Note: Descriptions are shown in the official language in which they were submitted.
CA 02241815 1998-06-29
WO 97124425 PCTICJS95117044
Hard-Surface Cleaning Compositions
~o
~s
2o Teyhnical Field
The present invention relates to compositions for cleaning hard-surfaces,
especially in-house hard-surfaces.
Bac ground
A variety of compositions for cleaning hard-surfaces have been disclosed in
the art. Much of the focus for such compositions has been on providing
outstanding cleaning on a variety of surfaces and soils. For some
specialised cleaners, such as glass cleaners, much effort has additionally
CA 02241815 1998-06-29
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2
been devoted to the formulation of so-called "streak-free" products, i.e.
products which leave no or little visible residues after use.
The object of the present invention is to formulate hard-surface cleaning
compositions which clean and provide gloss to the cleaned surface. That is
different from a "streak-free" composition, in that gloss additionally
requires
improved reflectance of light from the cleaned surface. A variety of
products are commercially available for delivering gloss to surfaces, and
they are disclosed for instance in US 3,960,575 and US 4,218,250. Both
1o references recommend the use of various silicones for delivering gloss.
Such compositions are not fully formulated hard-surface cleaners, so that
they do not clean efficiently, and indeed the formulation of silicone in hard
surface cleaners has not shown any gloss benefits. See for instance EP 374
471 which discloses a hard-surface cleaning composition with, amongst
other essentials, a silicone for improved resistance to soil redeposition.
We have now found that superior gloss on surfaces can be obtained by
formulating liquid .compositions comprising a surfactant, a carboxylate-
containing polymer and a divalent counterion in a molar ratio of said polymer
2o to said divalent counterion of from 12:1 to 1:32. Indeed, it has been found
that said compositions provide excellent cleaning performance on different
types of stains including typical greasy stains while delivering improved
gloss and less surface streaking/spotting.
An advantage of the present invention is that said compositions may be
used to clean in-house hard-surfaces made of a variety of material like
glazed and non-glazed ceramic tiles, vinyl, linoleum, melamine, both in
diluted and neat conditions.
3o Another advantage of the process of cleaning hard-surfaces according to the
present invention wherein the compositions herein is used in diluted form is
that enhanced gloss is provided to the surfaces treated without the need of
a subsequent rinsing, thereby facilitating its usage by the consumer.
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3
US 4784 786 discloses a composition for cleaning glass which can be
readily applied to and removed from a soiled glass surface to leave the
surface clean and free of streaking and cloudiness. Said compositions
comprise amongst other ingredients, surfactants, glycol ether, an anionic
polysulfonic acid and an anhydride compound comprising an olefin-malefic
anhydride copolymer. No divalent counterions are disclosed.
WO 94/26858 discloses a liquid hard-surface composition (pH 2-8) with
nonionic surfactants (1-30%) and anionic polymers having an average
molecular weight of less than 1 000 000. Said compositions bring a
surprising initial cleaning benefit in addition to the anti-soiling benefit.
Indeed, WO 94/26858 discloses that acrylic, methacrylic and malefic
anhydride derivatives such as copolymers of styrene with malefic produce a
streak-free finish after drying. No divalent counterions are disclosed.
~5
EP-A-658 184 discloses liquid or gel dishwashing detergent compositions
containing alkyl amphocarboxylic acid (5°~6-9596) and magnesium or
calcium
salts (0.1 %-4%). said compositions having a pH in a 10% solution in water
at 20°C of 7 to 10. As optional ingredients said compositions comprise
co-
2o surfactants, like nonionic surfactants (5%-95%). No carboxylate-containing
polymers are disclosed. Also no hard-surfaces application is disclosed.
EP-A-162 033 discloses heavy-duty liquid detergents comprising proteolytic
or amylolytic enzymes, an anionic surfactant (10%-50%1, optionally other
25 surfactants like nonionic ethoxylated surfactants (2%-2596), from 1 to 30
millimoles of calcium ions per liter of composition and detergent builders
(2%-15%) like polycarboxylates including water-soluble salts of specific
polymeric aliphatic polycarboxylic acids (e.g., polymers and copolymers of
mafeic acid). EP-A-162 033 further discloses that the level of calcium ions
3o should be selected so that there is always some minimum level available for
the enzyme, after allowing for complexation with fatty acids and the like in
the composition. Sources of calcium ions are for example calcium chloride
andlor calcium acetate. No hard-surface application is disclosed.
