U.S. patent number 3,720,621 [Application Number 05/046,472] was granted by the patent office on 1973-03-13 for aquenous detergent compositions.
Invention is credited to Alfred Smeets.
United States Patent |
3,720,621 |
Smeets |
March 13, 1973 |
AQUENOUS DETERGENT COMPOSITIONS
Abstract
The present invention provides a homogeneous liquid composition
containing by weight: A. from 14 to 35 percent of sodium
tripolyphosphate, B. from 0.1 to 50 percent at least of a potassium
and/or ammonium salt of an inorganic or organic acid, C. from 15 to
85.9 percent of water. The composition is especially useful as a
detergent for non-porous surfaces and textile materials.
Inventors: |
Smeets; Alfred (B-3300
Tirlemont, BE) |
Family
ID: |
10310799 |
Appl.
No.: |
05/046,472 |
Filed: |
June 15, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Jun 17, 1969 [GB] |
|
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30,640/69 |
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Current U.S.
Class: |
510/372; 510/339;
510/534; 510/533; 510/429; 510/424; 510/425; 510/426; 510/428;
510/427; 510/340 |
Current CPC
Class: |
C11D
3/06 (20130101); C11D 3/2075 (20130101); C11D
3/046 (20130101) |
Current International
Class: |
C11D
3/06 (20060101); C11D 3/20 (20060101); C11D
3/02 (20060101); C11D 17/00 (20060101); C11d
003/04 (); C11d 007/00 () |
Field of
Search: |
;252/99,135,137,138,152,161 ;8/111 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Weinblatt; Mayer
Claims
I claim:
1. A homogeneous aqueous solution consisting essentially of water
and (a) from 14 to 35 percent by weight of sodium tripolyphosphate
and (b) from 0.1 to 50 percent by weight of at least one salt
selected from the group consisting of potassium and ammonium
sulfate, chloride, nitrate, carbonate bicarbonate, orthoborate,
metaborate, tetraborate perborate, orthophosphate, metaphosphate,
pyrophosphate, maleate, adipate, aconitate, citrate, tartrate,
succinate, ethylenediaminetetraacetate, nitrilotriacetate and
diethylenetriaminepentaacetate.
2. A homogeneous liquid detergent composition in the form of an
aqueous solution consisting essentially of water and
a. from 14 to 35 percent by weight of sodium tripolyphosphate,
b. from 0.1 to 50 percent by weight of at least one salt selected
from the group consisting of potassium and ammonium sulfate,
chloride, nitrate, carbonate, bicarbonate, orthoborate, metaborate,
tetraborate, perborate, orthophosphate, metaphosphate,
pyrophosphate, maleate, adipate, aconitate, citrate, tartrate,
succinate, ethylenediaminetetraacetate, nitrilotriacetate and
diethylenetriaminepentaacetate,
c. from 0 to 35 percent by weight of at least one sodium, potassium
or triethanolamine salt of a sulfopolycarboxylic acid ester with at
least one hydroxy-containing non-ionic surface-active agent
selected from the group consisting of aliphatic alcohols containing
from eight to 22 carbon atoms ethoxylated with from 1 to 50 moles
of ethylene oxide per mole of alcohol, and alkylphenols containing
six to 12 carbon atoms in the alkyl chain and ethoxylated with from
3 to 25 moles of ethylene oxide per mole of alkylphenol, said
sulfopolycarboxylic acid being selected from the group consisting
of sulfosuccinic acid, sulfotricarballylic acid and the
sulfopolycarboxylic acid obtained by sulfonating and acidifying the
pyrolysis product of calcium citrate.
d. from 0 to 20 percent by weight of at least one anionic
surface-active agent selected from the group consisting of fatty
acid soaps containing from 10 to 22 carbon atoms, alkyl sulfonates
containing from 8 to 25 carbon atoms, alkylbenzene sulfonates
containing from 10 to 16 carbon atoms in the alkyl group, alkyl
sulfates containing from eight to 18 carbon atoms, alkyl
polyoxyethylene ether sulfates and alkylaryl polyoxyethylene ether
sulfates, the alkyl group of which contains eight to 18 carbon
atoms and the polyoxyethylene group of which contains from 1 to 4
ethylene oxide units,
e. from 0 to 15 percent by weight of at least one non-ionic
surface-active agent selected from the group consisting of
alkylphenols containing from six to 12 carbon atoms in the alkyl
chain and ethoxylated with from 3 to 25 moles of ethylene oxide per
mole of alkylphenol, aliphatic alcohols containing from eight to 22
carbon atoms ethoxylated with from 1 to 50 moles of ethylene oxide
per mole of alcohol, fatty acid ethanolamides and ethoxylated fatty
acid ethanolamides, and
f. from 0 to 20 percent by weight of at least one solubilizing
agent selected from the group consisting of potassium xylene
sulfonate, potassium toluene sulfonate and potassium cumene
sulfonate,
at least one of compounds (c), (d) and (e) being present.
3. A composition according to claim 2, wherein the salt (b)
potassium pyrophosphate is in a proportion of from 5 to 25 percent
by weight based on the amount of sodium tripolyphosphate.
4. A composition according to claim 2, wherein the salt (c) is a
potassium salt.
5. A composition according to claim 2, wherein the anionic
surface-active agent (d) is a potassium salt.
6. A composition according to claim 2, wherein salt (c) is present
in a proportion of from 1 to 20 percent by weight of the total
composition.
7. A composition according to claim 2, wherein at least one of
compounds (d) and (e) is present, compound (d) in a proportion of
from 1 to 15 percent by weight and compound (e) in a proportion of
from 1 to 10 percent by weight of the total composition, and
solubilizing agent (f) is present in a proportion of from 1 to 12
percent by weight of the total composition.
