the
same conditions.
tiary amine oxide having the general formula
R1R2R3N-> 0, where R; is an alkyl radical containing
Products B and G proved to be good
dishwashing products, being about equal to available built
liquid products.
Products B and C were also employed in washing soiled 15
clothes in a typical domestic washing machine. The suds
in the ?rst load was higher than for commercial built
liquid detergents tested under the same conditions.
The sodium silicate can be omitted from these formulas
methyl and ethyl radicals, at least about 50% of said
amine oxide having R1 containing 12 carbon atoms;
(b) from about 3% to about 15% of a non-soap de
tergent selected from the salts of the group of de
without substantially affecting appearance or performance 20
except for their corrosiveness to non-ferrous metals.
Dodecyl radicals and coconut radicals are substantially
equivalent, that is one can be substituted for the other in
the ingredients of this example with no substantial change
in appearance or performance of the product. Potassium 25
benzene sulfonate or potassium xylene sulfonate can be
used to replace potassium toluene sulfonate without losing
the homogeneous nature of the product or adversely
affecting its performance.
from about 10 to about 16 carbon atoms and R2 and
R3 are each selected from the group consisting of
30
Example I]
tergent anions consisting of R804“, R(OC2H4)xSO(,
where x is an integer from 1 to 5
R being an alkyl radical containing about 9 to about
16 carbon atoms, and mixtures thereof;
(0) from about 3% to about 10% of a salt of a hydro
trope anion selected from the group consisting of
toluene sulfonate, benzene sulfonate, and xylene sul
fonate;
(d) ‘from about 10% to about 30% of a salt of a
The following composition was prepared.
pyrophosphate anion; and the balance substantially
(e) water;
It was a
clear homogeneous pourable liquid at room temperature.
It remained clear at 30° F.
the cations of the salts of the group of detergent anions, of
35 the salts of the hydrotrope anions, and of the salts of the
Percent
Dimethyldodecylamine oxide __________________ __
said pyrophosphate anion being selected from the group
consisting of potassium, sodium, ethanolammonium, di
ethanolammonium, and triethanolammonium, ‘and the
6
Triethanolamine salt of polypropylene benzene sulfo
nate (a mixture of tri-, tetra-, and pentapropylene
averaging about C12) _______________________ __
6 40
mole ratio of the total of potassium and of alkanolarn
monium cations to sodium cations being greater than
about 3:1, said composition being substantially free from
amide suds-builders.
2. The liquid detergent composition of claim 1 wherein
Sodium silicate solids, Si02 to NazO is 1.6 _______ __ 5
Water _________________________________ __ Balance
in the tertiary amine oxide R3 and R3 are each methyl
K-l-triethanolammonium/Na, approx. mole ratio ___ 5.5 45 radicals.
3. A substantially clear high sudsing concentrated liquid
The suds during washing soiled dishes obtained from
detergent composition consisting essentially of:
Potassium pyrophosphate _____________________ __ 25
Potassium toluene sulfonate ___________________ -_ 8.5
this product were more stable than suds obtained from
(a) from about 3% to about 10% of an aliphatic ter
commercially available built liquid detergents. This prod
tiary amine oxide having the general formula
R1R2R3N->O where R1 is an alkyl radical containing
uct showed good sudsing and cleaning characteristics in
washing soiled clothing.
Example 111
from about 10 to about 16 carbon atoms and R2 and
R3 are each selected from the group consisting of
methyl and ethyl radicals, at least about 50% of said
amine oxide having R1 containing 12 carbon atoms;
The following compositions were prepared. They were
clear homogeneous pourable liquids at room temperature.
After freezing at 40° F. they again became clear and
(b) from about 3% to ‘about 15% of a non-soap de
tergent selected from the salts of the group of de
homogeneous on being warmed to room temperature.
I A l B
Dirnethyleoconut I amine oxide ................. __
5.0
tergent anions consisting of R804", R(OC2H4)XSO4"
where x is an integer from I to 5
60
6.0
Sodium coconut 1 ethylene oxide ether suit-ate
R being an alkyl radical containing about 9 to about
16 carbon atoms, and mixtures thereof;
(0) ‘from about 3% to about 10% of a salt of a hydro
trope anion selected from the group consisting of
(average of 3 ethylene oxide residues per mole
cule) __________________________________________ _.