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4
EP-A-602 179 discloses that the addition of calcium salts to compositions
containing a polyhydroxy fatty acid amide, and an anionic surfactant
improves the removal of greasy soils while delivering good hand mildness.
Indeed, EP-A-602 179 discloses dishwashing compositions comprising an
anionic surfactant (3°~-95%), a polyhydroxy fatty acid amide (3%-40%)
and
calcium ions (0.1 % to 3%). The compositions have a pH of from 5.5 to 10
in a 10°~ solution in water at 20°C. As optional ingredients
said
compositions comprise poiycarboxylate polymers having a molecular weight
of 750 000 to 4 000 000 (0.1 °~-10°r6). No hard-surface cleaning
application
~o is disclosed.
EP-A-fi70 884 discloses fully formulated liquid detergent compositions (pH
7.5-9.5) comprising a polyhydroxy fatty acid amide surfactant (596-
50°~), a
nonionic (596-506), a source of calcium (0.5°~-2°~) and soap.
Optional
ingredients are polycarboxylate builders such as copolymers of malefic
anhydride with ethylene or vinyl methyl ether and polymeric polycarboxylic
dispersing agents (0.1 °~-796) that can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers including acrylic acid, malefic
acid. Acryliclmaleic-based copolymers with a molecular weight of 2 000 to
100 000 are disclosed. No hard-surface application is disclosed.
GB 1430 204 discloses compositions suitable to clean various soiled
subtracts including hard-surfaces. Said compositions comprise a polymer
(396-3596) such as acrylic polymers and polycarbonates, optionally metal
ions such as calcium or magnesium (0.1 °r6-5%), and builders (0.1 %-5%)
such as copolymers of vinyl methyl ether and malefic anhydride, and
carboxymethyl cellulose. A surfactant may be used as optional but no levels
thereof are disclosed, let alone particular classes of surfactants. GB 1 430
204 also discloses a process of cleaning a soiled surface, said process
3o comprising the steps of applying to said surface said composition, allowing
said composition to form a tacky film to which soils adhere, allowing said
composition to dry, whereby as a result of said drying, said film fractures to
form a removable residue and then removing said residue. The presence of
the metal ions increases the brittieness of the film.
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WO 97124425 PCT/US95/17044
Actually, the benefit derivable from the use of a surfactant, a carboxylate
containing polymer and a divalent counterion in appropriate molar ratios of
said polymer to said divalent counterion, in a liquid hard-surface cleaning
composition, i.e. improved gloss to the surfaces treated therewith, has not
5 been acknowledged in the prior art.
Summary of the invention
The present invention encompasses a process of cleaning hard-surfaces
wherein a liquid composition comprising a carboxylate-containing polymer
and a divalent counterion in a molar ratio of said polymer to said divalent
counterion of from 12:1 to 1:32 and from 0.1 % to 5096 by weight of the
~5 total composition of a surfactant, is applied onto said surfaces.
The present invention also encompasses a liquid hard-surface cleaning
composition comprising a carboxylate-containing polymer and a divalent
counterion in a molar ratio of said polymer to said divalent counterion of
2o from 12:1 to 1:32 and from 0.1 °~6 to 50°r6 by weight of the
total
composition of a surfactant, said composition being free of a proteolytic or
amylolytic enzyme and of polyhydroxy fatty acid amide.
Detailed Description of the invention
In its broadest aspect, the present invention relates to a process of cleaning
hard-surfaces wherein a liquid composition comprising a carboxylate-
containing polymer and a divalent counterion in a molar ratio of said polymer
to said divalent counterion of from 12:1 to 1:32 and a surfactant, is applied
onto said surfaces.
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6
By "hard-surfaces" it is meant herein any kind of in-house hard-surfaces
with the exception of dishes and any ustensiles used for the cooking and for
eating/drinking. Preferred herein "hard-surfaces" has to be understood as
any fixed household hard-surface including floors, walls, windows, fixtures
and fittings and the like.
Said liquid composition may be applied to the surface to be cleaned in its
neat form or in its diluted form.
By "diluted form" it is meant herein that said liquid composition is diluted
by
the user typically with water. The composition is diluted prior use to a
typical dilution level of 10 to 200 times its weight of water. Usual
recommended dilution level is a 1.2% dilution of the composition in water
which corresponds to an active level of from 0.01 °~ to 0.5°~ by
weight of
the resulting washing solution.