8. A composition according to claim 2, wherein salt (c) is present
in a proportion of from 1 to 20 percent by weight of the total
composition and at least one of compounds (d) and (e) is present,
compound (d) in a proportion of from 1 to 15 percent by weight and
compound (e) in a proportion of from 1 to 10 percent by weight of
the total composition, and solubilizing agent (f) is present in a
proportion of from 1 to 12 percent by weight of the total
composition.
9. A homogeneous liquid detergent composition in the form of an
aqueous solution consisting essentially of water and
a. from 18 to 28 percent by weight of sodium tripolyphosphate,
b. from 1 to 10 percent by weight of at least one salt selected
from the group consisting of potassium and ammonium sulfate,
chloride, nitrate, carbonate, bicarbonate, orthoborate, metaborate,
tetraborate, perborate, orthophosphate, metaphosphate,
pyrophosphate, maleate, adipate, aconitate, citrate, tartrate,
succinate, ethylenediaminetetraacetate, nitrilotriacetate and
diethylenetriaminepentaacetate, and
c. from 1 to 20 percent by weight of at least one sodium, potassium
or triethanolamine salt of a sulfocarboxylic acid ester with at
least one hydroxy-containing non-ionic surface-active agent
selected from the group consisting of aliphatic alcohols containing
from eight to 22 carbon atoms ethoxylated with from 1 to 50 moles
of ethylene oxide per mole of alcohol, and alkylphenols containing
six to 12 carbon atoms in the alkyl chain and ethoxylated with from
3 to 25 moles of ethylene oxide per mole of alkylphenol, said
sulfopolycarboxylic acid being selected from the group consisting
of sulfosuccinic acid, sulfotricarballylic acid and the
sulfopolycarboxylic acid obtained by sulfonating and acidifying the
pyrolysis product of calcium citrate.
10. A composition according to claim 9, wherein the salt (b)
potassium pyrophosphate is in a proportion of from 5 to 25 percent
by weight based on the amount of sodium tripolyphosphate.
11. A homogeneous liquid detergent composition in the form of an
aqueous solution consisting essentially of water and
a. from 18 to 28 percent by weight of sodium tripolyphosphate,
b. from 1 to 10 percent by weight of at least one salt selected
from the group consisting of potassium and ammonium sulfate,
chloride, nitrate, carbonate, bicarbonate, orthoborate, metaborate,
tetraborate, perborate, orthophosphate, metaphosphate,
pyrophosphate, maleate, adipate, aconitate, citrate, tartrate,
succinate, ethylenediaminetetraacetate, nitrilotriacetate and
diethylenetriaminepentaacetate,
c. from 1 to 20 percent by weight of at least one sodium, potassium
or triethanolamine salt of a sulfopolycarboxylic acid ester with at
least one hydroxy-containing non-ionic surface-active agent
selected from the group consisting of aliphatic alcohols containing
from eight to 22 carbon atoms ethoxylated with from 1 to 50 moles
of ethylene oxide per mole of alcohol, and alkylphenols containing
six to 12 carbon atoms in the alkyl chain and ethoxylated with from
3 to 25 moles of ethylene oxide per mole of alkylphenol, said
sulfopolycarboxylic acid being selected from the group consisting
of sulfosuccinic acid, sulfotricarballylic acid and the
sulfopolycarboxylic acid obtained by sulfonating and acidifying the
pyrolysis product of calcium citrate, and
d. from 1 to 15 percent by weight of at least one anionic
surface-active agent selected from the group consisting of fatty
acid soaps containing from 10 to 22 carbon atoms, alkyl sulfonates
containing from eight to 25 carbon atoms, alkylbenzene sulfonates
containing from 10 to 16 carbon atoms in the alkyl group, alkyl
sulfates containing from eight to 18 carbon atoms, alkyl
polyoxyethylene ether sulfates and alkylaryl polyoxyethylene ether
sulfates, the alkyl group of which contains eight to 18 carbon
atoms and the polyoxyethylene group of which contains from 1 to 4
ethylene oxide unites, and/or
e. from 1 to 10 percent by weight of at least one non-ionic
surface-active agent selected from the group consisting of
alkylphenols containing from six to 12 carbon atoms in the alkyl
chain and ethoxylated with from 3 to 25 moles of ethylene oxide per
mole of alkylphenol, aliphatic alcohols containing from eight to 22
carbon atoms ethoxylated with from 1 to 50 moles of ethylene oxide
per mole of alcohol, fatty acid ethanolamides and ethoxylated fatty
acid ethanolamides, and
f. from 1 to 12 percent by weight of at least one solubilizing
agent selected from the group consisting of potassium xylene
sulfonate, potassium toluene sulfonate and potassium cumene
sulfonate.
12. A composition according to claim 11, wherein the salt (b)
potassium pyrophosphate is in a proportion of from 5 to 25 percent
by weight based on the amount of sodium tripolyphosphate.
Description
The present invention relates to aqueous detergent compositions
which, although containing proportions of sodium tripolyphosphate
greater than the saturation concentration of the said salt in
water, are nevertheless in the form of substantially homogeneous
solutions. Such compositions may be used particularly for the
cleansing of articles having non-porous surface and for the washing
of textile materials.
Sodium tripolyphosphate (hereinafter referred to as TPP) is the
alkali metal phosphate conventionally used in solid detergent
compositions for domestic and/or industrial use, for several
reasons: it is a sequestering agent for heavy cations in water and
provides water-softening properties, it reinforces the detergent
action of anionic and/or non-ionic surface-active agents currently
used in detergent compositions, it contributes to a marked degree
the removal of soil on articles during cleansing and ensures the
formation of stable suspensions of the detached soil particles in
the wash liquid, and it has little corrosive action on metals
and/or metal alloys used in the construction of washing machines,
wash-vessels and the like. To such diverse advantages of TPP there
is added a low manufacturing cost, which provides an explanation
why it is in practice pre-eminent over other alkali-metal
polyphosphates, for example sodium pyrophosphate or sodium
hexametaphosphate.
