Technical field
[0001] The present invention relates to the cleaning of different surfaces such as hard-surfaces,
fabrics, clothes and the like.
Background
[0002] A wide variety of cleaning compositions have been extensively described in the art.
Typically, cleaning compositions can be divided into hard surface cleaning compositions
and laundry cleaning compositions. Cleaning compositions of these two types are traditionally
very different in formulation and are sold as different products with different marketing
concepts. These differences impose on the consumer to have to purchase and use at
least two different products. Furthermore, compositions of the two types above, especially
hard surface cleaners, can be divided into sub-types. Indeed, many different kinds
of hard-surface cleaners are available, for instance bathroom cleaners, kitchen cleaners
or floor cleaners.
[0003] This variety in formulation is rendered necessary by the difference in nature between
the soils which can be found on laundry and on various hard-surfaces in kitchens and
bathrooms. For instance, kitchen soils comprise mainly edible oils, while bathroom
soils comprise mainly sebum and soap scum, also limescale; floor soils comprise mainly
particulate soils and laundry may have many different soils/stains including greasy
stains (e.g., olive oil, mayonnaise, vegetal oil make up), particulate stains and/or
bleachable stains (e.g., tea, coffee).
[0004] However, there is a trend for the development of liquid aqueous cleaning compositions
with better performance in several respect, i.e., liquid aqueous multi-purpose cleaners
which can be satisfactorily used on various surfaces as well as in laundry applications,
to clean various soils and stains. Such multi-purpose compositions are, for example,
disclosed in European patent application, EP-A-598973. Indeed, this patent application
discloses liquid aqueous compositions comprising hydrogen peroxide with a fully nonionic
system, i.e., at least one nonionic with an HLB above 15, at least one nonionic with
an HLB of from 13 to 15, at least one nonionic with an HLB of from 9 to 13 and at
least one nonionic with an HLB below 9. This patent application further discloses
the use of 2-alkyl alkanols as suds suppressors in said compositions.
[0005] But, it has been found that such liquid aqueous compositions comprising hydrogen
peroxide, a 2-alkyl alkanol and as the surfactant system, a specific nonionic system
of at least four nonionic surfactants having different HLB (hydrophilic lipophilic
balance) as defined hereinbefore, do not satisfactorily meet consumer's needs. Indeed,
such compositions based on a fully nonionic surfactant system and comprising a high
level of hydrophobic surfactants were found to have poor performance on some kind
of stains in laundry application. Although such hydrophobic nonionic surfactants have
good grease cutting properties and are particularly effective on greasy soils having
hydrophobic character, such as mineral oil and soap scum when used in hard surface
cleaning composition, it has been found that when said hydrophobic nonionic surfactants
are used in laundry applications bleachable stains are not satisfactorily bleached.
The wettability of the fabrics stains is seriously affected by the hydrophobicity
of the nonionic system of said compositions, i.e., good contact between hydrogen peroxide
and the stains on said fabric is prevented resulting thereby in poor performance on
bleachable stain. Also, it has been found that there is a problem associated with
the use of such ingredients, i.e., hydrophobic nonionic surfactants and 2-alkyl alkanols,
in that they may cause the final product to appear hazy, indicating insolubility and
phase separation.
[0006] Other multi-purpose liquid cleaning compositions have been disclosed like thus described
in EP-A- 666 308. Indeed, EP-A- 666 308 discloses compositions comprising hydrogen
peroxide or a source thereof, a 2-alkyl alkanol, a hydrophobic surfactant having an
HLB below 14 and an anionic surfactant. However, there is still room to further improve
such multi-purpose liquid aqueous cleaning compositions in respect of overall cleaning
performance on various types of stains including for example bleachable stains and
greasy stains.
[0007] It is thus an object of the present invention to provide a multi-purpose liquid aqueous
composition providing improved bleachable performance and improved stain removal performance
especially on greasy stains, when used in laundry applications including laundry pretreatment
applications, and/or in any household applications (e.g. cleaning of hard-surfaces
typically found in kitchens or bathrooms).
[0008] It is a further object of the present invention to provide such an improved liquid
aqueous cleaning composition which is also a clear composition in a broad range of
temperature, e.g. up to 45°C.
