Note: Descriptions are shown in the official language in which they were submitted.
~79~
LI~UID DETERGENT COMPOSITIONS
This inven-tion relates to liquid detergent compositions.
In particular, it relates to aqueous detergent compositions
suitable for use as general purpose household cleaning
compositions.
Gene~al purpose household cleaning compositions for
hard surfaces such as metal, glass, ceramic, plastic and
linoleum surfaces~ are commercially available in both
powdered and liquid form. Powdered cleaning compositions
consist mainly of builder or buf~ering salts such as phosph~tes,
carbonates, silicates etc., and although such composi-tions
may display good inorganic soil removal, they are generally
deficient in cleaning ability on organic soils such as the
grease/fatty/oily soils typically found in the domestic
environment.
Li~uid cleaning compositions, on the other hand, have
the great advantage that they can be applied to hard
surfaces in neat or concentrated form so tha-t a relatively
high level o~ ~uractant material is delivered directl~ -to
the soil~ Moreover, it ls a xather m~re straightEorward
kask to incorporake hi~h concentrations oE anionic or
~onionic sur~ac~ant in a lic~uicl rather than a granular
composltion. For both these reasons, thereEore, liquid
cleaniny compos.i-tion~ have the potenk.ial to provide superior
grease ancl oil~ soil removal ovcr powdered cleaning composi-
tions, ~
.
7~5~
Nevertheless, liquid cleaning compositions still
suffer a number of drawbacks which can limit their consumer
acceptability. Thus, they generally contain little or no
detergency builder salts and consequently they tend to have
poor cleaning performance on particulate soil and also lack
robustness under varying water hardness levels. In addition,
they can suffer problems of product for~, in particular,
inhomogeneity, lack of clarity, or inadequate viscosity
characteristics for consumer use D Moreover, the higher in-
product and in-use surfactant concentration necessary for
improved grease handling raises problems of extensive suds
formation requiring frequent rinsing and wiping on behal~ of
the consumer. Although oversudsing may be controlled to some
extent by incorporating a suds-regulating material such as
hydrophobic silica and/or silicone or soap, this in itself
can raise problems of poor product stability and homogeneity
and also problems associated with deposition of insoluble
particulate or soap residues on the items or surfaces being
cleaned, leading to filming, streaking and spotting.
It has now been discovered, however, that these defects
of prior art liquid cleaning composition can be minimized
or overcome through the incorporation therein of a specified
level of mono- or sesquiterpene material in combination with
a polar solvent of specified water-solubility characteristics.
Although the terpenes, as a class, have limited water-
solubility, it has now been found that they can be incorpor-
ated into liquid cleaning compositions in homogeneous form,
even under cold processing conditions, with the ability
to provide excellent cleaning characteristics across the
ran~e o~ water hardness on grease/oil~ soild and inorganic
par-tlcula-te soils, as well as on shoe polish, marker ink,
bath tub soil etc, and excellent shine per~ormance with low
soil redeposltion and little or no propensity to cause ~llm-
ing, ~treAking or spottin~ on sur~aces washed therewith.
Moreover, the terpenes herein specified, and in particular
those o~ the h~drocarbon class, are valuable in regulating
the sudsing behaviour of the instant compositions in
both hard and soft water and under both diluted and neat
-- 2 --
'
,
~ ~'7~-~S~
or concentrated usage, while terpenes of the terpene alcohol
class are also valuable for providing effective control of
product viscosity characteristics.
Terpenes are, of course, well~known components of
perfume compositions and are often incorporated into deter-
gent compositions at low levels via the perfume. Certain
terpenes have also been included in detergent compositions
at higher levels; for instance, German Patent Specification
~o. 2,113,732 discloses the use of aliphatic and alicyclic
terpenes as anti-microbial agents in washing compositions,
while British Patent 1,308,190 teaches the use of dipentene
in a thixotropic liquid detergent suspension base composition.
German Patent Specification No. 2,709,690 teaches the use of
pine oil (a mixture mainly of terpene alcohols) in liquid
hard surface cleaning co~positions. There has apparently
been no disclosure, however, of the combined use of a terpene
cleaning agent with a polar solvent of low-water solubility.
The present invention thus provides liquid detergent
compositions which are stable homogeneous fluent liquids
haviny excellent suds control across the range of usage and
water hardness conditions and which provide excellent shine
performance together with improved cleaning characteristics
both on greasy/oily soils and on inorganic particulate soils
with little tendency to cause filming or streaking on washed
surfaces.
According to the present invention there is provided
an aqueous liquid detergent composition characteri~ed by:
~a) from about }~ to about 20~ of a synthetic
anionlc, nonionic, amphoteric or zwitterionic
sur~actarlt or mixture thereoE,
~b) ~rom about 0.5~ to about 10~ of a mono- or
sesquiterpene or mixture thereof, the weight
ratio of surfactant:terpene lying in the range
5:1 to 1:3, and
-
~t~ ~ 5 ~
(c) from about 0.5 to about 10~ of a polar solvent
having a solubility in water at 25C in the
range ~rom about 0.2% to abo~t 10~.