TPP has a relatively low solubility in water, the saturation
concentration in water at room temperature being about 164 g/liter,
corresponding to about 14 percent by weight. Such low solubility is
not a disadvantage for solid detergent compositions, which may for
example be in the form of powder, granules, flakes or the like.
However such low solubility represents a practically insolvable
problem in the formulation of homogeneous liquid detergent
compositions, due to the fact that these normally require a TPP
content of about 18 to 40 percent by weight as this is the level of
concentration in most commercial solid detergent compositions. In
fact the proportion of TPP capable of being introduced into liquid
detergent compositions is substantially lower than the theoretical
14 percent by weight (which 9 the saturation concentration of TPP)
due to the presence particularly of surface-active agents. A
well-known effect is that surface-active agents and TPP have a
mutual effect on their respective solubilities, the higher the
concentration of surface-active agent in liquid compositions the
less the solubilitity of TPP, and vice versa. Another problem, also
affecting the solubility of TPP is its resistance to hydrolysis. It
is known that in the presence of water, the hydrolysis tends to
form an equilibrium according to the equation
TPP .revreaction. sodium pyrophosphate + sodium orthophosphate.
Such a condition detracts from the useful properties of TPP.
There is at the present time an increasing tendency to use liquid
detergent compositions instead of solid detergent compositions. The
superiority of such liquid compositions includes the following:
a. they are homogeneous, solid compositions presenting difficulty
due to differences in granulation and the specific gravity of the
constituent ingredients;
b. liquid compositions are more easily delivered in measured doses
than solid compositions in automatic washing machines (no blockage
or residue or formation of dust);
c. they may be applied locally to the article being cleaned,
etc.
Current liquid detergent compositions contain in practice
phosphates (pyrophosphate, tripolyphosphate) only in the form of
their potassium salts, as they are more soluble than the
corresponding sodium salts (cf. O. PFRENGLE and C. PIETRUCK,
Fette.Seifen.Anstrichmittel, 64, (1962), pages 321-326). By this
means, it is possible to provide concentrations of phosphates which
are approximately of the same order of magnitude as the
conventional solid compositions. But potassium pyrophosphate and
tripolyphosphate are more sensitive than their sodium equivalents.
There is interest therefore in providing liquid detergent
compositions in which the phosphate content is predominantly sodium
tripolyphosphate, and it is to solving this problem that the
present invention is directed.
The applicants have discovered that it is possible to prepare
liquid aqueous detergent compositions containing proportions of
sodium tripolyphosphate considerably higher than the limit of
solubility thereof in water, under normal conditions, in other
words in a concentration greater than 14 percent by weight and up
to 35 percent by weight, by the presence in the compositions with
sodium tripolyphosphate of a suitable proportion of an inorganic or
organic potassium and/or ammonium salt together subsequently with
desired surface-active agents, solubilizing agents, organic
sequestering agents, and other adjuvants conventionally used in
solid and/or liquid detergent compositions, per-compounds, the rest
being water.
The object of the present invention provides homogeneous liquid
detergent compositions comprising the following composition:
a. from 14 to 35 percent by weight of sodium tripolyphosphate,
b. from 0.1 to 50 percent by weight at least of a potassium and/or
ammonium salt of an inorganic or organic acid;
c. from 0 to 35 percent by weight at least of a salt of a
sulphonated ester of a polycarboxylic acid,
d. from 0 to 20 percent by weight at least of an anionic
surface-active agent,
e. from 0 to 15 percent by weight at least of a non-ionic
surface-active agent,
f. from 0 to 20 percent by weight at least of a solubilizing
agent,
g. from 0 to 20 percent by weight at least of an organic
sequestering agent,
h. from 0 to 20 percent by weight at least of a per-compound,
i. from 0 to 5 percent by weight in total of coloring agents,
scents, bodying agents, optical whiteners, anti-corrosion agents
and anti-staining agents,
j. water to make up to 100 percent.
a. The sodium tripolyphosphate, Na.sub. P.sub.3 O.sub.10, used in
the aqueous detergent compositions according to the invention, may
be used in any of its crystallographic forms and in any state of
hydration, from the anhydrous form Na.sub.5 P.sub.3 O.sub.10 to the
hexahydrate compound Na.sub.5 P.sub.3 PO.sub.10.sup.. 6H.sub.2 O.
It is present in the compositions according to the invention in a
concentration of from 14 to 35 percent by weight, preferably from
about 18 percent to about 28 percent by weight, depending on the
intended use of the composition and depending on the concentration
of other ingredients present therein.
b. The potassium and/or ammonium salt used to enhance the
solubility of the TPP in the aqueous detergent compositions
according to the invention may be a salt of an inorganic acid for
example a sulphate, chloride, nitrate, carbonate, bicarbonate,
borate, orthophosphate, metaphosphate, pyrophosphate and the like,
or may be a salt of an organic acid, for example a maleate,
adipate, aconitate, citrate, tartrate, ethylenediamine-tetracetate,
nitrilotriacetate, diethylene-triamine-pentacetate, succinate or
the like. Although inorganic and organic sodium salts diminish the
solubility of TPP in water, inorganic or organic potassium and/or
ammonium salts used according to the invention enhance the
solubility as hereinafter described. However the nature of the
inorganic or organic anion of the potassium and/or ammonium salt
incorporated in the compositions influences the solubility of TPP
to a considerable extent. Thus by way of example, potassium
sulphate is more effective than potassium chloride, and the
carbonate more effective than the bicarbonate. As a result, the
potassium and/or ammonium salt may be present in a proportion of
down to 0.1 percent by weight or up to 50 percent by weight, based
on the total aqueous detergent composition. For obvious economic
reasons, no more of the potassium salt should be used than is
necessary, a portion of from 1 to 10 percent by weight based on the
total composition, is preferred.