When applying said composition to the surface to be cleaned in its neat form
or in a so-called concentrated form ti.e. between 10°~-40°~
total activesl, it
is necessary to rinse the surface after the composition has been applied,
otherwise too many visible residues are left on the surface. In this
"concentrated" usage form, however, the gloss benefit provided by the
compositions of the present invention is still obtained after fewer rinses
than
would otherwise be required when using the same composition without said
surfactant or the same composition without said polymer and said divalent
counterion in a molar ratio of said polymer to said divalent counterion of
from 12:1 to 1:32.
In the preferred process of cleaning hard-surfaces according to the present
invention where said composition is used in diluted form, there is no need to
3o rinse the surface after application of the composition in order to obtain
the
gloss benefit.
In one embodiment the present invention is a liquid hard-surface cleaning
composition comprising a carboxylate-containing polymer and a divalent
counterion in a molar ratio of said polymer to said divalent counterion of
CA 02241815 1998-06-29
WO 97124425 PCT/US95117044
7
from 12:1 to 1:32 and from 0.1 % to 50% by weight of the total
composition of a surfactant, said composition being free of a proteolytic or
amylolytic enzyme and of polyhydroxy fatty acid amide.
As a first essential ingredient, the compositions according to the present
invention comprise a carboxylate-containing polymer, or mixtures thereof.
By "carboxylate-containing polymer" it is meant herein a polymer or
copolymer comprising at least a monomeric unit which contains at least a
carboxylate functionality. Any carboxyiate-containing polymer known to
those skilled in the art can be employed according to the present invention
such as homo- or co-polymeric polycarboxylic acids or their salts including
polyacrylates and polymers and copolymers of malefic anhydride or/and
acrylic acid and the like, or mixtures thereof. Indeed, such carboxylate-
containing polymers can be prepared by polymerizing or copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated
monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric acid, itacon.ic acid, aconitic acid, mesaconic acid, citraconic acid
and
methylenemalonic acid. The presence in the polymeric polycarboxylates
herein of monomeric segments, containing no carboxylate radicals such as
vinylmethyl ether, styrene, ethylene, etc. is suitable.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the
water-soluble salts of polymerized acrylic acid. The average molecular
weight of such polymers in the acid form preferably ranges from about
2,000 to 1,000,000, more preferably from about 10,000 to 150,000 and
most preferably from about 20,000 to 100,000. Water-soluble salts of such
acrylic acid polymers can include, for example, the alkali metal, ammonium
and substituted ammonium salts. Soluble polymers of this type are known
materials. Use of polyacrylates of this type in detergent compositions has
been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March
7, 1967.
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WO 97!24425 PCT/US95117044
8
Acrylic/maleic-based copolymers may also be used as a preferred
carboxylate-containing polymer. Such materials include the water-soluble
salts of copolymers of acrylic acid and malefic acid. The average molecular
weight of such copolymers in the acid form preferably ranges from about
2,000 to 100,000, more preferably from about 5,000 to 75,000, most
preferably from about 7,000 to 65,000. The ratio of acrylate to maleate
segments in such copolymers will generally range from about 30:1 to about
1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such
acrylic acidlmaleic acid copolymers can include, for example, the alkali
1o metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which are
described in European Patent Application No. 66915, published December
15, 1982. Particularly preferred is a copolymer of malefic I acrylic acid
with an average molecular weight of about 70,000. Such copolymers are
commercially available from BASF under the trade name SOKALAN CPS.
Other suitable carboxylate-containing polymers to be used herein include
cellulose derivatives such as carboxymethylcellulose. For example
carboxymethylcellulose may be used as a salt with conventional cation such
2o as sodium, potassium, amines or substituted amines.
As a second essential ingredient, the compositions according to the present
invention comprise a divalent counterion, or mixtures thereof. All divalent
ions known to those skilled in the art may be used herein. Preferred divalent
ions to be used herein are calcium, zinc, cadmium, nickel, copper, cobalt,
zirconium, chromium and/or magnesium and more preferred are calcium,
zinc and/or magnesium. Said divalent ions may be added in the form of salts
for example as chloride, acetate, sulphate, formats andlor nitrate or as a
complex metal salt. For example, calcium may be added in the form of
3o calcium chloride, magnesium as magnesium acetate or magnesium sulphate
and zinc as zinc chloride.
