Note: Descriptions are shown in the official language in which they were submitted.
I ~7816~
LIQUID HARD-SURFACE CLEANER
Ricardo Diez
Donald Brown Compton
Neil David Fraser
Michael Eugene Burns
TECHNICAL FIELD
This invention relates to novel homogeneous
aqueous liquid detergent compositions intended for
general purpose household usage for cleaning hard
surfaces.
Composit~ons lntended fo~r such purposes have
been commercially manu~actured for many years. They
have been available in both li~uid and granular form,
and often haYe been ~ormula~ed ~o perform especiall~
well in accomplishing some specific household task,
such as cleaning tile floors in kitchen and bath, or
tile walls in the bath, or bathroom tubs, or kitchen
sinks, or painted ~alls in the kitchen or elsewhere in
the house, or glass and porcelain surfaces. In general,
the requirements for these tasks differ sufficiently
from one another that no single composition is ideal
for all such usages. The compositions of the present
invention are effective across an unusually broad
spectrum of these tasks.
BACKGROUND ART
Pxoducts sold commercially for use in cleaning
hard surfaces around the house fall into several
categories. Solvent-based liquids such as Pine Sol (TM
American Cyanamid Co.~ and ~estoil ~TM Noxell Corp.)
~ . .
1 178160
typically contain about 25 to 35% o~ a solvent such
as pine oil together with about 10-15~ surfactant, but
with little or no sequestering builders or alkaline
buffers. When used full strength they are effective
on greasy soils, such as spots on kitchen walls, but
clean poorly on bathroom soils. They are also poor
when diluted with water for cleaning surfaces having a
broad area such as floors cr walls.
Built products have been formulated as both
granules and llquids. The formex contain large amounts
o~ se~uestering builders and alkaline buffers~ with
generally low levels of surfactant and no solvent.
They are especially effective when dissolved and used
on broad wall or ~loor Sux~aaes, but are somewha~ less
ef~ective as compared with other types o~ formulations
ln those appllcations where aoncentrated product is
needed. Li~uid products o~ this type, such as Mr.
Clean CTM Procter & Gamble Inc.l, typically con~ain up
to about 18~ builder, up to about 5~ surfactant, and
up to about 12% hydrotrope, with little or no solvent -
perhaps levels up to 2~ or thereabouts.
Other formulations such as Windex (TM Drackett
Company~, Fantastik tTM Texize Chemicals, Inc.~ and
~ormula 409 (TM Clorox Co.) have been prepared for use
as spray cleaners on glass ox appliances where freedom
from streaking is an important advantage because
xinsing is not normally done. These products may also
be used ~ull strength for spots on ~alls. They
typically contain from about 4~ to about 7% solvent,
about l-lQ~ surfactant, and about 1-3~ sequestering
builder/alkaline buffer.
~ till other formulations such as Comet CTM
Procter & Gamble IncO~ are sold as abrasive cleansers
1 ~781~0
for use on sinks, tubs and the like. They are most
commonly in dry form, and contain finely ground silica as
abrasive, together with relatively low levels of chlorine
bleach, surfactant, calcium sequestrant, and alkaline
buffer. A liquid cleanser containing suspended abrasive
has also appeared commercially. These cleanser formula-
tions contain no solvent.
Documents that make reference to liquid detergent
compositions containing surfactants, builders and selected
solvents, at levels that are high for the prior art but
low as compared with these of the present invention,
include Mausner, U.S. patent 3,232,880 issued February 1,
1966; Krusius, U.S. patent 3,360,476 issued December 26,
1967; Disch et al, U.S. patent 4,175,062 issued November
lS 20, 1979; and copending commonly assigne~ Canadian
application serial number 377,202 filed May 26, 1981
(~ofinet)~
~ he gist of the present invention is a range of
compositions in convenient li~uid form which contain
exceptionally high levels of both builders and of solvents
specifically chosen for their superb cleaning abilities,
together with surfactant and with other ingredients needed
to make the compositions homogeneous and physically stable
for convenient use and storage. The compositions of this
invention are novel and exhibit outstanding performance
characteristics that have not hitherto been achieved in a
single formula: cleaning of floors as well as commercial
li~uid or granular floor cleaners when both are used
diluted;
~ ~'781~0
cleaning of greasy walls as well as commercial wall
cleaners when both are used full strength; and cleaning of
bathtub soil, when used full strength, as well as abrasive
cleansers.
DISCLOSURE OF INVENTION
The detergent compositions of the present
invention are homogeneous aqueous liquids comprising the
following components:
a) from about 0.9% to about 10~ of a non-soap
anionic, amphoteric, zwitterionic or nonionic
surfactant;
b) from zero to about 5~ soap;
c) from about 10.5~ to about 19% of a polyphosphate
or polyphosphonate sequestrant;
d) from zero to about 6% oE an ~lkaline pH buffer,
with the proviso that the sum oE components (c)
and (d) is not greater than about 21% of th~
composition;
e) Erom about 6% to about 15~ oiE a Principal Solvent
having a molar volume below i~bout 2QO(cm.3/gm.
mol) and solubility paramete~s at 25C. as
follows: Polarity Parameter from zero to about
3.5(cal./cm3)1/2 and Hydrogen Bonding
Parameter from zero to about 6(cal./cm.3)1/2;
~5 f) from zero to about 10% of an Auxiliary Solvent
having a Polarity Parameter of about 3.51 or
above and/or a Hydrogen Bonding Parameter of
about 6.01 or above, with the proviso that the
sum of components (e) and (f) is not greater than
about 22~ of the composition;
~ ~ 7816~
--5--
g) from about 3% to about 25% of a hydrotrope;
and
h) the balance water;
wherein all percentages are by weight of the
composition; and wherein the pH of a 1% aqueous
solution of the detergent composition is from about
8.5 to about 11.
Surfactants. The surfactants of this invention are of two
general types, each of which is characterized separately
10 herein. The first such type is comprised of a wide range
of non-soap anionic, zwitterionic, amphoteric and nonionic
surfactants. A typical listing of the classes and species
of these surfactants is given in U.S. Patent 3,664,961
issued to Norris on ~ay 23, 1972. These surfactants can
15 be used singly or in combination at levels in the range
from about 0.9~ to about 10%, pre~erably at levels ~rom
about 2% to about 7~ by weight of the co~positions.