Potassium pyrophosphate is the preferred potassium salt. It is
effective not only as a sequestering agent which enhances the
solubility of TPP in water, but the applicants have discovered that
it effectively stabilizes the tripolyphosphate agent hydrolysis in
aqueous solution into sodium pyrophosphate and sodium
orthophosphate (as shown in the experiments hereinafter described).
It is therefore particularly interesting to introduce potassium
pyrophosphate in the aqueous detergent compositions of the present
invention. The content should not therefore be too great so as to
undergo a double-decomposition reaction with TPP to form sodium
pyrophosphate, which as is well known, has a very low solubility in
water and therefore tends to separate out as a precipitate. The
applicants investigations have shown that the optimum proportion of
potassium pyrophosphate incorporated in the liquid detergent
compositions according to the invention is between 5 and 25 percent
based on the TPP present in the said compositions.
c. The salts of sulphonated esters of a polycarboxylic acid which
may be used as surface-active agent according to the present
invention have properties superior to anionic and non-ionic
surface-active agents for the production of liquid detergent
compositions due to the face that (1) they are equally effective at
lesser concentrations, (2) they are more soluble in water, (3) they
have a greater resistance to salting out by electrolytes and (4)
they have solubilizing properties as shown in the Examples
hereinafter described.
Examples of such salts of sulphonated esters of polycarboxylic
acids are the potassium salts of sulphonated derivatives of one or
more alpha-beta unsaturated di- or tri-carboxylic acids esterified
with the hydroxyl group of one or more non-ionic surface-active
agents described in the Applicants British Pat. Specification No.
47677/67, or the potassium salts of sulphonated polycarboxylic
acids partially esterified by the hydroxyl group of one or more
non-ionic surface-active agents, as described in the Applicants
British Pat. Specification No. 31014/67, or the potassium salts of
sulphonated polycarboxylic acids esterified with the hydroxyl group
of a non-ionic surface-active agent, as described in the Applicants
British Pat. Specification No. 59220/68. Instead of such potassium
salts, it is possible to use sodium salts or organic amine salts,
for example triethanolamine salts.
The following specific examples of such compounds are provided: For
the compounds 1 to 6 inclusive, the starting acid is an unsaturated
polycarboxylic acid obtained by the pyrolysis of calcium citrate
according to the procedure described in the Applicants British Pat.
Specification No. 31014/67.
Compound No. 1 (termed ASP 1) is obtained by reacting the pyrolysis
product of calcium citrate with a sulphur-containing anhydride to
fix an SO.sub.3 H group across the double bond to obtain after
acidification a sulphonated polycarboxylic acid. A quarter of the
COOH groups of the said acid is esterified with a non-ionic
surface-active agent obtained by ethoxylating a C.sub.12 -C.sub.14
linear alcohol with 6 moles of ethylene oxide (E.O.). The remaining
three-fourths of the COOH groups and the SO.sub.3 H group are then
neutralized with potassium hydroxide (see British Pat.
Specification Nos. 59220/68 and 31014/67).
Compound No. 2 (ASP 2) is the same as ASP 1, except that the
non-ionic agent is a C.sub.12 -C.sub.14 alcohol ethoxylated with 3
moles of E.O.
Compound No. 3 (ASP 3) is the same as ASP 1, except that the
non-ionic agent is nonylphenol ethoxylated with 6 moles of E.O.
Compound No. 4 (ASP 4) is the same as ASP 1, except that the
non-ionic agent is a secondary C.sub.11 -C.sub.15 /ethoxylated with
7 moles of E.O.
Compound No. 5 (ASP 5) is similar to ASP 4, but it was neutralized
with sodium hydroxide.
Compound No. 6 (ASP 6) is similar to ASP 1, but the non-ionic agent
is a C.sub.16 -C.sub.18 alcohol ethoxylated with 9 moles of
E.O.
Compound No. 7 (ASP 7) is the sulphonated product of aconitique
acid, in other words sulphotricarballylic acid, a carboxyl group of
which is esterified with a non-ionic agent obtained by ethoxylating
nonylphenol with 8.5 moles of E.O. and then neutralizing two of the
remaining COOH groups and the SO.sub.3 H group with potassium
hydroxide (see British Pat. Specification No. 47677/67).
Compound No. 8 (ASP 8is the sulphonated product of maleic acid,
that is to say sulphosuccinic acid, a carboxyl group of which was
esterified with a non-ionic agent obtained by ethoxylating a
C.sub.12 -C.sub.14 linear alcohol with 6 moles of E.O. and
neutralizing the remaining carboxyl group and the SO.sub.3 H group
with potassium hydroxide (see British Pat. Specification
47677/67).
The sulphopolycarboxylic acids, represented by compounds 1 to 8
hereinbefore described, are able to be used in the liquid detergent
compositions according to the invention in a proportion of from 0
to 35 percent by weight based on the total composition, preferably
from 1 to 20 percent by weight.
d. Anionic surface-active agents for use in the liquid detergent
compositions according to the invention are particularly selected
from the group of soaps, sulphonates and organic synthetic
sulphates. The soaps are preferably C.sub.10 -C.sub.22 fatty acid
soaps, for example coconut fatty acids or tallow fatty acids. The
sulphonates and organic synthetic sulphates are preferably selected
from the following groups:
1. Sulphonates of olefines containing eight to 25 carbon atoms, for
example sodium or potassium dodecyl sulphonate,
2. Alkylbenzene sulphonates the alkyl groups of which contain from
10 to 16 carbon atoms and which may be straight-chain or branched,
for example potassium salts of decyl-, undecyl-, dodecyl-,
tridecyl- tetradecyl-, pentadecyl- or hexadecyl sulphonic
acids,
3. Secondary alkyl sulphates, of the type obtainable under the
Trade Mark "TEEPOL,"
4. primary aliphatic alcohol sulphates containing from eight to 18
carbon atoms, for example lauryl- or hexadecyl potassium
sulphates,
5. Alkyl- or alkylaryl-polyoxyethylene potassium sulphates of which
the alkyl group contains from eight to 18 carbon atoms, and the
alkylaryl group contains a C.sub.8 -C.sub.18 alkyl group and an
aryl group, preferably phenyl, and the polyoxyethylene group
preferably contains from 1 to 4 moles of E.P.