8. 5
Sodium coconut I alkyl sulfate ___________________ __
2. 5
10.0
________ ._
Sodium polypropylene benzene sullonate (a mix
ture oitri-, tetra, and penta’propyleue averaging
about C12) _____________________________________ __
Potassium pyrophosphate_..___ ___
_
Potassium toluene suli'onate _____ __
Color ________________ -_
4.0
12
5
0.0013
4.0
12
5
(I. 02
toluene sulfonate, benzene sulfonate, and xylene sul
fonate;
0 0013
Bonzotriazole _
0. 02
Water _______________ _ .
Balance
Balance
K/Na, approx. mole re
4. 2
4. S
1
i (‘oconut refers to the alkyls of middle out coconut alcohol containing
about 2€’—G1t, 6651-012, 2370-014, and9%—Cm.
These compositions gave good suds in washing dishes and
in hand washing of ?ne fabrics. They are highly suitable
(d) from about 3.5% to about 6% of silicate solids of
70
the composition SlOgIMgO their weight ratio being
from about 1.6:1 to about 2.6:] and wherein the M
of M20 is selected from the group consisting of
sodium and potassium;
(e) from about 10% to about 30% of a salt of a pyro
phosphate anion; and the balance substantially
3,085,982
7
8
(f) water;
said amine oxide having R1 containing 12 carbon
atoms;
the cations of the salts of the said detergent anions, of the
salts of the said hydrotrope anions, and of the salts of
the said pyrophosphate anion being selected from the
group consisting of potassium, sodium, ethanolammonium, 5
and triethanolammonium, the mole ratio of the total of
potassium and alkanolammonium cations to sodium ca
(b) ‘from about 3% to about 15% of a sodium salt of
a non-soap detergent anion selected from the group
consisting of R804", R(OC2H4)XSO4" where x is an
integer from 1 to 5
tions being greater than about 3:1, said composition being
substantially free from amide suds-builders.
4. The liquid detergent composition of claim 3 ‘where 10
in the amine oxide R2 and R3 are each methyl radicals.
5. The liquid detergent of claim 3 wherein the detergent
anion is
11%‘ “ >30,
R being ‘an alkyl radical containing about 9 to about
16 carbon atoms, and mixtures thereof;
(0) from about 3% to about 10% of potassium toluene
sulfonate;
114 >303“
(d) ‘from about 3.5% to about 6% of silicate solids of
15
16 carbon atoms.
phosphate; and the balance substantially
(f) water, said composition being substantially free
6. The liquid detergent composition of claim 3 wherein
the detergent anion is a mixture of
R<
the composition SiO2:Na2O, their weight ratio being
from about 1.6:1 to about 2.6:];
(e) from about 10% to about 30% of potassium pyro
R being an alkyl radical containing from about 9 to about
20
>~s Os-and R s or
from amide suds-builders.
References Cited in the ?le of this patent
UNITED STATES PATENTS
R being an alkyl radical containing from about 9 to about
16 carbon atoms.
7. The liquid detergent composition of claim 3 wherein
the hydrotrope anion is toluene sulfonate.
25
8. A substantially clear high-sudsing liquid detergent
composition consisting essentially of:
(a) from about 3% to about 10% of an aliphatic ter 30
2,060,568
2,169,976
2,581,677
2,877,186
Graenacher et al _______ __ Nov. 10,
Guenther et al _________ __ Aug. 15,
Machlis et al ____________ __ Jan. 8,
Krumrei _____________ __ Mar. 10,
1936
1939
1952
1959
FOREIGN PATENTS
tiary amine oxide having the general formula
R1R2R3N—>O where R1 is an alkyl radical containing
437,566
from about 10 to about 16 carbon atoms and R2 and
“The Chemistry of Fatty Amines,” 1948, pub. by Ar
R3 are each ‘methyl radicals, at least about 50% of
Great Britain __________ .. Oct. 31, 1935
OTHER REFERENCES
mour and Co., page 13.
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