Non-soap suractants as herein defined contribute
cleaning per~ormance to the compositions o~ this invention,
20 especially when used in d~luted form to clean broad sur-
aces such as floors and walls.
Suitable anionic non-soap surfactants are water-
soluble salts of alkyl benzene sulfonates, alkyl sulfates,
alkyl polyethoxy sulfates, paraffin sulfonates, alpha-
25 olefin sulfonates, alpha-sulfocarboxylates and their
esters, alkyl glyceryl ether sulfonates, fatty acid
monoglyceride sulfates and sulfonates, alkyl phenol
polyethoxy ether sulfates, 2-acyloxy-alkane-1-sulfonate,
and beta-alkyloxy alkane sulfonate.
A particularly suitable class of non-soap anionic
detergents includes water-soluble salts of
1 ~81~0
--6--
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 sul~onic 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 o the detergent
compositions of the present invention are the sodium
and potassium alkyl sulfates, especially those obtained
by sulfating the higher alcohols (ClQ-C18~ carbon atoms
lQ produced from the glycerides of tallow or coconut oil;
and sodium ancl potassium alkyl benzene sulfonates, in
which the alkyl group contains from about 9 to about
15, especially about 11 ~o about 13, carbon atoms, in
stralght chain or branched chain configuration, e.g.
those of the t~pe described in USP 2,220,099 and
2,477,383 and those prepared from alkylbenæenes obtained
by alk~lation with straight chain chloroparaffins
~using aluminum trichlori~e catalysis~ or straight
chain olefins ~using hydrogen fluoride catalysisl.
Especially valuable are linear straight chain alkyl
benzene sulfonates in which the average of the alkyl
group is about 11.8 carbon atoms, abbreviated as Cll 8L~S.
Other non-soap anionic detexgent compounds
herein include the sodium C10-C18 alkyl glycexyl ether
sulfonates, especially those ethers of higher alcohols
deri~ed from tallow and coconut oil; sodium coconut oil
fatty acid monoglyceride sul~onates and sulfates; and
sodium or potas~ium salts of alkyl phenol ethylene
oxide ether sulfate containing a~out 1 to about 10
units of ethylene oxide per molecule and wherein the
alkyl groups contain about 8 to about 12 carbon atoms.
Ot~er useful non-soap anionic detergent
compounds herein include the water-soluble salts or
1 ~781BO
esters of alpha-sulfonated fatty acids containing
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-al~ane-1-
sulfonic acids containing from about 2 to 9 carbonatoms in the acyl group and from about 9 to about 23
carbon atoms in the alkane moiety; alkyl polyethoxy
sulfates containin~ from about 10 to 18, especially
ahout 12 to 16, carbon atoms in the alkyl group and
lQ from a~out 1 to 12, especially 1 to 6, more especially
1 to 4 moieties of ethylene oxide per fatty alcohol
moiety; water-soluble salts of olefin sulfonates containin~
from about 12 to 24, preferably about 14 to 16 , carbon
atoms, especially those made by react:ion ~ith sulfur
trioxide ~ollowed by neu~ralizatio~ ~mder conditions
such that any sultones present are hydrolysed to the
corresponding hydroxy alkane sul~onates; water-soluble
salts of paraffin sulfonates aontaini.ng from about 8 to
24, especially 1~ to 18 carbon atoms r and beta-alkyloxy
alkane sulfonates containin~ from about 1 to 3 carbon
atoms in the alkyl ~roup and from a~out 8 to 2Q carbon
atoms in the alkane moiety.
The alkane chains o~ the foragoing non-soap
anionic surfactants can be derived from natural sources
such as coconut oil or tallow, or can be made synthet-
ically as fox example using the Ziegler or Oxo processes.
~ater solubility can be achiaved by using alkali metal
~r alkanol-ammonium cations; or magnesium or calcium
cations under circumstances described by Canadian
3Q patent 1,071,Q55 invented by Jones et al, i~sued
February 5, 198Q.
Mixtures of non-soap anionic surfactants are
contemplated by this inventi~n; a preferred mixture
contains alkyl benzene sulfonate having 11 to 13 carbon
1 1781BO
atoms in the alkvl group and either an alkyl sulfate
having 8 to 18, preferably 12 to 18, carbon atoms in
the alkyl group, or an alkyl polyethoxy sulfate having
10 to 16 caxbon atoms in the alkyl group and an average
degree of ethoxylation of 1 to 6.
Suitable ampholytic surfactants are water-
soluble derivatives o~ aliphatic secondary and tertiary
amines in which the aliphatic moiety is straight chain
or branched and wherein one of the aliphatic substituents
contains ~rom about 8 to 18 carbon atoms and one contains
lQ an anionic water-solubilizing group/ e.~. carboxy,
sulfonate, sulfate, phosphate, or phosphonate.
Suitable zwitterionic sur~actants are water
soluble derivati~es of aliphatic ~uaternary ammonium
phosphonium and sul~onium catlonic compounds in which
the aliphatic moieties are straight chain or branched,
and wherein one of t~e aliphatic substituents contains
rom about 8 to 18 carbon atoms and one contains an
anionic water-solubilizing group.
Preferred amphoteric and zwitterionic
su~actants have the general formula:
I
~1 N~ R2_ X
R4 n
wherein X is C02 or S03 , Rl ls alkyl or alkenyl group
having 8 to 22 caxbon atoms, possibly interrupted by
amide, ester ~x ether linkages, R2 is a methylene,
ethylene, propylene, isopropylene or iso~utylene radical,
R3 and R4 are independently selected from hydrogen, Cl 3
1 ~781~0
g
alkyl ox -R2-X, whereby one of the substituents R3
and R4 is hydrogen if the other one is represented by
the group -R2X, n ls an integer from 1 to 6, and A is
an equivalent amount of a neutralizing anion, except
that amphoteric sur~actants include amine salts of the
above formula and also the corresponding ~ree amines.