Preferred terpenes are mono- and bicyclic monoterpenes,
especially those of the hydrocarbon class, which can be
selected from terpinenes, terpinolenes, limonenes and pinenes.
Highly preferred materials of this type include d - limonene
dipentene,~ -pinene, ~-pinene and the mixture of terpene
hydrocarbons obtained from the essence of oranges (eg. cold-
pressed orange terpenes and orange terpene oil phase ex ~ruit-
juice).
Terpene alcohols, aldehydes and ketones can also be used,
however, the alcohols/ in particular/ providing valuable but
unexpected improvements in viscosity regulation when incorpor-
ated in the compositions of the invention at a level/
preferably/ of from about 1~ to about 3%, more preferably
from about 1.5% to about 2.5%. The terpene is used in
combination with a polar solvent (i.e. containing at least
one hydrophilic group) having a solubility in water of from
about 0.2% to about 10% by weight (g/100 g solution),
preferably from about 0.5% to about 6~ by weight, for example
benzyl alcohol. The compositions of the invention also
pre~erably contain from about 0.005% to about 2%, more
preferably from about 0.05% to about 0.7% of an alkali metal,
ammonium or alkanolammonium soap of a C13-C24, especially
C13-C18, fatty acid. Preferably, the fatty acid is fully
saturated, for example, by hydrogenation of naturally
occurring fatty acids. Additon o~ the soap, particularly
to compositions containing terpene hydrocarbons, is found to
provide slgnificant synergistic enhancement in the suds~
suppression effectiveness o~ the system.
~ calcium sequestrant is also desirable in the present
compositions, providing not only cleaning advantages on
partiaulate soil, but also, surprisingly, advantages in terms
of product homogeneity and stability. The sequestrant
component is a water-soluble inorganic or organic polyanionic
sequestrant having a calcium ion stability constant at 25C
of at least about 2.0 preferably at least about 3.0, the
- 4 -
.
:: :
.
5~L
weight ratio of surfactant:sequestrant preferably lying
in the range from about 5:1 to about 1:3, especially about
3:1 to about 1:1. In preferred embodiments the sequestrant
has an anion valence of at least 3 and is incorporated a~ a
level of from about 0.5% to about 13~ by weight. The compo-
sition itself preferably has a pH in 1% aqueous solution of
at least about 8Ø
Suitably, the sequestrant can be selected from the
water-soluble salts of polyphosphates, polycarboxylates,
aminopolycarboxylates, polyphosphonates and amino polyphos-
phonates and added at a level in the range from 1 to 9%,
especially 2 to 8%, more especially 3 to 7~ by weight of
the composition. Adjustment of the sequestrant level and
surfactant:sequestrant ratio within the above specified
ranges is important for providing compositions of optimum
stability.
A notable feature of the instant composi~ions is the
suds-suppression effectiveness of the terpenes in liquid
compositions based on ampholytic or zwitterionic surfactants.
Thus, it is notoriously difficult to control the sudsing
behaviour of these surfactants in a cost-effective manner
using conventional suppression agents such as soaps, waxes
etc. The terpenes are thus particularly valuable in this
respect.
We will now discuss the individual components of the
present compositions in more detail.
A wide range of anionic, nonionic, switterionic and
amphoteric surfactants can be used in the present compositions.
~ typical listing of the classes and species of these sur-
~actants ls glven ln U.S. Patent 3,663,961 issued to Norris
on May 23, 1972. These sur~actants can be used singly or in
aombination at levels in the range from about 1% to about 20~r
pre~erably at levels ~rom about 3~ to about 10% b~ weight of
the compositions.
Suitable anionic non soap sur~actants are water-soluble
salts of alkyl benzene sulfonates, alkyl sulfates, alkyl
polyethoxy ether sulfates, parafin sulfonates, alpha-olefin
,
.
L~ ~ S 'l
sulfonates, alpha-sulfocarboxylates and their esters, alkyl
glyceryl ether sulfonates, fatty acid monoglyceride sulfates
and sulfonates, alkyl phenol polyethoxy ether sulfates, 2~
acyloxy-alkane-l-sulfonate, and beta-alkyloxy alkane sul-
i-onate. Of all the above, the paraffin sulfonates are highly
preferred.
