Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02234407 1998-04-08
1
Hard Surface Cleaning Compositions
10
Technical Field
The present invention relates to compositions for cleaning hard surfaces.
Background
A variety of composfions for cleaning hard surfaces have been disclosed in the
art. Much of the focus for such compositions has been on providing
2 s outstanding cleaning on a variety of surfaces and soils. For some
specialised
cleaners, such as glass cleaners, much effort has additionally been devoted to
the formulation of so-called "streak-free" products, i.e. products which leave
no
or little visible nasidues after use.
3 o The aspect 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" compositan, 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
35 disclosed for instance in US 3,960,575 and US 4,218,250. Both references
recommend the use of various silicones for delivering gloss. Such
CA 02234407 1998-04-08
WO 97/13836 PCT/US96/15644
2
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 surface can be obtained from a hard
surface cleaning composition comprising a sulphonated homopolymer of (poly)
styrene or a sulphonated copolymer of styrene with an ethylenically
unsaturated
comonomer, or mixtures of said polymers.
Suitable Polystyrenes sulphonates for use herein are disclosed for instance in
"Multifunctional Sulphonated Polymers for Household Applications", J. Guth et
AI. Haapi, December '94. The Guth article mentions that the key benefit of
such polymers in the context of hard surface cleaners is anti soil
redeposition,
but does not discuss gloss.
Summary of the invention
in one embodiment, the present invention encompasses a hard surface
cleaning composition comprising an anionic surfactant, a nonionic surfactant,
a
perfume and a sulphonated (poly) styrene or a sulphonated copolymer of
styrene with an ethylenically unsaturated comonomer, or mixtures of said
polymers.
In a second embodiment, the present invention encompasses a process of
cleaning a hard surface by applying on said surface an effective amount of a
composition defined herein.
In a third embodiment, the present invention encompasses the use of a
sulphonated homopolymer of (poly) styrene or a sulphonated copolymer of
styrene with an ethylenically unsaturated comonomer, or mixtures of said
polymers, in a hard surface cleaning composition, for providing gloss to the
surfaces being cleaned with said compositions.
CA 02234407 1998-04-08
WO 97/13836 PCT/US96/15644
3
Detailed Description of the invention
The compositions herein are hard surface cleaning compositions. The
. compositions can thus be formulated either as solids or liquids, but are
used in
a liquid form to ensure even delivery of the polymer, as a layer, onto the
surface
being cleaned. In the case where the compositions are formulated as solids,
they will thus be mixed with an appropriate solvent, typically water, before
use.
In liquid form, the compositions are preferably but not necessarily formulated
as
aqueous compositions.
As a first essential ingredient, the compositions herein comprise a
sulphonated
homopolymer of (poly) styrene, or a sulphonated copolymer of styrene with an
ethylenically unsaturated comonomer. The polymers are present in the
compositions herein in preferred amounts of up to 20.0% by weight of the total
composition, most preferably 0.1 % to 5.0%. It is said polymers which, upon
use, is deposited on the surface being cleaned, which provides the gloss
benefit. Two different types of sulfonated polymers are useful herein.
The first type is a sulfonated homopolymer of styrene. The second type is a
sulfonated interpolymer of styrene with an ethylenically unsaturated
comonomer. The useful compounds herein include the partially or fully
neutralized salts of either the sulfonated polystyrene or the sulfonated
styrene
interpolymers, i.e. the soluble salts of these polymers, wherein the sulfonic
acid
groups are partially or fully neutralized.
Suitable ethylenically unsaturated comonomer units which can be
copolymerized with styrene to make the interpolymers suitable for sulfation
include acrylic and methacrylic esters of aliphatic alcohols such as methyl,
ethyl, butyl and 2-ethyl hexyl alcohols, acrylic acid, acrylonitrile,
methacrylonitrile, dibutyl maleate, vinylidene chloride, N-vinyl pyrrolidone
etc ...
Particularly preferred ethylenically unsaturated monomers for use herein
include ethylene, propylene, styrene, vinyl naphthalene, acrylic acid and
maieic
anhydride.