Highly preferred surfactants according to the
above formula include N-alkyl-2-aminopropionic acid, N-
alkyl-2-imino-diacetic acid, N-alkyl-2-iminodipropionic
la acid, N-alkyl-2-amino-2-methyl-propionic acid, N-alkyl-
propylened~amine-propionic acid, N-alkyl-dipropylene-
triamine-propionic acid, N-alkyl-dipropylenetriamine
dipropionlc acid, N-alkylglycine, N-alkyl-amino-succinic
acid, N-amidoalkyl-N'-carboxymethyl-N',N'-dimethyl-
ammonio -ethylene diamine, N-alk~l-amino-ethane-sulfonic
acid, N-alkyl-N,N-dimethyl-ammonio-h~droxy-propane-
sulfonic acid and salts thereo~, wherein alkyl xepresents
a C8 to C18 alk~l group, e~peclally coconut alky~,
lauryl and tallo~ alkyl. Speci~ic examples includ~
~rmeen~Z ~marketed ~y Armour-Dial, Inc.l, ~mphoram CPl,
Diamphoram~CPl, Triamphoram~CPl, Triamphora ~C2Pl and
Polyamphorams~ Pl, C2Pl and C3Pl ~markete~ by Pierrefitte-
Auby S.A.~ and Deriphat~70C and Deriphat 154 ~marketed
b~ General Mills, Inc.~.
Suitable nonionic surfactants are of several
classe~. Suitable semi-polar nonionic surfactants
include water-soluble amine oxides containing one alkyl
moiety of ~rom about 10 to 28 carbon atom~ and 2 moieties
selected from the group consisting of alkyl groups and
3~ hydroxyalkyl groups containing from 1 to about 3 carbon
atoms, and especially alkyl dimethyl amine oxides
wherein the alkyl group contains from about 11 to 16
carbon atoms; water-soluble phosphine oxide detergents
containing one alk~l moiety of about 10 to 28 carbon
1 1781BO
--10--
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 containing one alkyl moiety of
from about 10 to 28 carbon atoms and a moiety selected
from the group consisting of alkyl and hydroxyalkyl
moieties of from 1 to 3 carbon atoms.
Another and especially suitable class of
nonionic surfactants are alkyl mono- and di-alkanol
lQ amides, the alkyl group of which contains from about 10
to about 18 car~on atoms, such as coconut monoethanol
amide and oleyl diethanol amide. Particularly preferred
axe the ClQ to C18, more especially C12 to C14, diethanol
amides.
Alkoxylated nonionic sur~actants are another
class that is suitable for use in th:ls inventio~, ;
especially when used in mixtures at levels no more than
about 50% o~ the total non-soap surfactant system,
pre~erably at ~evels from about 5% t~3 abou~ 35% thereo~.
2Q Alkoxylated nonionic suractant materials can be ~roadly
defined as compounds produced by the condensation of
alkylene oxide groups ~hydrophilic in nature~ with an
organic h~drophobic compound, which may be aliphatic or
alkyl aromatic in nature~ The length of the poly-
oxyalkylene group which is condensed with an~ particularhydrophobic group can be readily adjusted to yield a
w~ter-solu~le compound having the desired degree of
balance between hydrophilic and hydrophobic elements,
Examples of suitable noniontc surfactants
include (a~ 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
.~
- . :
8 1 6 ~)
--11--
configuration xeacted with ethylene oxide in amounts
equal to from 1 to about 25 mols of ethylene oxide per
mol of alkyl phenol. The alkyl substituent in such
compounds may be derived, for example, from polymerised
propyLene, di-isobutylene, octene and nonene. Other
S examples include dodecylphenol condensed with 3 mols of
ethylene oxide per mol of phenol; dinonylphenol condensed
with la mols of ethylene oxide per mol of phenol; and
nonylphenol and di-isooctylphenol condensed with 20
mols of ethylene oxide; ~I The condensation products
of primary or secondary allp~atic alcohols having from
8 to 24 carbon atoms, ln elther stralght chain or
branched chain configuration, with from 1 to about 30
mols o~ alkylene oxide per m~l o~ alcohol. Preferably,
the alip~atic alcohol comprises between 9 and 15
caxbon atoms and às ethoxylated ~ith between 2 and 12,
desira~ly between 3 and 9 mols o~ ethylene oxide per
mol o~ aliphatic alcohol. Pre~erred nonionic surfactants
o this type aXe prepared from primary alcohols which
are either li~ear (such as tho~e dexived ~rom natural
~ats or prepared by t~e Zlegler process from et~ylene,
e.g. myristyl, cetyl, stearyl alcohols~, s~r partly
branched such a~ the Dobanols~and Neodols~which have
about 25~ 2-methyl branching tDobanol and Neodol being
Trade Marks of Shell Chemical Co.~ or Synperonics~
~hich are understood to have about 50% 2-methyl branching
(Synperonic is a Trade ~ark o~ Imperial Chemical
Industries Ltd~ or the primary alco~ols ha~ing more
than 50% ~ranched chain structure sold under the Trade
Mark Làal by Liquigas S.p.A. Specific examples of
3Q nonionic surfactants ~all~ g within the~scope of the
invention in ~ude Dobano ~ 4, Dobanol 4~ 7, Dobanol
45-9, Doba~o r 91-3, Doba~ol~~1-6, Dobanol'~1-8,
S~nperonic`~6, Synperonic'~14, the condensation products
of coconut alcohol with an a~erage of between 5 and 12
mols of ethylene oxide per mol of alcohol, the coconut
I :l781BO
alkyl portion having from 10 to 14 carbon atoms, and
the condensation products o~ tallow alcohol with an
average of between 7 and 12 mols of ethylene oxide per
mol of alcohol, the tallow portion comprising essentially
between 16 and 22 carbon atoms. Secondary linear alkyl
ethoxylates are also suitable in the present compositions,
especially those ethoxylates of the Tergito ~ (T.M.Union
Carbide Corp.~ sexies haYing from about 9 to 15 carbon
atoms in the alkyl gxoup and up to about 11, especially
from about 3 to 9, ethoxy residues per molecule; and
(c~ bloc~ polymers formed b~ condensing ethylene oxide
~ith a hydxophobic base formed by the condensation of
propylene oxide ~rith either propylene glycol or ethylene -
diamine. Such synthetic nonionic detergents are ~
com~ercially available under the names "~luronic' and
Tetronic", respectively ~T.M. BAS~ W~andotte Corp].