A particularly suitable class of anionic detergents
includes water-soluble salts, particularly the alkali metal,
ammonium and alkanolammonium salts of organic sulfuric
reaction products having in their molecular structure an
alkyl or alkaryl group containing from about 8 to about 22,
especially from about 10 to about 20 carbon atoms, and a
sulfonic acid or sulfuric acid ester group. (Included in the
term alkyl~> is the alkyl portion of acyl groups). Examples
of this group of synthetic detergents which form part of the
detergent compositions of the present invention are the sodium
and potassium alkyl sul~ates, especially those obtained by
sulfating the highest alcohols ~C8-C18) carbon atoms produced
by reducing the glycerides of tallow or coconut oil and
sodium and potassium alkyl benzene sulfonates, in which the
alkyl group contains from about 9 to about 15, especially
about 11 to about 13, carbon atoms, in straight chain or
branched chain configuration, e.g. those of the type described
in USP 2,220,099 and 2,477,383 and those prepared from
alkylbenzenes obtained by alkylation with straight chain
chloroparaffins (using aluminium trichloride catalysis) or
straight chain olefins (using hydrogen fluoride catalysis).
Especially valuable are linear straight chain alkyl benzene
9ulfonates in which the average of the alkyl group is about
11.8 carbon atoms, abbr~viated as Cl1 8LAS.
~th~r anionic detergent compounds herein include the
sodium C10-Cl8 alkyl glyceryl ether sulEonates, especially
those others of higher alcohols dexived from tallow and
coconut oil sodium coconut oil ~atty acid monoglyceride
sulfonates and sulfates; and sodium or ptoassium salts of
X
5~
alkyl phenol ethylene oxide ether sulfate containing about 1
to about 10 units of ethylene oxide per molecule and wherein
the alkyl groups contain about 8 to about 12 carbon atoms.
Other useful anionic detergent compounds herein include
the water-soluble salts or esters of ~-sulfonated fatty acids
containiny from about 6 to 20 carbon atoms in the fatty acid
group and from about 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids
containing from about 2 to 9 carbon atoms in the acyl group
and from about g to about 23 carbon atoms in the alkane moiety;
alkyl ether sulfates containing from about 10 to 18, especially
about 12 to 16, carbon atoms in the alkyl group and from about
1 to 12, especially 1 to 6, more especially 1 to 4 moles of
ethylene oxide; water-soluble salts of olefin sulfonates
containing from about 12 to 24, preferably about 14 ~o 16,
carbon atoms, especially those made by reaction with sulfur
trioxide followed by neutralization under conditions such that
any sultones present are hydrolysed to the corresponding
hydroxy alkane sulfonates; water-soluble salts of paraffin
sulfonates containing from about 8 to 24, especially 14 to 18
carbon atoms, and ~-alkyloxy alkane sulfonates containing from
about 1 to 3 carbon atoms in the alkyl group and from about
8 to 20 carbon atoms in the alkane moiety.
The alkane chains of the foregoing non-soap anionic
surfactants can be derived from natural sources such as
coconut oil or tallow, or can be made synthetically as for
example using the Ziegler or Oxo processes. Water solubility
can be achieved by using alkali metal, ammonium or alkanol-
ammonium cations; sodium is pre~erred. Magnesium and calcium
are preferred cations under circumstances described by
~el~ian patent 843,636 invented by Jones et al, issued
December 30, 1976. Mixtures of anionic surfactants a.re
contemp.1ated by this invention; a pre~erred mixture contains
alkyl benzene sulfonate having 11 to 13 carbon atoms in the
~.t7~SS~
alkyl group or paraffin sulfonate having 14 to 18 carbon
atoms and either an alkyl sulfate having 8 to 18, preferably
12 to 18, carbon atoms in the alkyl group, or an alkyl
polyethoxy alcohol sulfate having 10 to 16 carbon atoms in
the alkyl group and an average degree of ethoxylation of 1
to 6.
Suitable nonionic surfactants include alkoxylated
nonionic surfactants and also those of a semi-polar character.
Alkoxylated nonionic surfactant materials can be broadly defined
as compounds produced by the condensation of alkylene oxide
groups (hydrophilic in nature) with an organic hydrophobic
compound, which may be aliphatic or alkyl aromatic in nature.
The length of the polyoxyalkylene group which is condensed
with any particular hydrophobic group can be readily adjusted
to yield a water-soluble compound having the desired degree of
balance between hydrophilic and hydrophobic elements.
Examples of suitable nonionic surfactants include:
1. The polyethylene oxide condensates of alkyl phenol,
e.g. the condensation products of alkyl phenols having an
alkyl group containing from 6 to 12 carbon atoms in either a
straight chain or branched chain configuration, with ethylene
oxide, the said ethylene oxide being present in amounts
equal to 5 to 25 ~oles of ethylene oxide per mole of alkyl
2S phenol. The alkyl substituent in such compounds may be
derived~ for example, rom polymerised propylene, disobutylene,
octene and nonene. Other examples include dodecylphenol
condensed with 12 moles of ethylene oxide per mole of phenol;
dinonylphenol condensed with 15 moles o~ ethylene oxide per
mol~ o phenol; nonylphenol and di-isoisooctylphenol condensed
wlth 15 moles of ethylene oxide.