Sulphonated styrene homopolymers suitable for use herein are commercially
available under the trade name Versaflex~ from National Starch. Most suitable
polymers and copolymers for use herein will be water soluble, and the
CA 02234407 1998-04-08
WO 97/13836 PCT/US96/15644
4
molecular weight for these polymers is preferably between 5000 and
10,000,000, most preferably between 50,000 and 1,000,000.
As a second essential ingredient, the compositions herein comprise an anionic
surfactant or mixtures thereof, preferably in amounts of up to 50% by weight
of
the total composition, most preferably from 0.1 % to 10.0%.
Particularly preferred 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 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 fatty 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% Clg, 23% Clg, 2% palmitoleic, 41.5% oleic and 3% linoleic (the first three
fatty acids listed are saturated). 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 have an approximate carbon chain length distribution of about 8% Cg,
~% C10, 48% C12, 17% C14, 9% Clg, 2% Clg, 7% oleic, and 2% linoleic (the
first six fatty acids listed being saturated). Other sources having similar
carbon
CA 02234407 2001-12-21
chain length distribution such as palm kernel oil and babassu oil are included
with the term,~oconut oil.
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, - podium alkyl glyceryl ether
sulfonates, especially those ethers of the higher alcohols derived from tallow
and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and
sulfonates; 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
alcohols) 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 the alkyl radicals contain about 9 carbon
atoms; the reaction product of fatty acids esterfied 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
methyle taurine in which the fatty acids, for example, are derived from
coconut
oil; and others known in the art, a number being specfically set forth in U.S.
Pat. Nos. 2,488,921, 2,488,922 and 2,396,278.
As a third essential ingredient, the compositions herein comprise a nonionic
surfactant or mixtures thereof, preferably in amounts of up to 50.0% by weight
of the total composition, most preferably from 0.1 % to 20.0%.
Suitable 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
CA 02234407 2001-12-21
6
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, a well-known class of nonionic synthetic detergents is made
available on the market under the trade name "PluronicT""". These compounds
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 character of the products is retained up to
the point where polyoxyethylene 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, for example;
(ii) Those derived from the condensation of ethylene oxide with the product
resumng 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°r6 to about 80% polyoxyethylene by
weight and having a molecular weight of from about 5000 to about 11000
resu~ing 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, are
satisfactory;
CA 02234407 2001-12-21
7
(iii) The condensation product of aliphatic alcohois 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 substituents; specific
examples are dodecyl di(2-hydroxyethyl)amine oxide and tetradecyl dimethyl
phosphine oxide.
The compositions herein can further comprise other surfactants, cationics,
zwitterionics, and mixtures thereof. Zwitterionic detergents comprise the
betaine and 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, -
Suitable rnritterionic detergent compounds have the formula
R2
I
R1 -N+-CH2-R4-Y-
I I
R3 X
wherein R1 i5 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 sulfonyl radicals and wherein the sum of R1, R2 and
R3 radicals is from about 14 to about 24 carbon atoms.
Amphoteric and amphoiytic detergents which can be either cationic or anionic
depending upon the pH of the system are represented by detergents such as
dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting
CA 02234407 2001-12-21
8
dodecylamine with sodium isethionate according to the teaching of U.S. Pat.
No. 2,658,072, N-higher alkylaspartic acids such as those produced according
to the teaching of U.S. Pat. No. 2,438,091, and the products sold under the
trade name «MiranolT""", and described in U.S. Pat. No. 2,528,378.
Additional synthetic detergents and listings of their commercial sources can
be
found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980 (MC
Publishing Company, Ridgewood, NJ)
As a fourth essential ingredient, the compositions herein comprise a perfume
ingredient, or mixtures thereof, preferably in amounts of up to 5.0% by weight
of
the total composition, most preferably 0.1 % to 1.5%.
Suitable perfumes herein include materials which provide an olfactory
aesthetic
benefit and/or cover any "chemical" odor that the product may have. The main
function of a small fraction of the highly volatile, low boiling (having low
boiling
points), 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 flesh and clean impression to the surfaces, and
it
is desirable that these ingredients be deposited and present on the dry
surface.