Of the above, preferred alkoxylated nonionic
surfactants have an averaye HLB ~hydrophilic-lipophilic
balance~ ln the range from about 9.5 to about 13.5,
especially ~rom lQ to 12,5. ~ighly su~tabl~ nonionic
sur~actants of this type are ethoxylated primary or
secondary Cg 15 alcohols having an average degree of
ethoxylation from about 3 to 9.
Expecially pre~erred non-soap surfactants are
ClQ_18 alkyl diethanol amlde and the sodium sal~s of
straight or ~ranched chain C~ 15 alkyl benzene sulfonate,
C~ 8 alkyl sulfate, and Cl0-l8 alkyl polyethoxy
sulfate containing from 1 to about 12 ethylene oxide
moieties per fatty alcohol moiety.
3~ Soaps are speci~ically excluded from the
surfactants disclosed hereinabove. Howe~er, soaps
derived from fatty acids, natural or synthetic, saturated
or unsaturated, havin~ alkyl ¢hains ranging from about
I ~7~160
-13-
10 to about 18 carbon atoms in length, are also useful
in the compositions of the present invention. Examples
of preferred soaps are sodium and potassium laurate,
myristate, palmitate, oleate and stearate; and sodium
and potassium soaps dérived from coconut and tallow
fatty acids.
Soaps are effective not only as supplemental
cleaning agents, bu~ also aid in the solubilization of
othex ingredients of the composition. In addition they
control sudsing, which is hi~hly desirable ~or compo-
~itions that are intended to not require rinsing.
~ccordingly, use of ~xom about 0.5~ to about 5% soap is
preferred in khe compositions of t~is invention. T~is
usage is, however, by no means essential to obtain
superb cleaning performance characteristics and the
requisite product homogeneity, and ~he broad limits of
soap usage are there~ore ~rom zero to about 5~.
Builders. The builders o~ this invention are of two
general types, each of which is charac~erized separately
2a hexein. Materials useful'as Sequestrants are hardness
sequestering builders selected from the alkali metal
salts of polyphosphates a~ p~lyphosphonates.
~
~ 178~0
-14-
Sequestrants are used in amounts rrom about
10.5~ to about 19% by weight of the composition,
preferably from about 12~ to about 16~o It has been
found that amounts up to about 10.5~ do not fully meet
the multipurpose cleaning objectives of this invention
while amounts over 19~ are unnecessary to meet these
objectives, difficult to solubilize, and add to costs
not only directly but also indirectly by increasing
hydrotrope requirements.
Suitable polyphosphates include pyrophosphates
such as tetrasodium pyrophosphate decahydrate and
tetrapotassium pyrophosphate; tripolyphosphates such
as pentapotassium tripolyphosphate; and higher poly-
phosphates and metaphosphates such as sodium penta-
polyphosphate and sodium hexametaphosphate.
Among preferred Sequestrants can be mentioned
the al~ali metal salts, more particularly, the sodium
and potassium salts, of pyrophosphoric acid and tri-
polyphosphoric acid. Especially preferred is the
potassium salt o~ pyrophosphoric acid.
.: ~
~ ~781~0
-15-
Alkalaine pH Buffers are a second type of
builder. These materials include alkali metal carbon-
ate, bicarbonate, orthophosphate, borate and silicate
salts and ethanolamines. Buffers are not essential
ingredients of the compositions of this invention.
However they are preferably used in amounts rom about
0.5% to about 6~ by weight of the composition to
provide a source of reserve alkalinity. They are
selected according to the conventional wisdom of the
detergent arts to provide pH buffering from about 8.5
to about 11.0 for a 1% aqueous solution of the com-
plete composition of this invention. The lower pH
boundary was selected in relation to cleaning effect-
iveness and the upper boundary in relation to mildness
and safety to surfaces.
So long as the composition has the proper pH
as defined herein, it is an effective cleaner without
the presence of buffer for soils that do not contain
an acidic component.
)
0
Acco~dingly the broad limits for buffer are
zero to about 6% by weight of the composition. There
is a further limitation ~hat the total o Sequestering
Builder plus pH Buffer be no* greater than about 21%
by weight o~ the composition; this limitation is in
relation to solubilization requirements ~or the
homogeneous liquids o~ this invention.
Solvents. The solvents of this invention are of two
types that are characterized separately herein. The
~irst is a Principal Solvent that is required to meet
the detergency ob~ectives. T~e second is an Auxiliary
Solvent that under certain circumstances as described
herein is utilized to solubilize the Princlpal Solvent
in the composition in order to prepare a clear,
homogeneous ~inished product.
The Principal Solvent o~ this inventlon is
used in an amount ~rom about 6~ to about 15% by weight
o~ the compos~tion, pre~er~ rom about 8~ to about
12%. ~t has the ~oll~wing physical properties at
20 25~C.:
Molar Volume: below about 200~cm3~g.mol)
solubility parameters:
Polarit~ Parameter: zero to about
3.5 Ccal.~cm.3~1~2
H~drogen Bonding Parameter: zero to
about 6 (cal.~cm.311~
The molar volume o~ a compound is the quotient
o~ its molecular weig~t divided ~y its density. This
has metric units of tgrams per g. mol~ divided ~y
~grams per cubic centimeterl which result~ in a unit of
volume per ~ram mol Qf the compound in ~uestion.
1 1~81BO
The solubility parameters defined above are those
of Hansen and Beerbower, "Solubility Parameters", Kirk-
Othmer Encyclopedia of Chemical Technology, second ed.,
Supplementary Volume pp. 889-910, John Wiley & Sons, N.Y.
(1971). Hansen characterized the solubility behavior of
liquids according to three modes of interaction between
molecules: (1) dispersion (London) forces arising from
fluctuating atomic dipoles caused by electrons rotating
about a nucleus; (2) interaction between permanent or
induced molecular dipoles; and (3) hydrogen bonds. These
are frequently indentified as ~D~ ~p and ~H respectively,
and are herein designated by the terms dispersion para-
meter, polarity parameter, and hydrogen bonding parameter,
respectively.
A listing of these four parameters at 25C. for
over 200 solvents appears as Table L, of Hansen et al
op. cit. The criteria for the Principal Solvents o~ the
present invention have been selected as follows: Solvents
having molar volumes above about 200 are so large that
they do not penetrate and disperse soils rapidly and well.