In one embodiment of the present invention said carboxylate-containing
polymer and said divalent counterion may be added as one ingredient
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WO 97124425 PCTIUS95117044
9
provided that the molar ratio of said carboxyiate-containing polymer to said
divalent counterionlsalt is from 12:1 to 1:32.
According to the present invention, said polymer and said divalent
counterion are present in the compositions for cleaning hard-surfaces herein
in a molar ratio of said polymer to said divalent counterion of from 12:1 to
1:32, preferably of from 8:1 to 1:1 fi, more preferably of from 6: 7 to 1:12
and most preferably of from 4:1 to 1:6. Preferred molar ratios of said
polymer to said divalent counterion are those where improved gloss is
1o obtained in the most economic way.
By "molar ratio of said polymer to said divalent counterion" it is meant
herein the number of moles of carboxylate-containing monomer to the
number of moles of divalent ion. For example, in a preferred embodiment of
~5 the present invention where said carboxyiate-containing polymer is an
acrylic acid/maleic acid copolymer the molar ratio is stated as a range based
on the theoretical molar ratio of a pure acrylic acid polymer to divalent ions
and a pure malefic acid polymer to divalent ions.
20 Accordingly, the compositions for the cleaning of hard-surfaces according
to
the present invention comprise from 0.01 % to 20% by weight of the total
composition of said carboxylate-containing polymer, or mixtures thereof,
preferably from 0.1 % to 10%, more preferably from 0.1 % to 5°~ and
from
0.0196 to 4% by weight of the total composition of said divalent counterion,
25 or mixtures thereof, preferably from 0.02 r6 to 2%, and more preferably
from
0.02% to 1 %.
By "improved gloss" it is meant herein that the gloss observed, when
cleaning a hard-surface according to the present invention with a
3o composition comprising a surfactant, a carboxylate-containing polymer and a
divalent counterion in a molar ratio of said polymer to said divalent
counterion of from 12:1 to 1:32, is improved as compared to the gloss
observed when cleaning said surface with the same composition without
said surfactant, or with the same composition without said divalent
35 counterion and said carboxylate-containing polymer in a molar ratio of said
CA 02241815 1998-06-29
WO 97/24425 PCTIUS95l17044
polymer to said divalent counterion of from 12:1 to 1:32. This gloss
improvement is observed in both neat or diluted usage conditions, and
especially in the embodiment where the diluted usage is performed with soft
water, i.e. a water with a water hardness of less than 10 grains/gallons.
5 This gloss benefit may be evaluated by reflectance as judged by a gloss
meter and/or by a visual grading as judged by a panel of graders.
As a third essential ingredient, the compositions according to the present
invention comprise a surfactant, or mixtures thereof. Said surfactant is
1o present in the compositions according to the present invention in amounts
of
from 0.1 % to 50% by weight of the total composition, preferably from
0.1 °r6 to 20°rb and more preferably of from 1 °~ to 10%.
It is said surfactant
which in combination with said polymer and divalent counterion, is
deposited on the surface cleaned and contributes to the gloss benefit.
Surfactants to be used herein include nonionic surfactants, anionic
surfactants, cationic surfactants, amphoteric surfactants, zwitterionic
surfactants, and mixtures thereof.
Particularly preferred surfactants are the nonionic surfactants. Suitable
2o nonionic surfactants for use herein include a class of compounds which may
be broadly defined as compounds produced by the condensation of alkylene
oxide groups (hydrophilic in nature) with an organic hydrophobic compound,
which may be branched or linear aliphatic (e.g. Guerbet or secondary
alcohols! or alkyl aromatic in nature. The length of the hydrophilic or
polyoxyalkylene radical 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.
For example, s well-known class of nonionic synthetic detergents is made
available on the market under the trade name "Pluronic". These compounds
3o are formed by condensing ethylene oxide with an hydrophobic base formed
by the condensation of propylene oxide with propylene glycol. The
hydrophobic portion of the molecule which, of course, exhibits water-
insolubility has a molecular weight of from about 1500 to 1800. The
addition of polyoxyethylene radicals to this hydrophobic portion tends to
increase the water-solubility of the molecule as a whole and the liquid
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WO 97124425 PCTIUS95117044
11
character of the products is retained up to the point where polyoxyethyiene
content is about 50% of the total weight of the condensation product.