Perfume ingredients can be readily solubilized in the compositions, for
instance
by the nonionic detergent surfactants.
The perfume ingredients and compositions of this invention are the
conventional ones known in the art. Selection of any perfume component, or
amount of perfume, is based solely on aesthetic considerations. Suitable
perfume compounds and compositions can be found in the art including U.S.
Pat. Nos. : 4,145,184, Brain and Cummins, issued March 20, 1979; 4,209,417,
Whyte, issued June 24, 1980; 4,515,705, Moeddel, 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
CA 02234407 2001-12-21
9
perfumes contain at least about 1 %, preferably at least about 10%,
substantive
perfume materials.
Substantive perfume materials are those odorous compounds that 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 200 and above, and are detectable at levels below those of the average
perfume material.
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 Chemicals)," Steffen
Arctander, published by the author, 1969. -
Examples of the highly volatile, low boiling, perfume ingredients are :
anethole,
benzaldehyde, benzyl acetate, benryl alcohol, benryl formate, iso-bomyl
acetate, camphene, ciscitral (neral), citronellal, citronellol, citronellyl
acetate,
para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl
carbinol, eucaliptol, geranial, geraniol, geranyl acetate, geranyl nitrite,
cis-3-
hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide,
linatyl
acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl
nonyl acetaldehyde, methyl phenyl carbinyl acetate, laevo-menthyl acetate,
menthone, iso-menthone, mycrene, myrcenyi acetate, myrcenol, nerol, neryl
acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene, beta-pinene,
gamma-terpinene, alpha-terpineoi, beta-terpineol, terpinyl acetate, and
vertenex (pare-tertiary-butyl cyclohexyl acetate). Some natural oils also
contain
large percentages of highly volatile perfume ingredients. For example,
lavandin
contains as major components : linalool; linalyi acetate; geraniol; and
citronellol.
Lemon oil and orange terpenes both contain about 95% of d-limonene.
Examples of moderately volatile perfume ingredients are : amyl cinnamic
aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol,
coumarin, dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-
eugenol,
flor acetate, heliotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial
(para-
tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma-methyl ionone,
nerolidol, patchouli alcohol, phenyl hexanol, beta-selinene, trichloromethyl
CA 02234407 2003-06-19
phenyl carbinyl acetate, methyl citrate, vanillin, and veratraldehyde.
Cedarwood teFpenes are composed mainly of alpha-cedrene, beta-cedrene,
and other C15H124 sesquiterpenes.
Examples of the less volatile, high boiling, perfume ingredients are
benzophenone, benzyl salicylate, ethylene brassylate, galaxolide (1,3,4,6,7,8-
hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gama-2-benzopyran), hexyl
cinnamic aidehyde, lyrai (4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-10-
carboxaldehyde), methyl cedrytone, methyl dihydro jasmonate, methyl-beta-
naphthyi 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 additionally comprise a variety of other,
optional,-
compounds. A preferred class of optional compounds are chetating agents
selected from the group of aminophosphonates. Suitable amino phosphonate
compounds for use herein include amino alkylene poly (alkylene phosphonate),
nitrilo trimethylene
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 available from Monsanto under the trade
name DEQUEST~.
Chelants can be incorporated in the compositions herein in amounts ranging
from 0.0% to 10.0% by weight of the total composition, preferably 0.1 % to
5.0%. Aminophosphonate chelants are particularly desirable for use herein as
it has been found that they further improve the gloss benefit across a wide
range of water hardness conditions which may be encountered in use, most
particularly during the dilution of the product prior to use. Typically, the
sulphonated polystyrenes herein perform well in a range of water hardness
conditions. Aminophosphonate chelants alone can provide a gloss benefit in
soft water, less in hard water. But we have found that, surprisingly, the
CA 02234407 1998-04-08
WO 97/13836 PCT/US96/15644
11
combination of sulphonated polystyrenes and aminophosphonate chelants will
provide better gloss than the chelant or the sulphonated polystyrenes alone. A
suitable weight ratio of chelant and polymer to observe this benefit is
between
10:1 and 1:10, most preferably between 2:1 and 1:2.