A solvent's dispersion parameter has been ~ound incon-
sequential to detergent efEectiveness. However, it has
been determined that the Polarity and Hydrogen Bonding
Parameters of a solvent must be lower than about 3.5 and
6.0, respecti~ely, to provide the superb detergency proper-
ties across the great variety of detergency applications
that this invention is intended to accomplish. Mixtures
of Principal Solvents having molar volumes and solubility
parameters within the range defined above are also
suitable for use in the instant invention.
It has further been found that solvents having
Polarity Parameters and/or Hydrogen Bonding
~ 178~60
,~ .
_~g _
Para~etexs at or below about 2.0, while they perform
superbly as cleaners in the compositions of the present
invention, are often not sufficiently miscible with the
other ingredients to form clear, stable, homogeneous
S liquid composltions, even with the addition o~ hydro-
txopes as hereinafter defined. Accordingly, Auxiliary
Solvents having Polarity and/or Hydrogen Bonding
Parameters highex than 3.51 and 6.01, respectively
(i.e. higher than the limits defined hereinbefore for
the Principal Solventl, can be added to compatibilize
the ~rincipal Solvents in these compositions. As a
guide to formulation, each parameter o~ a solvent
rnixture can be estimated according to the weighted
avexage of its components.
The ~uxiliary Solvents o~ this invention can
be used in an amount up to about ~ o~ the composition
b~ we~ght, i.e. ~rom zero to abou~ 10%. When used,
pxefexred amounts are ~rom a~out 2% to about la%
~y weig~t o~ the comp~s~tion. Because o~ solubiliæation
re~u~re~ents, the total o~ Princ~pal Solvent plus
Auxiliar~ Solvent should not ~e greatex than about 22
o~ the composit~on by weight.
When the Polarity and Hydrogen Bonding
Parametexs o~ the Principal Solvent are both above about
2.Q, an Auxiliar~ Solvent is in general not necessary
fox solubilization and preferably is used in an
in5ignlficant amount if at all; i.e. less t~an about
2% by weight o~ the composition.
Auxiliary solvents used in this manner have
3Q sometimes been described in the priox art as "coupling
agents". This texm is avoided herein, as the solubilizing
~unction can often be accomplished not only ~y Auxilia~y
Solvents as defined herein, ~ut also by Principal
1 1781B10
l~
Solvents of relatively high Polarity and Hydrogen
Bonding Parameters. So doing not only accomplishes the
solubilizing function but also contributes effectively
to cleaning. According to these principles, it may be
preferred, for example, to solubilize xylene with
diethylene glycol mono-n-butyl ether than with isopropyl~
alcohol. l
Examples of ho~ solvents meet these definitions
are as ~ollows;
~ydrogen
Molar Polarlty Bonding
Volume Parameter Parameter
cm.'3 ' cal, 1/2 ' cal 1/2
Code Sol~ent ' '' ~ mol '' cm.3 ~.
A Dodecane 228 ~ a- ~
B Toluene 106 0.7 1.0
C Naphthalene 112 1.0 2.~
D ~sopropyl ~lcohol77 3.0 8.0
E Glycerol 73 S.9 14.3
~exylene Glycol 123 4.1 8.7
G Propylene Carbonate 85 8.8 2.0
H ~thylene glycol
monoethyl ether ~8 4.5 7.0
~iethylene ~lycol
mono-n-butyl ether 170 3.4 5.2
J But~l acetate 133 1.8 3.1
K Pine Oil ~ 126 ~ 2.0 ~ 5.6
L Orange te~pene ~ ~4 ~ 0 ~ a.3
Di~cussin~ ~ese solYents individually:
A. T~e molar ~olume o dodecane is too high to
s~tisfy the requirements of this invention as
to Rrincipal SolYe~t.
~,C. Toluene o~ n~phthalene can ~e used as Principal
~olyent, ~ut ~e~u~re t~e addition o~ an
~uxil~ SolYent to satis~y the solu~ility
xequixements of t~is invent~on.
.
î ~7818~
, ~,o
~"~,.
D,~,~,G,H. Isopropyl alcohol, hexylene glycol-, glycerol,
propylene carbonate and ethylene glycol
monoethyl ether are too high in Polarity
Parameter and/or-Hydrogen Bonding Parameter
to satisfy the re~uirements of Principal
Solvent. However the~ are acceptable as
Auxiliary Solvents.
I,J,K,L. Diethylene glycol mono-n-butyl ethex can ~e
used as Principal Solvent of this invention.
In the foregoiny table, parameters ~ox solvents
~-J a~e those appearing in Hansen et al, op. cit.
Parameters ~or solvents K and L wexe estimated, as
~ollows:
Pin~ oil, according to the Pine Oil Foxmular~,
Hercules Powder Compan~ ca. 1963, is derived from
extracts of p~ne wood and is compx~sed predominantl~ of
cyclic texpene alcoh~ls. Its chief con~tituent is
alpha terpineol, a tertlary alcohol having the structure
~c(cH3l2oH~ Wh~ch is present at levels ran~ing ~rom
below 70~ to as high as 85~, depending upon the
commercial grade, with`the remaindex being a mixture of
terpene hydrocarbons, ethers and ketones. Values for
the molar volume, Polarity Parameter and Hydrogen
B~nding Parametex of alpha terpineol and pine oil are
not available in the literature. However, based on
literatuxe value~ ~or chemicals of closely related
structure and upon ~leanin~ data, these three values
axe estimated ox ~oth su~stances to ~e approximately
those appeaxin~ in the foregoing ~able for solvent K.
Orange terpenes and limonenes, also, are
mixtures of chemicals derived from naturally occurring
materials that Vary somewhat accord~ng to source.
These three values ~Qr both substances are estimated to
~e approximately t~ose appearing in the foregoing table
for solvent L.
11 17816~ -
~ t ~ill be understood that selection of
Principal Solvents ànd Auxiliary Solvents for particular
applications of this inve~ntion will take into
consideration not only the parameters discussed
hereinabove but also such usual criteria as cost,
availability, odor, ~lammability, safety, etc.