2. The condensation product o primary or secondary
aliphatic alcohols having rom 8 to 24 carbon atoms, in
either stral~ht chain or branched chain confi~uration, with
from 1 to about 30 moles o~ alkylene oxide per mole of
-- 8 --
~ .
.
~.
5S~
alcohol. Preferably, the aliphatic alcohol comprises between
9 and 15 carbon atoms and is ethoxylated with between 2 and
12, desirably between 3 and 9 moles of ethylene oxide per
mole of aliphatic alcohol. Such nonionic surfactants are
preferred from the point of view of providing good to
excellent detergency performance on fatty and greasy soils,
and in the presence of hardness sensitive anionic surfactants
such as alkyl benzene sulfonates. The preferred surfactants
are prepared from primary alcohols which are either linear
(such as those derived from natural fats or, prepared by the
Ziegler process from ethylene, e.g. myristyl, cetyl, stearyl
alcohols), or partly branched such as the Dobanols and
<~Neodols which have about 25% 2~methyl branching(<~Dobanol
and aNeodol>> being Trade Marks of Shell) or Synperonics,
which are understood to have about 50% 2-methyl branching
(Synperonic is a Trade Mark of I.C.I.~ or the primary
alcohols having more than 50% branched chain structure sold
under the Trade Mark ~Lial by Liquichimica. Specific examples
of nonionic surfactants falling within the scope of the inven-
tion include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9,
Dobanol 91-3, aDobanol 91-6, Dobanol 91-8, Synperonic 6,
Synperonic 14, the condensation products of coconut alcohol
with an average of between 5 and 12 moles of ethylene oxide
per mole of alcohol, the coconut alkyl portion having from
10 to 14 carbon atoms, and the condensation products of
tallow alcohol with an average of between 7 and 12 moles of
ethylene oxide per mole of alcohol, the tallow portion compris-
ing essentially between 16 and 22 carbon atoms. Secondary
linear alkyl ethoxylates are also suitable in the present
compositions, especially those ethoxylates of the <~Tergitol*
series having from about 9 to 15 carbon atoms in the alkyl
group and up to about 11, especially from about 3 to 9,
etlloxy xesidues per molecule.
*Trademar]c
g
~7
.~
~ ~t7~55~
- 10 -
3. The compounds formed by condensing ethylene oxide with
a hydrophobic base formed by the condensation of pxopylene
oxide with either propylene glycol or ethylene ciia~ine.
Such synthetic nonionic detergents are available on the
i market under the Trade Marks o "Pluronic" and "Tetronic"
respectively supplied by Wyandotte Chemicals Corporation. .
Of the above, highly preferred are alkoxylated nonionic
surfactants having an average HLB in the range from about
9.5 to 13.5, especially 10 to 12.5. Highly suitable nonionic
0 surfactants of this type are ethoxylated primary or secondary
Cg 15 alcohols having an average degree of ethoxylation from
about 3 to 9, more preferably from about 5 to 8.
Suitable semi-polar surfactants are water-soluble amine
oxides containing one alkyI moiety of from about 10 to 28
carbon atoms and 2 moieties selec~ed from the group consisting
o alkyl groups and hydroxyalkyl groups containing from 1 to
about 3 carbon atoms, an~ especially alkyl dimethyl amine
oxides wherein the alkyl group contains from about 11 ~o 16
carbon atoms; water-soluble phosphine oxide detergents
~o containing one alkyl moiety o about 10 to 28 carbon atoms
and 2 moieties selected from the group consisting of alkyl
groups and hydroxyalkyl groups containing from about 1 to 3
carbon atoms; and water-soluble sulfoxide detergents con-
taining one alkyl moiety of from about 10 to 28 carbon atoms
an a moiety selected from the group consisting o~ alkyl and
hydroxyalkyl moieties oE from 1 to 3 carbon atoms.
Suitable amp}lol~tic surfactants are water-soluble
d~rivatives o~ allphatic secondary and tertiary amines in
Which the aliphatic moiety can be straight chain or branched
o and whereln one o~ the aliphatic substituents con~ains ~rom
about 8 to 18 carbon atoms and one contains an Ani~nic
water-solubilizing cJroup/ e.g. carboxy, sulfonate, sulate,
phosphate, or phosphonate.
.
.. . .
"
551
Suitable zwitterionic surfactants are water soluble
d~rivatives of aliphatic quaternary ammonium,phosphonium and
sulfonium cationic compounds in which the aliphatic moieties
can be straight chain or branched, and wherein one of the
aliphatic substituents contains from about 8 to 18 carbon
atoms and one contains an anionic water-solubilizing group.