Other suitable nonionic synthetic detergents include
(i) The polyethylene oxide condensates of alkyl phenols, e.g., the
condensation products ~of alkyl phenols having an alkyl group
containing from about 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 10 to 25 moles of ethylene
oxide per mole of alkyl phenol. The alkyl substituent in such
compounds may be derived from polymerized propylene, diisobutylene,
octane, and nonane;
(ii) Those derived from the condensation of ethylene oxide with the
product resulting from the reaction of propylene oxide and ethylene
diamine products which may be varied in composition depending upon
the balance between the hydrophobic and hydrophilic elements which
is desired. Examples are compounds containing from about 40% to
2o about 80°~ pofyoxyethylene by weight and having a molecular weight
of from about 5000 to about 11000 resulting from the reaction of
ethylene oxide groups with a hydrophobic base constituted of the
reaction product of ethylene diamine and excess propylene oxide, said
base having a molecular weight of the order of 2500 to 3000;
(iii) The condensation product of aliphatic alcohols having from 8 to 18
carbon atoms, in either straight chain or branched chain configuration,
with ethylene oxide, e.g.. a coconut alcohol ethylene oxide condensate
having from 10 to 30 moles of ethylene oxide per mole of coconut
alcohol, the coconut alcohol fraction having from 10 to 14 carbon
atoms;
(iv) Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl
group ranges from 10 to 18 carbon atoms and two alkyl groups range
from 1 to 3 carbon atoms; the alkyl groups can contain hydroxy
CA 02241815 1998-06-29
WO 97124425 PCT/US95/17044
12
substituents; specific examples are dodecyl di(2-hydroxyethyl)amine
oxide and tetradecyl dimethyl phosphine oxide.
Particularly preferred surfactants include also the anionic surfactants.
Suitable anionic surfactants for use herein include alkali metal /e.g., sodium
or potassium) fatty acids, or soaps thereof, containing from about 8 to
about 24, preferably from about 10 to about 20 carbon atoms.
The fatty acids including those used in making the soaps can be obtained
1o from natural sources such as, for instance, plant or animal-derived
glycerides
(e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow,
whale
oil, fish oil, tallow, grease, lard and mixtures thereof). The tatty acids can
also be synthetically prepared (e.g., by oxidation of petroleum stocks or by
the Fischer-Tropsch process). Alkali metal soaps can be made by direct
saponification of fats and oils or by the neutralization of the free fatty
acids
which are prepared in a separate manufacturing process. Particularly useful
are the sodium and potassium salts of the mixtures of fatty acids derived
from coconut oil and tallow, i.e., sodium and potassium tallow and coconut
soaps.
The term "tallow" is used herein in connection with fatty acid mixtures
which typically have an approximate carbon chain length distribution of
2.5% C14, 29% C16, 23% C18, 2°rb paimitoleic, 41.5% oleic and
3°/a
finoleic (the first three fatty acids listed are saturatedl. Other mixtures
with
similar distribution, such as the fatty acids derived from various animal
tallows and lard, are also included within the term tallow. The tallow can
also be hardened (i.e., hydrogenated) to convert part or all of the
unsaturated fatty acid moieties to saturated fatty acid moieties. When the
term "coconut" is used herein it refers to fatty acid mixtures which typically
3o have an approximate carbon chain length distribution of about 8% C8, 7%
C10, 48% C12, 17% C14, 9°~ C16, 2°~ C18, 7% oleic, and
2°~ linoleic
(the first six fatty acids listed being saturated). Other sources having
similar
carbon chain length distribution such as palm kernel oil and babassu oil are
included with the term coconut oil.
~ i ii ...I~~, ~ ~ ~~I ~ ' ~~ I
CA 02241815 2002-07-15
13
Other suitable anionic surfactants for use herein include water-soluble salts,
particularly the alkali metal salts, of organic sulfuric reaction products
having
in the molecular structure an alkyl radical 'containing from about 8 to about
22 carbon atoms and a radical selected from the group consisting of sulfonic
acid and sulfuric acid ester radicals. important examples of these synthetic
detergents are the sodium, ammonium or potassium alkyl sulfates, especially
those obtained by sulfating the higher alcohols produced by reducing the
glycerides of tallow or coconut oil; sodium or potassium alkyl benzene
sulfonates. in which the alkyl group contains from about 9 to about 15
carbon atoms, especially those of the types described in U.S. Pat. Nos.