The anionic surface-active agent of the types hereinbefore
described is used in the liquid detergent compositions according to
the invention in proportions of from 0 to 20 percent by weight
based on the total composition, preferably from 1 to 15 percent by
weight.
e. The non-ionic surface-active agent which may be used in the
liquid detergent compositions of the present invention is
preferably selected from the following groups:
1. ethoxylated alkylphenols containing from six to 12 carbon atoms
in the alkyl chain and from 3 to 25 moles of E.O. per mole of alkyl
phenol,
2. Primary or secondary ethoxylated C.sub.8 -C.sub.22 alcohols
derived from natural or synthetic alcohols and containing from 1 to
50 moles of E.O. per molecule of alcohol,
3. Alkanolamides and ethoxylated alkylamides, for example the
diethanolamide of ethoxylated coconut fatty acids,
4. Copolymers derived from different alkylene oxides, known
commercially under the Trade Mark "PLURONIC," and polymers such as
polyethylene glycol and propylene glycol,
5. Esters of polyhydroxy compounds, for example sucrose stearate,
lauryl sucrose and the like,
6. Tertiary amine oxides and tertiary phosphine oxides, for example
dimethyldodecylamine oxide, N-dodecylmorpholine oxide,
dodecyldimethylphosphine oxide and the like.
The non-ionic surface-active agent hereinbefore described is
incorporated in compositions according to the invention in
proportions of from 0 to 15 percent by weight based on the total
composition, preferably from 1 to 10 percent by weight.
As will be shown in Example 2, the anionic surface-active agents
quoted as (d), as do the non-ionic surface-active agents quoted as
(e), provide a substantially lower resistance to salting out the
surface-active agents of the sulpho-polycarboxylic acid ester type
quoted under (c). This is because they are used in the minimum
quantities to provide the detergent properties required without
salting out in the aqueous liquid detergent compositions of the
invention. If it is desired to use considerably greater
proportions, in other words close to the upper limit of the
concentration hereinbefore specified, it is then necessary to
employ a solubilizing agent or a mixture of a solubilizing agent
with a sulphopolycarboxylic acid of the type quoted under (c).
f. The solubilizing agent is an organic compound which enhances the
water-solubility of a sparingly-soluble substance. Known examples
of such agents are xylene sulphonic acids, p-toluene sulphonic
acids, p-cumene sulphonic acids and the like, preferably used in
the form of their potassium salts. However, as is shown
particularly in Example 3, the solubilizing agent may be replaced
partially by a potassium salt of an ester of a sulpho-carboxylic
acid described under (c). Such partial replacement is advantageous
because the ester of the sulpho-polycarboxylic acid has excellent
detergent properties, such properties being absent from the
solubilizing agent therein which therefore constitutes an inactive
component in the aqueous liquid detergent compositions of the
invention.
The solubilizing agent is used in proportions of from 0 to 20
percent by weight of the total aqueous liquid detergent
composition, preferably in proportions of from 1 to 12 percent by
weight.
g. The organic sequestering agent used according to the invention
is an aminopolycarboxylic acid such as ethylene-diamine-tetracetic
acid (EDTA), nitrilo-triacetic acid (NTA),
diethylene-triamine-pentacetic acid acid (DTPA) or a
hydroxylpolycarboxylic acid, or the like, preferably used in the
form of the potassium salt. The sequestering agent may be in the
form of water-soluble complexes with heavy ions responsible for
water hardness (calcium, magnesium and the like). The compositions
of the invention may contain from 0 to 20 percent by weight based
on the total composition, preferably from 0.5 to 10 percent by
weight.
h. The per-compound subsequently incorporated in the compositions
of the invention is a water-soluble per-compound, for example
hydrogen peroxide, perborate, percarbonate or a persulphate,
preferably the potassium compound thereof. The quantity of
per-compound added is from 0 to 20 percent by weight based on the
total aqueous liquid detergent composition, preferably from 1 to 5
percent by weight.
i. Compositions according to the invention may contain adjuvants
conventionally used in liquid and/or solid detergent compositions.
Such adjuvants are for exaMple coloring agents, scents, thickening
agents such as carboxymethyl cellulose, polyvinylpyrollidone,
polyvinyl alcohol or the like, optical whiteners, anti-corrosion
agents, anti-staining agents or the like. The total proportion of
such adjuvants is from 0 to 5 percent by weight based on the total
liquid detergent composition, preferably from 1 to 4 percent by
weight.
j. The compositions of the invention contain water in at least the
proportion necessary to obtain a liquid detergent composition.
From the foregoing it is apparent that a wide variety of liquid
detergent compositions according to the invention may be obtained
containing many different constituents as hereinbefore described.
The common factor is that they must contain a proportion of TPP
more than 164 g/liter (i.e., 14 percent by weight), which to the
knowledge of the applicants has not previously been in liquid
detergent compositions, and that they must contain a potassium or
ammonium salt of an inorganic or organic acid in a proportion
sufficient to ensure the solubility in water of the TPP. The other
constituents of the compositions of the invention are optional and
are selected in a proportion according to the end use of the
compositions.