Preferred ampho~eric and zwitterionic surfactants have
the general formula:-
1 T ~ X A
wherein X is C02 or S03 , Rl is alkyl or alkenyl grouphaving 8 to 22 carbon atoms, possibly interrupted by amide,
ester or ether linkages, R2 is a methylene, ethylene,
propylene, isopropylene or isobutylene radical, R3 and R4 .
are independently selected from hydrogen, Cl 3 alkyl or -R2-
X, whereby one of the substituents R3 and R4 is hydrogen if
the other one is represented by the group -R2X, ~.is an
integer from 1 to 6, and A is ~n equivalent amount of a
neutralizing anion, except that amphoteric surfactants
include amine salts of the above formula and also the corre-
sponding free amines.
Highly preferr~d surfactants according to the aboveformula, include N-alkyl-2-aminopropionic acid, N-alkyl-2 -
imino-diacetic acid, N-alkyl-2-iminodipropionic acid, N-
alkyl~ mino-~-methyl-propionic acid, N-alkyl-propylenediamine-
propionic acid, N-alkyl-dipropylenetriamine-propionic acid,
N~alkyl-dlpropylenetriamino dipropionic aci.d, N-alkylglycine,
N-alkyl-amino-succinic acid, N-amidoalkyl- N'-carboxymethyl-
N',N'-dimethyl-ammonio -e~hylene diamlne, N-alkyl-c~mino-
othane-sulonic acid, N-a~kyl-N,N-dimethyl-ammonio-hydroxy-
propene-sulonic acid and salts thereo~, wherein alkyl
represents a C8to C18 alkyl group, especially coconut alkyl,
lauryl and tallow alkyl. Speci~ic examples include"Armeen Z"
* Trademark
.
C~,
l !- ,
~'7~-~5
- 12 -
(marketed by Armour),"Amphos~ol"AA and SP ~marketed by I.C.V.),
"~mphoram CP~', Diamphoram CPl,"Triamphora~ CPl~"Triamphoram
C2Pl and~olyamphorams CPl, C2Pl an~ C3Pi" (marketed by
Pierrefitte-Auby) and"Deriphat 170C and~Deriphat 15~"
(marketed by General ~lills).
Of all the above surfactants, highly preferred composi-
tions comprise as the single or major sur~c~ant component,
surfactants selected from the anionic, amphoteric and
zwitterionic classes. The nonionic surfactants ~hen present
are preferab-y included in only a minor amount, i.e. at a
level of about 5 to about 50% by weight of the surfactant
system.
THE SEQUESTRANT
The sequestrant can be selected from ~he water-soluble
salts of polyphosphates, polycarboxylates, aminopolycarboxy-
lates, polyphosphonates and aminopolyphosphonates having a
logarithmic calcium ion stability constant (pKCa++) of about
2 or greater and an anion valence o~ at least 3. The stability
constant is defined as follows:-
pKCa++ = log10 KCa
wh~re Ca + = ~ A~ 2)-
~
and An is the ionic species of sequestrant which predomina~esat the in-use pH of the composition ~defined as the pH of a
1% a~euous solutlon o~ the composition) and n ls at least 3.
Pre~erabl~, the se~uestrant has a pKCa~ in the ran~e
~om about 2 to about 11, especially from about 3 to about 8.
Literatu~e v~lues of stability constan~s are taken where
possible ~see ~abiliky Constants of Metal-Ion Complexes,
Special Publi~ation No. 25, The Chemical Society, London);
wh~re dQubt ~ises, the stability constant is defined at
25C and at ~e~o ionic strength using a glass electrode
method o~ meagurement as described in Complexation in
~nalytical Chemistry by Anders Rlngbom (1963).
1-8 inclusive. The terms bearing these superscript numerals are
trademarks.
S5~..
- 13 -
Suitable polyphosphates include ~yrophosphates such as
tetrasodium pyrophosphate decahydrate, and tetrapotassiwn
pyrophosphate; tripolyphosphates such as pentapotassium
tripolyphosphate; and higher polyphosphates and metaphos-
phates such as sodium pentapolyphosphate and sodium hexameta-
phospha~e.
The carhoxylate-type sequestrants can be described as
monomeric polycarboxyla-te materials or oligomers or polymers
derived from carboxylate or polycarboxylate monomers. The
se~uestrants can be acyclic, alicyclic or aromatic in na-ture.
Suitable polycarboxylates include the salts of citric
acid, aconitic acid, citraconic aci~, carboxymethyloxy
succinic acid, lac~oxysuccinic acid, and 2-oxa-1,1,3-propane
tricarboxylic acid; oxydisuccinic acid, l,1,2,2-ethane tetra
carboxylic acid, 1,lr3,3-propane tetracarboxylic acid and
1,1, 2,3-propane tetracarboxylic acid; cyclopentane-cis,
cis, cis-tetracarboxylic acid, cyclopenta dienide penta-
carboxylic acid, 2,3,4,5-tetrahydrofuran-cis, cis, cis-
carboxylic acid, 2,5-tetrahydrofuran-cis-dicarboxylic acid,
1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid,
pyromellitic acid and the phthalic acid derivatives disclosed
in British Patent No. 1,425,343.