2.220.099 and 2,477,383. . . . sodium alkyl
giyceryl ether sulfonates, especially those ethers of the higher alcohols
derived from tallow and coconut oil; sodium coconut oil fatty acid
~ 5 monogiyceride sulfates and sulfonstes; sodium or potassium salts of
sulfuric
acid esters of the reaction product of one mole of a higher fatty alcohol
(e.g., tallow or coconut oil afcoholsl and about three moles of ethylene
oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether
sulfates with about four units of ethylene oxide per molecule and in which
2o the alkyl radicals contain about 9 carbon atoms: the reaction product of
fatty acids esterified with isothionic acid and neutralized with sodium
hydroxide where, for example, the fatty acids are derived from coconut oil;
sodium or potassium salts of fatty acid amide of a methyl taurine in which
the fatty acids, for example, are derived from coconut oil; and others known
Zs in the art, s number being specifically set forth in U.S. Pat. Nos.
2,486.921,
2.488,922 end 2.398.278, .
Suitable zwittsrionic detergents to be used herein comprise the betaine and
30 betaine~like detergents wherein the molecule contains both basic and acidic
groups which form an inner salt giving the molecule both cationic and
anionic hydrophilic groups over a broad range of pH values. Some common
examples of these detergents are described in U.S. Pat. Nos. 2,082,275,
2.702.279 and 2,255.082. Preferred
35 zwitterionic detergent compounds have the formula
. . ;. : ,. # ".~# : ~r f #I
CA 02241815 2002-07-15
14
R2
s I
R1 -N+-CHZ-R4-Y_
I I
R3 X
wherein R1 is an alkyl radical containing from about 8 to about 22 carbon
atoms, R2 and R3 contain from 1 to 3 carbon atoms, R4 is an alkylene chain
containing from 1 to about 3 carbon atoms, X is selected from the group
consisting of hydrogen and a hydroxyl radical, Y is selected from' the group
consisting of carboxyl and sulfonyi radicals and wherein the sum of R1, R2
is and R3 radicals is from about 14 to about 24 carbon atoms.
Amphoteric and ampholyt~ detergents which can be either cationic or
anionic depending upon the pH of the system are represented by detergents
such as dodecylbeta-alanine, N-alkyttaurinss such as the one prepared by
2o reacting dodecylamine with sodium isethionate according to the teaching of
U.S. Pat. No. 2.888.072. N-higher alkylaspartic acids such as those
produced according to the teaching of U.S. Pat. No. 2,438,091, and the
products sold undr the trade name "Miranol", and described in U.S. Pat.
No. 2.528~378~ .
2s Addidonsl syrrd»dc detergents and iisd~gs of their commercial sources can
be found in McCutcheon's Detergent: and Emulsifiers. North American Ed.
1980.
,.
F 'F
The compositbns according to the present invention are liquid hard-surface
3o cleaning compo:itirans. The liquid compositions of the present invention
are
preferably but not necessarily formulated as aqueous compositions.
Aqueous compositions typically comprise from 50% to 98% by weight of
the total composition of water, preferably from 80% to 95%, and more
preferably from 80% to 95%.
3s
. , ~:E.~i,~ , an ~i ~ .
CA 02241815 2002-07-15
t5
The compositions according to the present invention have a pH of from 6 to
13, preferably of from 6.5 to 12, and more preferably of from 7 to 11. The
pH of the compositions herein can be adjusted by any of the means well
known to the man skilled in the art such as addition of NaOH, KOH, K2C03,
Na2C03 and the like.
The compositions herein can further comprise a variety of optional
ingredients. Suitable optional ingredients for use herein include builders,
chelants, solvents, buffers, bactericides, hydrotropes, colorants, stabilizers
to and/or perfumes.
Suitable perfumes to be used herein include materials which provide an
olfactory aesthetic benefit andlor cover any "chemical" odor that the
product may have. The main function of a small fraction of the highly
t5 volatile, low boiling (having low boiling poirttsl. perfume components in
these perfumes is to improve the fragrance odor of the product itself, rather
than impacting on the subsequent odor of the surface being cleaned.