To prepare the compositions according to the invention, a method
may be used as hereinafter described which is given by way of
example only and which is not intended to be limiting:
About 50 to 60 percent of the final water is introduced into a
vessel, and there is added thereto with agitation the
surface-active agents of type (c), (d) and/or (e), coloring agent,
scent, thickening agent, anti-corrosion agent and anti-staining
agent. The solubilizing agent and then the optical whitener is
added, and agitation is continued until a homogeneous solution is
obtained. Subsequently, while agitation is continued, the potassium
salts and then water up to about 85 percent of the final quantity
is added, and the TPP is then added with vigorous agitation, and
when it is dissolved the solution is filtered. The per-compound is
then added, and to adjust the pH to between about 7 and 9, either
sulphuric acid or potassium hydroxide is added, and the water made
up to the full quantity.
Amongst the particular uses to which the liquid compositions of the
invention may be put, there may be mentioned water-softening, the
cleansing of articles having a non-porous surface, for example
glass, porcelain, enamel, wood, metal, layers coated with plastics
materials for example in vehicle building, and the like, and
similarly the washing of textile materials of all kinds, i.e.
natural or synthetic textiles, whether for light duty washing or
heavy duty washing.
The following non-limiting Examples are provided to illustrate
liquid detergent compositions according to the invention.
EXAMPLE 1
Effect of Potassium Salts on the solubility in water of TPP
Solutions were prepared containing increasing quantities of
solubilizing salt (potassium or ammonium salt). To 100 mls. of each
of the solutions were added, with vigorous agitation, sodium
tripolyphosphate in a quantity such that a proportion thereof
remained undissolved. The suspension thus obtained was agitated
during a period of 1 hour with a magnetic agitator, and then left
overnight at room temperature.
The suspension was then filtered and the proportion of sodium
tripolyphosphate in solution determined using the following
analytical techniques:
a. determination of sodium in solution by flame photometry,
b. colorimetric determination of the phosphate ion in the form of
ammonium molybdate and ammonium monovanadate, using a
spectrophotometer.
Other substances were measured by classical chemical analytical
procedures.
The sodium tripolyphosphate was used in the form of the
hexahydrate, because the anhydrous form produces a supersaturated
solution which subsequently crystallizes out. In all the following
Examples, the contents are expressed in grams per liter. The TPP is
expressed as g/liters as the anhydride equivalent.
Effect of NaCl and KCl NaCl Na.sub.5 P.sub.3 O.sub.10 KCl Na.sub.5
P.sub.3 O.sub.10 0 163 0 163 50 86 35 194 101 46 74 202 201 34 195
185 ##SPC1##
effect of KBO.sub.2 and KBO.sub.2.sup.. H.sub.2 O.sub.2 KBO.sub.2
Na.sub.5 P.sub.3 O.sub.10 KBO.sub.2.sup.. H.sub.2 O.sub.2 Na.sub.5
P.sub.3 O.sub.10 0 164 0 164 15 198 22 230 39 223 52 285 76 259 100
336 191 291
effect of sodium citrate.sup.. 2H.sub.2 O and pot assium
citrate.sup.. H.sub.2 O Na.sub.3 citrate Na.sub.5 P.sub.3 O.sub.10
K.sub.3 citrate Na.sub.5 P.sub.3 O.sub.10 0 164 0 164 65 130 17 185
114 102 45 220 262 54 87 240 543 22 218 264
effect of potassium aconitate and potas sium maleate K.sub.3
aconitate Na.sub.5 P.sub.3 O.sub.10 K.sub.2 maleate Na.sub.5
P.sub.3 O.sub.10 0 164 0 164 40 207 39 193 83 224 79 215 207 245
201 221 412 231
effect of K salts of E.D.T.A..sup.(.sup.+) and
N.T.A..sup.(.sup.+.sup.+) K.sub.4 E.D.T.A. Na.sub.5 P.sub.3
O.sub.10 K.sub.3 N.T.A. Na.sub.5 P.sub.3 O.sub.10 0 164 0 164 25
176 25 174 70 182 70 185 140 188 140 187 270 179 (+) E.D.T.A. :
ethylene-diamine-tetracetic acid. (++) N.T.A. : nitrolo-triacetic
acid.
The preceding tables show that invariably sodium salts lower the
solubility of the sodium tripolyphosphate and that potassium and
ammonium salts increase the solubility thereof. It is equally to be
seen that certain salts used according to the invention are
substantially better than potassium tripolyphosphate in their
solubilizing effect on TPP.
EXAMPLE 2
Resistance to salting out of surface-active agents by
electrolytes
The method of determining the resistance to salting out is as
follows:
For each surface-active material used, three aqueous solutions were
prepared containing respectively 1 percent, 5 percent and 10
percent by weight of active material. A solution was prepared
containing 900 g/liter of potassium citrate monohydrate and used
for titrating the three solutions of active material. The quantity
of citrate was noted which was required to be added to each of
these solutions to produce phase separation. On a graph of the
three quantities of citrate corresponding to three concentrations
of surface-active material; there is obtained a straight line which
on extrapolation determines the notional concentration of citrate
corresponding to 0 percent of surface-active material, in order to
be able to compare their resistance to salting out of the several
active materials by electrolytes.
Surface-active material Resistance to salting out: concentration in
g/l of potassium citrate anhydride extrapolated to 0% of active
material
__________________________________________________________________________
ASP 1 555 ASP 2 potassium salts 620 ASP 3 of esters of sulpho- 330
ASP 4 polycarboxylic acids 482 ASP 5 (ASP 5 = sodium salt) 425 ASP
7 292 ASP 8 316 Potassium-linear alkyl-benzene- sulphonate very
slightly soluble lauryl-ether-sulphate with 3.5 moles of E.O. 180
C.sub.12 -C.sub.14 alcohol ethoxylated with 6 moles of E.O. 70
nonyl phenol ethoxylated with 8.5 moles of E.O. 25 C.sub.11
-C.sub.15 secondary alcohol with 7 moles of E.O. 50
the table shows that the salts of esters of sulphopolycarboxylic
acids of group (c), preferably used as surface-active agents, have
a resistance to salting out by electrolytes clearly superior to
anionic and non-ionic surface-active agents of groups (d) and
(e).