Suitable pol~meric polycarbox-ylates include homo- and
copolymers o~ polycarboxyl monomers such as maleic acid,
citraconic acid, aconitic acid, fumaric acid, mesaconic
acid, phenyl maleic acid, benzyl maleic acid, itaconic acid
and methylene malonic acid; homo- and copolymers of acrylic
monomers suh as acrylic acid, methacrylic acid or ~-hydroxy
acrylic acid; or copolymer.s o~ one or more o~ the above
pol~carboxyl. and acryllc monomers with another unsaturated
polymerizable monomer, such as vinyl ethe~s, acrylic esters,
ole~ins, vln~l pyrrolidones and styrenes.
Suikable aminopolycarboxylates include especially the
amino polyacetates, e.g sodium, potassium, ammonium and
alkanolammonium ethylenediamine tetraacetates, d~ethylene
triamine pentaacetates and nitrilotriacetates.
Polyphosphonate and aminopolyphosphonate materials
suitable for use herein can be exemplified by nitrilo tri-
(~ethylenephosphonic acid), ethylenediamine tetra(methylene-
phosphonic acid), diethylenetriamine penta(methylenephosphonic
acid) and the water-soluble salts thereof.
The terpene component of the instant compositions
belongs to the class of mono- or sesquiterpenes or mixtures
thereof and can be acyclic or preferably monocyclic or
bicyclic in structure. It is preferably liquid at room
temperature ~25C). Preferred terpenes belong to the class
of terpene hydrocarbons ~nd terpene alcohols. Examples of
acyclic terpene hydrocarbons suitable for use herein include
2-methyl-6-methylene-2, 7-octadiene and 2,6-dimethyl-2, 4,
~-octadiene. Preferred monocyclic terpene hydrocarbons
belong to the terpinene, terpinolene and limonene classes,
for example, the ~ , ~ and ~-terpinenes, the d and 2 -limonenes
and dipentene (essentially a limonene racemate). The
limonenes occur naturally in certain fruit and vegetable
essences and a preferred source of limonene is the essence
or orange and other citrus fruits. Preferred bicyclic terpene
hydrocarbons include ~ and ~ -pinene. The terpene is added
at a level of about 0.5~ to about 10%, preferably 1~ to about
5% by weight of the composition.
The terpene alcohol can be a primary, secondary or
tertiary alcohol derivative of a cyclic or acyclic terpene
hydrocarbon. Suitable tertiary alcohols include terpineol,
usually sold commercially as a mixture of ~ , ~ and ~ isomers
and linalool; suitable secondary alcohols include borneQl;
suit~ble primary alcohols include geraniol. Complex mixtures
3~ oP kerpene alcohols are also suitable, especially the mixture
o alcohols manufactured by distilling the oils extracted
from pine wood, cones and needles and 801d commercially as
pine oils>). The terpene alcohol ~.s preferably added at
a level in the range from abou-t 1% to abou-t 3~, more
3~
- 14 -
~,
.~.
preferably~from about 1.5~ to about 2.5% by weight o~ the
compositions in order to provide optimum control of product
viscosity characteristics. Preferably such compositions have L
a viscosity in the range from about 80 to 200 cp (0.08 to 0.2
Pa.s) measured in a Brookfield viscometer, using Spindle No.
2 at 60 r.p.m. and at 21C.
The polar solvent component of the present compositions
has a solubility in water at 25C in the range from about
0.2% to about 10~, preferably from about 0.5~ to about 6%.
The solvent contains at least one hydrophilic group and is
liquid at room temperature. The solvent can be at a level
of about 0.5% to about 10% especially 1% to about 5%, by
weight of the composition and at a weight ratio of terpene:
solvent in the range from about 5:1 to 1:5,especially 2:1 to
1:2. Highly preferred materials include aromatic alcohols
such as benzyl alcohol, polye~hoxylated phenols containing
from 2 to 6 ethoxy groups and phenylethyl alcohol; esters of
Cl-C6 fatty acids with Cl-C6 alcohols containing a total of
from 5 to 9 carbon atoms, eq, n-butyl butyrate, n-butyl
propionate and n-propyl acetate; and mono C6~Cg and di-C4-Cg
alkyl or aryl ethers of ethylene glycol such as hexyl, benzyl
and phenyl <~Cellosolves)> (Registered Trade Mark) and ethylene-
glycol dibutyl ether.
The compositions of the invention can be supplemented
by all manner of detergent components compatible with a fluent,
liquid system.
A non-aqueous solvent is a particularly suitable
a~ditional ingredient, especially water miscible or high}y
soluble (at least 20~w/w) aliphatic mono-, di- and tri alcohols.