Solvents meetin~ the criteria herein expressed
~or Principal Solvents o~ this invent~on, that ordinarily :
do not require the use of Auxiliary Solvents, include
ethylene glycol mono-n-butyl ether, ethylene glycol ..
mono-n-hexyl ether, diethylene gl~col mono-n-butvl
eth.er, diethylene glycol mono-n-hexyl ether, isopropylene
glycol mono ethyl ether, isopropylene glycol mono
propyl ether, lsopropylene glycol mono butyl ether,
methyl cycloh.exane, butyl acetate, amyl acet~te, butyl
~utyrate, ~ut~l lactate, diethyl ca~bonate, dlet~lyl
sucainate, m~th~l ~-amyl ketone, morpholine, and anisole.
$olvents meeting the criteria herein expressed
for Principal Solvents of this invention, for which
~uxiliary Solvents are ordinarily required, include n-
hexane, n-decane, cyclohexane, toluene, xylene, naphtha-
lene, diethyl ~enzene, chlorobenzene, trichloroethylene,
pine oil, alpha texpineol, d~limonene, and orange
terpene.
Solvents wh~ch can be used as Auxiliary
Solvents in thls invention, that do not meet the
criteria ~or Principal Solvents, include propylene
car~onate, meth~1 eth~1 ~etone, acetone, et~ylene
glycol mono meth~l ether, ethylene glycol mono ethyl
3Q ether, diethylene glycol mono methyl ether, diethylene
glycol mono ethyl ether, benzyl alcohol, diethylene
~lycol, glycexol, hexylene glycol, propylene glycol,
ethylene glycol, l-butanol, l-propa~ol, and ethanol.
~:,
,
~ ~781~ `
_22-
The ~oregoing lists are not intended to be
exhaustive but rather to exemplify the varied kinds of
solvents that meet the parameters of this invention as
defined hereinbefore. Provided solvents meet the molar
volume, polarit~ parameter and hydrogen bonding parameter
limits as hereinbefore defined, the Principal Solvents
of this invention can be selected from among aliphatic,
aromatic and chlorinated hydrocarbons; alcohols;
esters; ethers; glycol ethers; ketones; and amines.
Preferred Principal Solvents are ethylene
glycol mono-n-~ut~l ether, ethylene glycol mono-n-
hexyl ether, diethylene gl~col mono-n-butyl ether,
diethylene ~lycol mono-n-he~yl ether, isopropylene
glycol mono ethyl ether, mixed isopropylene glycol
mono-butyl, et~l and propyl ethers, pine oil, alpha
terpineol, orange ter~ene, met~yl cyclohe~ane, toluene,
xylene, but~l acetate and amyl acetate. Especially
preferred is diethylene glycol mono-n-butyl ether,
used in the essential absence of an ~ux~liary Solvent.
2a Hydrotrope. Solubilization of ingredients of dissimilar
characteristics such as solvents and electrolytes is
achieved by the use o~ hydrotropes. ~ater soluble
salts o low molecular weight organic acids are suitable
hydrotropes. Among such materials are sodium and
potassium salts of toluene, benzene and cumene sulfonic
acids, and sodium and potassium sulfosuccinate. Urea
is also a suitable hydrotrope. Hydrotropes are used
in amounts from about 3~ to about 25~ by weight of the
composition, pr~ferably ~rom about 6~ to about 14%.
Optional Ingredients. T~e compositions of the present
invention can optionally contain minor amounts of
colorants; perfumes;
... .. .
. . .
1 ~781~0
soil suspending agents such as carboxymethyl cellulose,
sodium polyacrylate, and polyethylene glycols having a
molecular weight from about 400 to about 10,000;
fluorescers; suds boosters; suds regulants; opacifiers;
enzymes and enzyme stabilizers; germicides; and other
materials known to the liquid detergent arts.
INDUSTRIAL APPLICATION
The following examples describe the ~ormulation
of compositionS o this invention and the benefits
derived therefrom. The~ axe illustrative of the
~nvention and ~re not ko be construed as limiting
t~ereof.
Example_l.
Composition ~ wa~ prepared by mixing the
followin~ components together in the order listed:
wt.~ of active
Component ~rams ~ngredient_
~ater 67.5 S9.1
KTS (51.5~ 38.8 10.0
Na2C3 3.1 1.55
NaHCO3 2.5 1.25
Coconut ~atty Acid 3.6 1.8
NaAE3S ~27~ active pastel 18.5 2.5
TKPP (60~ solution)46.0 13.8
diethylene glycol mono
n-butyl ether- 20.0 10.Q
20Q.0 100.Q
In the table above, NaAE3S designates the
sodium salt o~ the condensation product of 3 mols of
ethylene oxide ~ith coconut fatty alcohol. TKPP
designates tetrapotassium pyrophosphate. ~TS designates
potassium toluene sulfonate. The coconut fatty acid
1 178160
, ~
was neutralized during the mixing process to form
coconut soap. The pH of the composition was measured
to be 9.5 when measured full strength and 9.3 when
measured as a 1~ aqueous solution.
This composition was tested for cleaning
performance against 5 kinds of artificial soil designed
to simulate in a reproducible manner a liXe number of
natural soils ~ound around a house:
1~ Greasy~waxy soil found on kitchen floors: a
mixture of cooking oil and floor-wax applied
to vinyl-as~estos tiles; and aged.
21 Greas~ soil ~ound on kitchen walls: a mixture
of cooking oil and humus applied to vinyl-
asbestos tiles; baked; ancl aged.
lS 3~ Bathroom soil found in bat:htubs: a mixture
o~ skin o~1, soap and humus applied to
etched porcelain plates; three coats applied
and ~aked; aged.
41 Bathroom soil found on walls above the tub
or in shower stalls or in toilet bowls:
calcium stearate applied to smooth porcelain
plates; baked.
All soils were pigmented with small amounts of carbon
black to aid in the evaluation of cleaning per~ormance.
Cleaning tests were performed on a modi~ied Gardner
straight line tester (Gardner Lab Inc., Bethesda,
Maryland, U.S.A~). In this machine, a rectangular
sponge is moved back and forth across the test surface
with constant, uniform pressure applied. The cleaning
product was applied to the sponge, and a ~ixed number
of strokes was made across the sur~aces. The total
number of strokes for each test was fixed at the point
where the cleaning level of approximately 7Q to qO%
was visually estimated for the ~est composition in
that particular test. Each product was replicated
four times on different tiles.