These results are confirmed by the following data of the
determination of the maximum quantity (in g/liter) of the
surface-active agents that it is possible to introduce in an
aqueous detergent solution containing 200 g/liter of TPP, 20
g/liter of potassium pyrophosphate and 20 g/liter of potassium
sulphate, without phase-separation (see the Tables hereinafter set
forth):
ASP 2 potassium salts of esters of 220 g/l ASP 3
sulphopolycarboxylic acids 200 g/l ASP 5 (ASP 5 = sodium salt) 220
g/l potassium linear alkyl(C.sub. 10 -C.sub.13)-benzene- sulphonate
<30 g/l potassium lauryl-ether-sulphate with 3.5 moles of E.O.
<80 g/l potassium alkyl(C.sub. 12 -C.sub.14)-sulphate <20 g/l
C.sub.12 -C.sub.14 alcohol ethoxylated with 6 moles of E.O <20
g/l nonylphenol ethoxylated with 8.5 moles of E.O. <20 g/l
EXAMPLE 3
The solubilization of salts of esters of sulphopolycarboxylic
acids
It is to be seen from Example 2 that current anionic and non-ionic
surface-active agents have a tendency to be salted out by
electrolytes at relatively low concentrations of surface-active
agents. To militate against this tendency there may be added to the
detergent compositions a solubilizing agent (hydrotropic
agent).
In the present Example there is used a liquid detergent composition
which contains a potassium salt of an ester of a
sulphopolycarboxylic acid (ASP 1), the commercially-available
non-ionic surface-active agent TERGITOL 15S3 which is the
condensation product of a C.sub.11 -C.sub.15 secondary alcohol with
3 moles of E.O., TPP, potassium pyrophosphate and potassium
xylene-sulphate (P.X.S.), the latter being the solubilizing
agent.
It is to be seen from Table I that for preventing the detergent
composition from separating out into two phases, it is necessary to
increase the concentration of P.X.S. as the concentration of
TERGITOL 15S3 is increased.
It is to be seen from Table II that the content of P.X.S. may be
diminished as the content of ASP 1 is increased, thus demonstrating
the solubilizing effect of this compound.
In the said two Tables, the numerical values are expressed as
g/liter.
TABLE I
Test No. ASP 1 Tergitol TPP K.pyro- P.X.S. 15S3 phosphate 1 80 0
180 20 0 2 80 10 180 20 5 3 80 20 180 20 20 4 80 30 180 20 50 5 80
40 180 20 60
TABLE II
Test No. ASP 1 Tergitol TPP K.pyro- P.X.S. 15S3 phosphate 1 0 40
180 20 108 2 20 40 180 20 82 3 40 40 180 20 72 4 60 40 180 20 70 5
80 40 180 20 60
EXAMPLE 4
Inhibiting effect of the hydrolysis of TPP by potassium
pyrophosphate
Aqueous solutions of sodium tripolyphosphate hydrolyze rapidly to
an equilibrium comprising about 2 percent of orthophosphate and
about 15 percent of pyrophosphate based on the total phosphate
concentration (cf. CHABEREK and MARTELL, "Organic Sequestering
Agents," New York, John Wiley Inc., page 304).
To show the inhibiting effect of pyrophosphate on the hydrolysis of
TPP, the following detergent composition was prepared:
100 g/liter ASP 4
10 g/liter of TERGITOL 15S3 (secondary C.sub.15 alcohol ethoxylated
with 7 moles of E.O.)
4 g/liter of potassium diethylene-triamine-pentacetate (Trade Mark
VERSENEX 80)
200 g/liter of TPP containing 2.5 percent of sodium pyrophosphate
and 1 percent of sodium orthophosphate
20 g/liter of potassium pyrophosphate
50 g/liter of potassium xylene-sulphonate
20 g/liter of potassium sulphate (pH = 8.62)
The said composition was kept at 25.degree.C and the content of
tripolyphosphate, pryophosphate and orthophosphate determined (as
percent by weight) at different intervals of time. The results are
shown in the following Table:
Time Ortho- Pyro- Tripoly- phosphate phosphate phosphate after 0
day 0.9 11.4 87.7 after 11 daYs 1.0 11.3 87.7 after 20 daYs 0.9
11.4 87.7 after 27 days 1.0 11.8 87.2 after 57 days 1.2 12.7
86.1
It is to be observed that the content of TPP changed from 87.7
percent to 86.1 percent in a period of 57 days, and that the
hydrolysis was practically halted by the presence of potassium
pyrophosphate.
EXAMPLE 5
Liquid detergent compositions containing surface-active agents of
group (d) and (e)
All the detergent compositions contained:
200 g/liter of TPP
20 g/liter of potassium pyrophosphate
20 g/liter of potassium sulphate
150 g/liter of potassium xylene-sulphonate.
Into such compositions surface-active agents of group (d) and (e)
were incorporated in the proportions indicated in the following
Table.
d. Potassium C.sub.10 -C.sub.13 alkyl-benzene sulphonate 200
g/liter Lauryl-ether-sulphate with from 3.5 moles of E.O. 200
g/liter e. C.sub.12 -C.sub.14 alcohol ethoxylated with 3 moles of
E.O. 100 g/liter Nonylphenol ethoxylated with 6 moles of E.O. 100
g/liter
EXAMPLE 6
Liquid detergent compositions containing surface-active agents of
group (c) together with surface-active agents of group (d) or
(e)
In the following Table, the concentrations of the various
constituents are expressed in g/liter. ##SPC2##
EXAMPLE 7
Liquid detergent compositions for heavy duty at high
temperature
The efficiency of the heavy duty compositions was tested in a
Launder-O-Meter at a temperature of 85.degree.C, for 20 minutes, at
a concentration of 5 mls/liter in water of hardness 17.degree.C
(French units). Standard artificially soiled swatches were supplied
by TEST FABRICS Inc. STANDARD (referred to as TF) and by US TESTING
CY STANDARD (referred to as U.S.T). In the said test the percentage
of soil removed from the swatches was measured.