Speci~lc examples are e~hanol, propanol, lsopropanol, ancl
propane-1,3-dlol. Other suitable solvents are ethylene-,
propylene-, diethylene- and dipropylene glycol and the mono-
alkyl ether and Cl 4 ester derivatives thereo such as
the ethylene glycol monomethyl-, monoethyl- and monobutyl
ethers, propylene glycol propyl ether, dipxopylene
glycol methyl ether, ethylene glycol mono acetate
- 15 -
`
745~
and ethylene glycol monoethyl ether acetate. The non-aqueous
solvent can be added in amounts up to about 10~, preferably
6% by weight of the composition.
Hydrotropes such as urea, monoethanolamine,
diethanolamine, triethanolamine and the sodium, potassium,
ammonium and alkanol ammonium salts of xylene-, toluene~,
ethylbenzene-, isopropyl- benzene sul~onates, can also be
added to the compositions of the present invention in amounts
up to about 10% by weight. It is a feature of the present
invention, however, that stable, homogeneous formulations can
be prepared without the need for hydrotropic materials of this
kind, or with only very minor levels li.e. less than about 4%
by weight).
Other suitable ingredients of the present compositions
include pH buffering materials such as alkali metal and ammonium
carbonates, bicarbonates, metasilicates and ortho phosphates.
These can be added, if appropriate, at levels up to about 10~
by weight to provide a compositional pH equal to or greater than
about pH 8, preferably greater than about pH9 and more prefer-
ably greater than about pH10. Dyes, perfumes,enzymes, chlorine-
releasing agents, polypeptides and protein hydrolysates, soil
suspending agents such as carboxy methyl- cellulose, hydroxy-
methyl cellulose and polyethylene glycols having a molecular
weight of about 400 to about 10,000, fluorescers such as
disodium 4,4'-bis(2-morpholino-4 anilino-s-triazin-6-yl amino)
stilbene-2,2'-disulfonate, preservatives such as Preventol ON>~
marketed by Bayer, thickeners such as xanthan gum, and addition-
al suds regulants such as tributylphosphate and silicone oil
can all be included in~-the instant compositions.
~ ~ germicide such as o-phenyl phenate can also be added
~o the present composltions, providing excellent hard surface
germiaidal activity.
*Trademark
)~ - 16 -
~ 7~ ~3~
In the examples which follow, the abbreviations used
have the following descriptions:-
PS : Sodium Cl to Cl paraffin sulfonate
marketed by Hoec~st under Trade Mark
Hostapur SAS.
LAS Sodium salt of linear Cll 8 alkyl
benzene sulfonate.
3 Sodium linear Cl 14 alcohol sulfate
including 3 ethy~ene oxide moieties.
Dobanol 91-8 : A C 11 oxo-alcohol with 8 moles of
ethylene oxide, marketed by Shell.
~Dobanol 45-7 : A Cl -15 oxo-alcohol with 7 moles of
ethy~ene oxide, marketed by Shell.
aPluronic L-42 : A condensation product of ethylene
- oxide and propylene oxide, marketed
by BASF-Wyandotte.
Deriphat 170C : N-C 2 1 alkyl-~ -amino propionic acid
mar~ete~ by General Mills.
Amphoram CPl : N-cocoyl- ~-amino propionic acid
marketed ~y Pierrefitte-Auby.
Deriphat 154 : Disodium-N-tallow- ~-amino propionate
marketed by General Mills.
Ethylan HB-4 : Phenol ethoxylated with 4 moles of
ethylene oxide, marketed by Diamond
Shamroc~..
HT Soap : Sodium soap prepared from hydrogenated
tallow.
CN Soap : Monoethanolamine soap of coconut fatty
acids.
TEA : Triethanolamine.
CS : Sodium cumene sulfona,te.
TPP : Tetrasodium pyrophosphate.
~DTA : Tetrasodium salt o~ ethylenediamine
tetraacetic acid.
NTA : Trisodium salt of nitrilotriacetic
acid.
~Dequest 2060 : Dlethylenetriamlne penta(methylene
phosphonic acid), marketed by Monsanto.
~Dequest 20~1 : Ethylenediamine tetra(methylene
phosphonic acid) marketed by Monsanto.
* Trademark
** Trademark
*** Trzdemark
- 17 -
-~7~
EXAMPLES 1 TO 7
The following liquid compositions were prepared by
mixing the ingredients in water:-
1 2 3 4 5 6 7
~ _ _ _ _ _ _
PS 4.54.0 - 8.0 5.0 - 6.0
LAS - - 4.0 - - 4.0
Dobanol 91-8 2.0 - - - - 2.00.5
TP2 - - - - 3.0
Sodium citrate .2H2O 3.5 3.5 - - - - 8.0
Sodium metasilicate ~ - - 3.0 - - 1.0
Sodium carbonate 3.0 3.0 2.5
EDTA - - - 2.5
NTA - - 3.0 - - 6.0
Orange terpenes 2.0 2.0
Dipentene - - 2.0
D-limonene - - - 6.0 - - -
~-pinene - - - - 2.0
~-pinene - - - - ~ 3.0
Terpinolene - - - - - - 2.0
Benzyl alcohol 2.0 - 2.06.0 - 1.5
Hexyl <~Cellosolve - 3.0 - - - - 2.0
Ethylan HB-4 - - - - 1.0
Ethanol - - - 2.0
Xanthan gum - - - - 0.5
CS 2.0 2.02.0 3.0 3.5 2.0 2.0
Water, Perfume &
minors To 100
The above compositions were hono~eneous fluent liquids
having good stability, excellent surface-shine and cleaning
characteri~tics on both inoryanic particulate soils and
olly/greasy soils with oontrolled sudsing in both dilute
and concentrated usage under both hard and sof t water
conditions.