1 1 7 ~
---~6~
Cleaning results were quantitively evaluated
by using the L (lightness~ values of a Hunter colorimeter
(Hunter Associates Laboratory, Fairfax, Virginia,
U.S.A.). Performance was measured as the percentage
of soil removed. Quantitatively, where Lb ~ the L --
value of the substrate before soil was applied; Ls =
the L value after soil was applied; and Lc = the L
value after cleaning; the cleaning performance in %
was calculated to be (lOO~Lc-Lb~/~Ls-L~l.
In the performance tests described infra,
li~uid cleaning compositions were used full strength
on both bathroom soils ~nd on the greasy kitchen wall
soil; while the liquid compositions were used in
dilute foxm on both k~tchen soils; making 5 teSts in
15 all. These practices simulated consumer practices in
cleaning these surfaces, either full strength from the
~ottle or diluted in a scrub bucket. For tesk purposes,
2 grams of the liquid compositions were applied to
each Gardner test sponge and used for full strength
cleaning; while a mixture o~ 0.15 ~rams ol the li~uid
composition with 9.85 ~rams of water was used for
dilute cleaning. To simulate consumer use of dr~
abrasive cleanser, 2 grams of the composition plus 2
grams of water was applied to the sponge.
Cleaning ~erformance was as follows:
Percentage of Soil Removed
Simulated Product Ccmp. Commercial Products
Soil Collc. A Mr.Clean Pine Sol Ca~et
Kitchen floor dilute 6~% 71% 7% -
" wall " 83 74 57
" " full str. ~Q 38 81
Bathroom tub " " 85 57 52 85
Shower wall " " 77 25 1~ 4a
1 17~160
~6
.. ., ~
In the above comparison, Mr. Clean ~TM Procter &
Gamble Inc.~ is a built liquid composition sold
commercially for hard sur~ace cleaning, containing
sodium nitrilotriacetate and mixed diethanol amide/
ethoxylated nonionic surfactant as principal cleaning
ingredients; Pine Sol (TM American Cyanamid Co.~ is a
liquid composition sold commercially for hard surface
cleaning, containins pine oil, isopropanol and soap;
and Comet (TM Procter & Gamble Inc.~ is an abrasive
cleanser sold for Scouring tu~s and sinks, containing
finel~ divided s~lica as the scouring agent, and
lesser a~ounts o~ anionic surfactant, chlorine bleach,
and builder.
In the fore~oin~ table, cleaning differences
between products greater than about 3~ are significant.
Acco~dlngly, Composition A, fo~mulat~d according to
this invention, was approximately e~ual to or was
superior to each o~ these commercial products in evexy
application. This same conclusion was also reached by
a panel of ~rade~s w~o ~lsuall~ examined t~e tile
surfaces after cleaning.
N~te that it is appropriate to compare
cleaning results or each type of soil as obtained fox
the 4 products tested ~i.e. numbers within each single
row of the table ~ove~. ~t is not appropriate to
compare numbers ~ithin columns of the table, because
the number of strokes on the test machine were different
for each type of soil.
~ second composition of this invention, B,
~as prepaxed that differed from A only in that 2
diethanolamine was used as ~uffer, replacing the
mixture of 1.55~ Na2CO3 plus 1.25~ NaHC03, ~ith a
I ~ 781~
-27-
minor adjustment in the water content. The cleaning
tests were repeated with approximately the same
results.
Composition C of this invention was like that
of Composition A except that it contained 6~ instead
of 10% of diethylene glycol mono-n-butyl ether, with
the difference made up by water.
Composition C was tested on the two bathroom
soils in the manner hereinbefore described, and in the
same series of tests, with the following results: 75
removal of simulated bathtub soil and 46% removal
of simulated shower wall soil. It is apparent that
the 6% solvent level, which is at the lower end of
the formulation range of the compositions of this
invention, while it reduces performance against both
types of soil, is still well within the range of
commercial products against bathtub soil and remains
superior to all commercial products against shower
wall soil.
Compositions ~, B, and C were homogeneous and
were stable indefinitely at room temperature.
Example 2
The following homogenous liquid compositions
were similarly prepared, with all figures being percent
11781BO
_2~
by weight, ~nd the balance being water:
D E F G
NaAE3S 2.5 0 2.5 2.5 wt.%
TKPP 13.8 13.8 10.0 13.8
5 dieth~lene glycol
mono n-but~l ether 10.0 10.0 10.0 5.0
coconut fatty acid 1.8 1.8 1.8 1.8
Na2C~3 1.55 1.55 1.55 1.55
NaHCO3 1.25 1.25 1.25 1.25
10 KTS 12.0 12.0 12.0 12.0
The a~oVe compositlons were tested in the
m~nner described in Example 1, With the following
results:
.
Product ~excenta~ie o~ Soil Removed
Soil Conc D ~ F G
~ .. ... . . . . ~
Kltchen Floor dilute 72 53 ~7 75
" ~all " 56 41 49 55
" " full str. 78 76 79 70
Bathroom Tub " "89 8~ 87 79
20 ~hower Wall" " 72 79 51 69
Composition D is the onl~ one of the foregoing
that is according to t~s invent~on. It is clearly
apparent from the above results that removal of surfactant
or reduction of builder to a level outside the scope of
this invention caused a significant reduction in cleaning
when the compositions were used in dilute form on either
simulated floor soil or wall soil; builder reduction
diminished effectiveness against simulated shower wall soil
as well. It is also clear that reduction of a solvent to a
level outside tha scope of this invention caused a signi-
ficant reduction in cleaning when the compositions wereused full strength on all three soils: simulated kitchen
wall, bathroom tub and shower wall soils. These data
~' ~
1 1781BO
.. . .. . . ....... . ..
. -29.-
demonstrate both the need and the effectiveness of
concurrent high levels of both builder and solvent, in
liquid compositions containing surfactant and other
ingredients, to obtain the multiple cleaning objectives
of this invention: a standard of accomplishment that
has not been achieved heretofore.