In the following Table, Tests 1 to 3 were effected with
compositions according to the invention, all of which
contained:
100 g/l of ASP 2
6 g/l of tetrasodium EDTA
2 g/l of polyvinylpyrollidone
100 g/l of potassium xylene-sulphonate
20 g/l of K.sub.4 P.sub.2 O.sub.7, and
200 g/l of TPP.
In addition, the composition for test No. 1 contained 20 g/l of
nonylphenol ethoxylated with 6 E.O., 50 g/l of boric acid and 12.5
g/l of KOH; the composition for test No. 2 contained 20 g/l of
nonylphenol ethoxylated with 6 E.O. and 50 g/l of potassiumcitrate;
the composition for test No. 3 contained 20 g/l of C.sub.16
-C.sub.20 alcohol ethoxylated with 6 E.O. and 50 g. of
KHCO.sub.3.
Tests No. 4 and No. 5 were carried out with commercial "heavy duty"
powders, namely "ALL" (No. 4) and "PRODIXAN" (No. 5), respectively,
used in a proportion of 5 g/liter.
Test No. TF U.S.T. 1 64.7 18.1 2 64.5 18.7 3 65.1 18.0 4 54.9 15.6
5 56.0 16.9
it is to be noted that tests No. 1 to 3 were superior to tests No.
4 and 5.
EXAMPLE 8
Demonstration of the greater concentration of TPP in liquid
detergent compositions
The test carried out in this Example is the same as that of Example
7, using similar swatches TF and U.S.T. and in the comparison of
the use of washing powders "ALL" and "PRODIXAN." The water used had
a hardness of 40.degree. in French units.
Tests No. 1 to 5 were carried out with liquid compositions
according to the invention containing increasing proportions of
TPP, namely: 0, 50, 100, 150 and 200 (g/liter), the compositions
containing also the following:
100 g/l of ASP 2
20 g/l of nonylphenol ethoxylated with 6 E.O.
20 g/l of polyvinylpyrollidone
6 g/l of tetrasodium EDTA
100 g/l of potassium xylene-sulphonate
20 g/l of K.sub.4 P.sub.2 O.sub.7 and
20 g/l of K.sub.2 SO.sub.4.
Tests No.6 and 7 were carried out with "ALL" and "PRODIXAN":
test No. TF U.S.T. 1 23.2 3.7 2 32.2 5.5 3 53.9 7.4 4 64.6 11.5 5
67.6 16.0 6 52.7 14.6 7 56.2 15.7
the Table clearly shows the effectiveness of the compositions with
increasing TPP content.
EXAMPLE 9
Liquid detergent compositions for heavy duty at low temperature
The compositions are expressed in g./liter:
Composi- Composi- tion I tion II ASP 3 50 50 nonylphenol
ethoxylated with 6 moles of E.O. 40 -- C.sub.11 -C.sub.15 secondary
alcohol ethoxylated with 3 moles E.O. -- 25 C.sub.11 -C.sub.15
secondary alcohol ethoxylated with 7 moles E.O. -- 25 pentasodium
DTPA 4 4 polyvinyl pyrollidone 1 1 potassium xylene-sulphonate 100
100 K.sub.4 P.sub.2 O.sub.7 20 20 K.sub.2 SO.sub.4 20 20 TPP 180
180
example 10
liquid detergent compositions for light duty
The tests were carried out in a Tergometer for 10 minutes at a
temperature of 40.degree.C, using 5 mls. of detergent composition
per liter of water having a hardness of 17.degree. French
units.
Artificially soiled swatches were used marketed by the firm
TESTFABRICS Inc., U.S.A. These consisted of nylon (N), a 65/35
polyester/cotton (P) and wool (L).
Four compositions according to the invention were used, each
containing:
60 g/l of ASP 2
6 g/l of tetrasodium EDTA
90 g/l of potassium xylene-sulphonate
1 g/l of polyvinyl pyrollidone
20 g/l of K.sub.2 SO.sub.4
20 g/l of K.sub.4 P.sub.2 O.sub.4
200 g/l of TPP
but being different from each other by the presence of the
following compounds:
Composition for Test No. 1
20 g/liter of C.sub.15 secondary alcohol ethoxylated with 3 moles
of E.O.
20 g/liter of C.sub.15 secondary alcohol ethoxylated with 7 moles
of E.O.
20 g/liter of the diethanolamide of ethoxylated coco fatty
acids
Composition for Text No. 2
40 g/liter of nonylphenol ethoxylated with 6 moles of E.O.
20 g/liter of the monoethanolamide of coco fatty acids.
Composition for Test No. 3
40 g/liter of nonylphenol ethoxylated with 6 moles of E.O.
Composition for Test No. 4
40 g/liter of nonylphenol ethoxylated with 6 moles of E.O.
10 g/liter of the diethanolamide of lauric acid
10 g/liter of lauryl-ether-sulphate with 2.5 moles of E.O.
Test No.5 and No.6 were carried out with the commercial light duty
liquids "OSA" (No. 5) and "SOLILAINE" (No.6) respectively, both
used in the tests at a concentration of 5 ml/liter.
The results obtained are shown in the following Table:
Test No. N P L 1 80.3 36.2 90.1 2 80.1 41.1 92.9 3 75.5 41.8 92.3 4
81.7 40.0 76.4 5 71.1 23.5 25.2 6 64.6 30.9 65.9
the superiority and polyvalence of the compositions according to
the invention (Test Nos. 1 to 4) are shown despite the fact that
the commercial compositions (Test No. 5 and 6) contained greater
portions of surface-active material (more than 25 percent). The
compositions according to the invention are as well suited for hand
washing as for machine washing.
* * * * *