However, some of the less volatile, high boiling perfume ingredients provide
a fresh and clean impression to the surfaces, and it is desirable that these
20 ingredients be depos'tted and present on the dry surface. Perfume
ingredients can be readily aolubilized in the composit'rons. for instance by
the
nonionic detergent surfactsnts.The perfume ingredients and compositions
suitable to be used herein are the conventionsl ones known in the an.
Selection of any perfume coAnponent. or amount of perfume, is based solely
2s on aesthetic considerations.
Suitable perfurtw compounds end compositions can .be found in the art
;_ ;. inching U.S. Pet. Nos. : 4.145.184. Brain and Cummins. issued March 20,
1979: 4,209,417, Whyte, issued June 24. 1980: 4,515,705. Moeddel,
3o issued May 7, 1985; and 4,152.272, Young, issued May 1, 1979. -
In general, the degree of
substantivity'of a perfume is roughly proportional to the percentages of
substantive perfume material used. Relatively substantive perfumes contain
at least about 1 %, preferably at least about 10%, substantive perfume
35 materials.Substantive perfume materials are those odorous compounds that
~; ''~ I ~ ili~ il,:'v ~i ~
CA 02241815 2002-07-15
16
deposit on surfaces via the cleaning process and are detectable by people
with normal olfactory acuity. Such materials typically have vapor pressures
lower than that of the average perfume material. Also, they typically have
molecular weights of about 240 and above, and are detectable at levels
below those of the average perfume materiai.Perfume ingredients useful
herein, along with their odor character, and their physical and chemical
properties, such as boiling point and molecular weight, are given in "Perfume
and Flavor Chemicals (Aroma Chemicalsl." Steffen Arctander; published by
the author, 1989. - .
Examples of the highly volatile, low boiling, perfume ingredients are .
anethole. bsnzaldehyds, benzyl acetate, benzyl alcohol, bens~l formats, iso-
bomyl acetate. csmphene. ciacitral Inerali. citronellal, citronellol,
citronehyl
acetate, pare-cymene. decanai, dihydrolinalool, dihydromyrcenoi, ' dimethyl
t5 phenyl carbinol, eucaliptol, geranial, geranioi, geranyl acetate, geranyi
nitrite,
cis-3-hexenyl acetate, hydroxycitfonellal, d-limonene, linalool, linalool
oxide.
linalyl acetate. linaiyl propionate, methyl anthrsnilate. alpha-methyl ionone,
methyl nonyl acetaldehyde, methyl phenyl csrbinyl acetate, laevo-menthyi
acetate, msnthone, iso-menthone, mycrene. myrcenyl acetate, myrcenol,
2o neroi, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene,
beta-
pinsne. gamma-terpinene, alpha-terpineol, bete~tsrpineoi, terpinyl acetate.
and vertenex Ipara-tertiary-butyl cyclohexyi acetate). Soma natural oils also
contain large percentages of highly volatile perfume ingredients. For
example, iavandin contains as mayor components : linalool; linalyl acetate:
25 geranaol; and cit<onsibi. Lemon oil and orange terpenes both contain about
9~9i of d-limonene.
Examples of moderately volatile perfume ingredients are : amyl cinnamic
aklehyde. iso-amyl saiicylats. beta-caryophyllene, cedrene, cinnarmic alcohol,
30 coumarin, din>~yl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-
augenol, fior acetate, heliotropine, 3-cis-hexenyl saiicylats. hexyl
salicylste.
liliai (pare-tsrtiarybutyhalpha-methyl hydrocinnamic aldehyde?. gamma-
methyl ionons. neroiidol, patchouli alcohol, phenyl hexanol, beta-aslinene,
trichloromethyi phenyl carbinyl acetate, tristhyl citrate, vanillin, and
CA 02241815 1998-06-29
WO 97/24425 PCTIUS95/17044
17
veratraldehyde. Cedarwood terpenes are composed mainly of alpha-
cedrene, beta-cedrene, and other C15H24 sesquiterpenes.
Examples of the less volatile, high boiling, perfume ingredients are
benzophenone, benzyl salicylate, ethylene brassylate, galaxolide
( 1, 3, 4, 6, 7, 8-hexahyd ro-4, 6, 6, 7, 8, 8-hexamethyl-cyclopenta-gama-2-
benzopyran), hexyl cinnamic aldehyde, lyral (4-(4-hydroxy-4-methyl pentyl)-
3-cyclohexene-10-carboxaldehyde), methyl cedrylone, methyl dihydro
jasmonate, methyl-beta-naphthyl ketone, musk indanone, musk ketone,
musk tibetene, and phenylethyl phenyl acetate.