The compositions herein can further comprise a variety of optimal ingredients.
Suitable optimal ingredients for use herein include builders, other chelants,
solvents, buffers, bactericides, enzymes, hydrotropes, colorants, stabilizers.
The present invention further encompasses a process of cleaning a hard
surface by applying on said surface an effective amount of a composition
defined herein. When the composition is used in a so-called concentrated form
(i.e. between 10%-20% total actives), 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 polymer is still obtained after few rinses. Preferably, the
composition is diluted prior to use (to reach a total active level in the
order of
0.5%). In this dilute usage mode, there is no need to rinse the surface after
application of the composition in order to obtain the gloss benefit.
Examples
The following compositions were made by mixing the listed ingredients in the
listed proportions. All proportions are % by weight of the total compositions.
1 2
C7/C9/C11 EOfi.5 3.0 00.0
C12/C13 E03 1.0 2.0
C13/C15 E021 2.0 5.0
Palm Kernal Fatty Acid 0.4 0.4
Perfume 0.45 0.45
Sulfonated Polystyrene (*1) 3.0 3.0
Water and minors up to 100%
pH 10.5 10.5
CA 02234407 1998-04-08
WO 97/13836 PCT/US96/15644
12
3 4
C7/C9/C11 E06.5 3.0 0.0
C 12/C 13 E03 1.0 2.0
C 13/C 15 E 021 2. 0 5. 0
Sodium cumene sulfonate0.5 0.5
Palm Kernal Fatty Acid 0.4 0.4
Perfume 0.45 0.45
Sulfonated Polystyrene 3.0 3.0
(*1)
Water and Minors up
to 100%
PH 10.5 10.5
(*1 ) The tested polymer was a Sulfonated Polystyrene of Molecular weight
6,000,000 from Monomer-Polymer 8~ Dajac Laboratories, INC.
6
C7/C9/C11 E06.5 2.0 0.0
C12/C13 E03 1.0 1.0
C13/C15 E021 2.0 5.0
Sodium alkyl benzene 1.0 1.0
sulfonate
Palm Kernal Fatty Acid 0.4 0.4
Perfume 0.45 0.45
Sulfonated Polystyrene 3.0 3.0
(*2))
Water and Minors up to
100%
PH 10.5 10.5
CA 02234407 2001-12-21
13
Z 8 9
C7/C9/C 11 E06.5 2.5 2.5 2.5
C12/C13 E03 1.0 1.0 1.0
C13/C15 E021 1.6 1.6 1.6
Potassium Carbonate 1.0 1.0 1.0
Palm Kernal Fatty Acid 00.4 0.4 0.4
Sulfonated Polystyrene 1.0 3.0 6.0
('2)
Perfume 0.45 0.45 0.45
Water and Minors up
to 100%
PH 10.5 10.5 10.5
1_Q 11 12 13
Sulfonated polystyrene 1.0 1.0 1.0
('2) 1.0
NaCS 1.0 1.0 1.0 1.0
C121C13 E03 0.6 0.6 0.6 0.6
C7/C11 E06.5 1.4 1.4 1.4 1.4
Ammonia 0.0 0.1 0.0 0.0
K2C03 0.0 0.0 1.0 0.0
NaOH 0.0 0.0 0.0 0.1
Water and Minors up to
1000
pii 8.5 10.0 10.9 10.8
(*2) The tested Sulfonated Polystyrene: VersaflexT"" 7000 (National Search)
CA 02234407 1998-04-08
WO 97/13836 PCT/US96/15644
14
14
K2C03 1.0
C7/C11 E06.5 2.5
C12/C13 E03 1.0
C13/C15 E030 1.2
perfume 0.45
Poly(sodium styrene-sulfonate-co-vinyl naphthalene) 1.0
Water and Minors up to 100%