Other composi~ions are prepared like
Composition D except for the followlng differences:
Coconut fatty acid:
i~. omitted
~il lncreased to 4%
iiil oleic acid su~st~tutecl ~or coconut
atty acid
Su~stituted for NaAE3S:
vi~ C16 diethanolamide
viil coconut monoethanolam~de
viil~ sodium coconut alkyl sulfate
ixl C14 sodium paraffin sulfonate
x) C12 magnesium AE6S
xi~ coconut d~meth~l amine oxide
xii~ sodium salt of N-lauryl-N,N-dimethyl
- ammonio-hydroxy-propane-sulf~onic acid
xiii~ 1.8% NaAE3S plus 0.7% C14AE6 ~linear
alkyl ethoxylate containing 6 moieties
of ethylene oxide per moiety of myristyl
alcoholl
Substituted for car~onate~bicarbonate:
xi~l sodium orthophosphate
xvl sodium metasilicate
x~il sodium tetraborate
.
1 178~60
-30-
The cleaning performance of the foregoing compositions
is comparable to that of Composition D.
Example 3.
Compositions H and I were prepared according
to this invention as follows:
H
Na-Cll 8 linear al~yl
benzene sulfonate CLASl 10.0 - wt.
Na-~E3~ - 2.3
10 TKPP 13.8 13.8
diethylene glycol
mono-n-butyl ether lO.Q
diethyl succinate - 10.0
coconut atty acid 1.8 ~.6
15 Na2C3 1.6 1.6
Na~lCO3 1.2 1.2
KTS 12.0
Na cumene sulfonate - 7.Q
Na2SO3~ammonta~opacifier~color - 3.3
20 water bal. bal~
Each of t~e a~ove compositions ~as homogeneous
and stable indefinitely at room temperature. A number
of other compositions were pre~ared t~at ~ere identical
to Composition H except ox differences in sol~ent.
2~ They too were homogeneous and sta~le indefinitely at
room temperature. These solvents were: a mixture of
3% n-decane and 7% diethylene glycol mono-n-butyl
ether Chereinafter ~eferred to as DGBEI; a mixture of
3% cyclohexane and 7% DGBE; a mixture of 3% xylene and
7% DGBE; a mixture of 5% xylene and 5% DGBE; a mixture
o 2.2% diethyl benzene and 7.8~ DGBE; 10% but~l
acetate; 10~ amyl acetate; 10% diethyl carbonate; 8%
. . . . . . . .. .
Ba
-31-
diethyl succinate; 7.5% methyl i-amyl ketone; lQ%
methyl i-amyl ketone; 10% ethylene glycol mono-n-butyl
ether; 10~ ethylene glycol mono-n-hexyl ether; 10~
diethylene glycol mono-n-hexyl ether; 10% isopropylene
glycoL mono propyl ether; 10~ of a mixture of isopropylene
glycol mono-butyl, ethyl and propyl ethers tpropa
BEP, TM Union Carbide Corp.~; 6~ pine oil and 4
isopropyl alcohol; 2% pine oil and 8~ DGBE.
~11 of the compos~tions descri~ed in Example
3 hexein ~exe tested for cleaning performance on both
bathx~om soils ~n the manner described ~erein~efore.
Results were comparable to thase of compositions A and D.
Example 4.
.
The following composition was prepared,
was homogeneous and stable at room tempexature;
and cleans well accoxding to the tests described herein-
before,
J
NaLAS 8.~
20 Coconut fatt~ acid 1.4
TKPP 16.Q
KTS 1~.3
diethanola~ine 1.6
diethylene glycol mono-
n-butyl ether 12.Q
isopropyl alco~ol -
w~ter bal.
Example 5.
- Certain pure solvents were screened for
cleaning as de~cri~ed belo~. T~e Gardner test mac~ine
_.___ .... .. . .. .. ...... . .. . ... .. . .. .
!L 1~781GO
-32-
was used with simulated bathtub soil tiles and 2
grams of solvent per sponge. The data are consistent
with the selection of solvent parameters that define
the invention herein. The numbers which follow are
the number of strokes required, as judged visually,
to completely clean the tiles. Solvents meeting the
criteria herein for principal solvent: trichloro-
eth~lene - 4; xylene - 5; hexane - 5; chloroform - 5;
carbon tetrachlor~de - 6. Solvents not meeting the
criteria herein for principal solvent: meth~l ethyl
ketone - 18; l-hutanol - 2Q; dieth~lene glycol mono ~-
ethyl ether - 35; et~anol - 40; acetone - more than
4$; methanol - more than 45; dimethylfoxmamide -
more than 45,
Example 6.
The ~ollowing compositions o~ this invention
were prepared in greater quantlty ~or the purpose of
stabilit~ testing:
-K L M
NaLAS 10.0 4.0 ~ wt.%
NaAE3S 2.5
Coconut fatty acàd 1.8 1.8 1.2
TKPP 13.8 13.3 13.3
KTS 12.0 7.0 12.0
Na2C3 1.6
NaHC~3 1.2
diethanolamine - 2.0 2.0
diethylene ~lycol
~ono-n-butyl et~er lQ.0 8.5 8.5
30 pexfume - - Q.75
water bal. ~al. ~al.
Composition N was prepared identical to
that of Compos~tion Kexcept that its sol~ent ~as 10~
ethylene ~l~col mono-n-butyl ether. Compositions ~ and
", . '-
1 6 ~
N were clear, homogeneous liquids and remained so
after storaye for 3 months at 4, 21 and 49C. ~oth
fully recovered to their original homogeneoùs appearance
after 3 cycles alternating between 24 hours at -18C.
and 72 hours at +10C.
Composition O ~as prepared identical to that
of Composition L except that the KTS level was 12~.
Compositions L, ~ and O were tested using procedures
and obtainin~ results the same as for Compositions R
and N except that the storage tests at 4, 21 and
49C. we~e d~scontinued after 2 weeks, wit~ no visi~le
changes having occurred during that time.
Co~positions containing ~igher or lower
amounts of ~uilder and~or solvent ~ithin tAe scope of
this invention can be stabiliæed ~ adjusting levels
of ICTS and fatt~ acid within the ranges specified herein,
accordlny to principles known in the art. Diethanolamine
is pre~e~red to inorganic ~u~fers rom the standpoint
of inc~easing st~bilit~ under severe storage conditions.
i~
.. . ,
,' ~ '