Selection of any particular perfume ingredient is primarily dictated by
aesthetic considerations.
The compositions herein may comprise a perfume ingredient, or mixtures
thereof, in amounts up to 5.0°~ by weight of the total composition,
preferably in amounts of 0.1 % to 1.5%.
Another class of optional compounds are chelating agents such as those
selected from the group of aminophosphonates. Suitable amino
phosphonate compounds for use herein include amino alkylene poly
(alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates,
nitrilo trimethyfene phosphonates, ethylene diamine tetra methylene
phosphonates, and diethylene triamine yenta methylene phosphonates. The
phosphonate compounds may be present either in their acid form or as salts
of different cations on some or all of their acid functionalities. Preferred
amino phosphonate chelant to be used herein is diethylene triamine yenta
methylene phosphonate. Such phosphonate chelant is commercially
3o available from Monsanto under the trade name DEQUEST~.
Chelants can be incorporated in the compositions herein in amounts ranging
from 0.0°i6 to 10.0% by weight of the total composition, preferably 0.1
% to
5.096.
CA 02241815 1998-06-29
WO 97/24425 PCTIUS95/17044
18
The present invention will be further illustrated by the following examples.
10
The following compositions were made by mixing the listed ingredients in
the listed proportions. All proportions are °~6 by weight of the total
composition. These compositions were used neat and diluted to clean hard
surfaces like floors. Excellent cleaning performance and excellent gloss were
~5 delivered to the surfaces cleaned.
Compositions (weight96) 1 2 3 4
C7JC9/C11 EOfi.5 3.0 3.0 3.0 3.0
2o C 12/C 13 E03 1.0 1.0 1.0 1.0
C13/C15 E030 2.0 2.0 2.0 2.0
Palm Kernal Fatty Acid 0.4 0.4 0.4 0.4
Perfume 0.45 0.45 0.45 0.45
Sokolan~ CP5' 1.0 0 0 0
25 Sokolan~ CP7 * ~ 0 1.0 0 0
Carboxymethyl cetlulose 0 0 1.0 0
Primal~ B 924' ~ 0 0 0 1.0
CaC12.2H20 1.0 1.0 1.0 1.0
Water and minors --------up 100%--------
to
30 pH 10.5 10.5 10.5 10.5
The molar ratio of said carboxylate-containing polymer to calcium ions in
examples 1 to 3 is from 2.1:1 to 1.2:1.
35 ~ Malefic acid-acrylic acid copolymer (MW = 70 0001
CA 02241815 1998-06-29
WO 97/24425 PCT/C1S95117044
19
"' Polycarboxylate copolymer (MW = 50 000?
'" * *' Polyacrylate containing emulsion commercially available from Rohm
and
Hass.
s
Compositions Iweight96) 5 6 7 8 9 10 11
C7/C9lC 11 E06.5 3.0 3.0 3.0 3.0 3.0 0.0 0.0
C12/C13 E03 1.0 1.0 1.0 1.0 1.0 1.0 1.0
1o C13/C15 E030 2.0 2.0 2.0 2.0 2.0 4.0 4.0
Palm Kernal Fatty Acid 0.4 0.4 0.4 0.4 0.4 0.4 0.0
Perfume 0.45 0.45 0.45 0.45 0.450.3 0.3
Sokolan CP5' 1.0 1.0 1.0 1.0 3.0 0.5 0.5
CaC12.2H20 0.5 0 0 0.5 1.0 1.0 0.0
15 MgS04.7H20 0 1.68 0 0 0 0 0.5
ZnCl2 0 0 0.93 0 0 0 0
Water and minors ---------------------up to
10096------------------------
pH 10.5 10.5 10.5 10.5 10.510.5 10.5
20 The molar ratio of said containing to
carboxylate- polymer said
divalent
ions
in examples 5 and 8 is from 4.2:1to examples and is
2.4:1, 6 7 from
in
2.1: 7 to 1.2:1, in example s to example is
9 i from 3.6:1, 10 from
6.3:1 in
1.1:1 to 1:1.7, and from to
3.5:1 2.1:1
in
example
11.
Malefic acid-acrylic acid copolymer (MW = 70 000?