- 18 -
~ .
~l~7~
EXAMPLES 8 TO 13
8 9 10 11 12 13
PS g.5 8.0 4.0 - 5.0
LAS - - - 5.0 - 6.0
Dobanol 91-8 2.0 - - l. 5 2.0 0.5
TPP - - - 6.0
Sodium citrate .2H2O3.5 - 3.0 - - 3.0
Sodium metasilicate - 3.0 - 1.0
Sodium carbonate 3.0 - 3.0 - - -
EDTA - 2.5 - - 0.5
NTA - - - - 6.0
Orange terpene - - 2.0
Dipentene - 6.0 - - - -
D-limonene 4.0 - - - - -
15 ~-pinene - - - 2.0
-pinene - - - - - 4.0
Terpinolene - - - - 3.0
n-Butyl butyrate 3.0 - - - 2.0
Benzyl alcohol - 6.0 l. 5
Benzyl Cellosolve - - - 3.0 - 2.0
CN Soap 1.5 1.5 0.3 0.05
HT Soap - - - - 0.1 0. 5
Xanthan gum - - 0.5
Ethanol - 2 - - - 1.5
TEA 1.0 3.0 - - - 2.0
CS - - 2~0 - - 1.0
Water, Perfume &
mlnors --- - To 100 - - -- -
~he above compositions were homoqenous fluent liqu:Lds
having good stability, excellent surface shine and cleaning
characteristics on both inorganic particula-te soils and
ol.ly/greasy soils with con-trolled sudsing in both dllute and
concent.rated usage under both hard and soft water conditions.
-- 19 --
:~7455~
EXAMPLES 14 TO 20
14 15 16 17 18 19 20
PS ~ 2.0 -
LAS ~ 1.0
<~Dobanol 91-8 2.7 2.0 3.2 2.0 1.0 - -
<~Deriphat 170C - 5.0 - 2.5
Amphoram CPl 3.2 - 3.2 - - - 5.0
Deriphat 154)> - - - 1.0 2.0 4.0
CN Soap - - - - - 0.5
Sodium citrate
.2H2O - - - - 6.0 8.0
Sodium carbonate 3.0 - 2.0 - - - -
Sodium metasilicate - - - - 1.0 - 2.0
TPP - 4.0
EDTA - - 2.5
NTA 3.0 - - - ~ 4-0
<~Dequest 2060 - - - ~ 0-5
Ethylene glycol
dibutyl ether 1.5 - - - 1.0
Benzyl alcohol - 2.0 - 3.0 - 2.0
Ethylan HB-4 - - 1.0 - - - 2.0
CS - 5.0 - 7.0 - 2.0
Orange terpenes - - 1.0 - - 2.5
Dipentene - - - - 2.0 - -
D-limonene 3.0 - - - - - -
a-pinene - 2.0 - - - - -
~-pinene - - - - - - 2.0
T~rpinolene - - - 5,0
Ethanol - - 1.0 2.0
Water, Per~ume &
minors ~ -To 100
The above compositions were homogeneous ~luent liquids
having good stability, excellent cleaning characteristics
on both inorganic particulate soils and oily/greasy soils
with controlled sudsing in both d:ilute and concentrated
usage under both hard and soft water.
- 20 -
: ,
~7~5~
EXAMPLES 21 TO 2 4
21 22 23 24
PS 4.5 5.0 4.03.0
LAS - - 2 . 0
Dobanol 91-8 - - O. 5 3 0
CN Soap ~ ~ ~ 0 5
Sodium Citrate 3 . 5 3 . 5 - 6.0
. 2H20
Sodium carbonate 3 . 0 2 6 . 01. 0
Pine oil 2 . 0
~-terpineol - 1.8
Linalool - - 2 . 2
Geraniol - - - 2 . 5
Benzyl alcohol 1.5 1.5 4.0
Phenyl ethyl alcohol- - - 2 . 5
o-Phenyl phenate1.3 1.5 1. 3 1. 3
CS 1.4 1.5 1.0 2.0
Water, Perfume and minors To 100
The above compositions were homogeneous, fluent
liquids having good stability at both normal and low
temperatures, as well as excellent germicidal activity,
surface shine and cleaning performance on both inorganic
particulate soils and oily/greasy soils.
-- 21 --
,.
'J