[0009] It has now been found that these objects can be efficiently met by formulating a
liquid aqueous cleaning composition having a pH up to 7 and comprising a peroxygen
bleach, at least an ethoxylated nonionic surfactant and at least a zwitterionic betaine
surfactant at a weight ratio of the ethoxylated nonionic surfactant to the zwitterionic
betaine surfactant of from 0.01 to 20. Indeed, it is by combining these ingredients
at the appropriate ratios that a multi-purpose liquid aqueous cleaning composition
is provided which exhibits a great flexibility in the soils it may clean.
[0010] It has now been found that such a composition when used for example in a laundry
application, especially in a pretreatment application, boosts the removal of various
types of stains including greasy stains like lipstick, olive oil, mayonnaise, vegetal
oil, sebum, make-up, and more surprisingly the bleaching performance, as compared
to the stain removal and bleaching performance delivered by the same composition comprising
only one of these surfactants (i.e., ethoxylated nonionic surfactant or zwitterionic
betaine surfactant) at equal total level of surfactants. Also the compositions of
the present invention significantly boost the removal of kitchen dirt when used to
clean hard-surfaces, as compared to the same compositions comprising only one of these
surfactants (i.e., ethoxylated nonionic surfactant or zwitterionic betaine surfactant)
at equal total level of surfactants. Indeed, the compositions of the present invention
provide excellent stain removal performance on a broad range of stains and soils and
excellent bleachable performance when used in any laundry application, e.g., as a
laundry detergent or a laundry additive, and especially when used as a laundry pretreater,
or even in other household applications like in hard surface cleaning applications.
[0011] A further advantage is that the aqueous compositions herein are physically and chemically
stable upon prolonged periods of storage.
[0012] Yet another advantage of the compositions according to the present invention is that
they are able to perform in a variety of conditions, i.e., in hard and soft water
as well as when used neat or diluted. Advantageously, they also provide satisfactory
shine performance and surface safety when used as hard surface cleaners and satisfactory
fabric and color safety when used as laundry cleaners.
Summary of the invention
[0013] The present invention encompasses a liquid aqueous composition having a pH up to
7 and comprising from 0.01% to 20% by weight of the total composition of a peroxygen
bleach, from 0.001% to 30% by weight of the total composition of an ethoxylated nonionic
surfactant, from 0.001% to 20% by weight of a zwitterionic betaine surfactant at a
weight ratio of the ethoxylated nonionic surfactant to the zwitterionic betaine surfactant
of from 0.01 to 20, with the proviso that said composition is free of an antimicrobial
essential oil or an active thereof or a mixture thereof.
[0014] The present invention further encompasses processes of cleaning a surface, e.g. a
fabric or a hard-surface, starting from a liquid aqueous composition as defined herein.
For example, the processes of cleaning fabrics include the steps of contacting said
fabrics with the liquid aqueous composition herein neat or diluted, and subsequently
rinsing said fabrics. In the preferred embodiment, when the fabrics are "pretreated",
the composition is applied neat on the fabrics, and the fabrics are subsequently washed
in a normal wash cycle.
Detailed description of the invention
The liquid aqueous cleaning composition
[0015] The compositions according to the present invention are liquid compositions as opposed
to a solid or a gas. As used herein "liquid" includes "pasty" compositions. The liquid
compositions herein are aqueous compositions. The liquid compositions according to
the present invention have a pH up to 7, preferably from 1 to 6, and more preferably
from 2 to 5. Formulating the compositions according to the present invention in the
acidic pH range contribute to the chemical stability of the compositions and to the
stain removal performance of the compositions. The pH of the compositions may be adjusted
by any acidifying agents known to those skilled in the art. Examples of acidifying
agents are organic acids such as citric acid and inorganic acids such as sulphuric
acid.
[0016] As a first essential element the compositions according to the present invention
comprise a peroxygen bleach or a mixture thereof. Indeed, the presence of peroxygen
bleach contributes to the excellent bleaching benefits of said compositions. Suitable
peroxygen beaches to be used herein are hydrogen peroxide, water soluble sources thereof,
or mixtures thereof. As used herein a hydrogen peroxide source refers to any compound
which produces perhydroxyl ions when said compound is in contact with water.
[0017] Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates,
persilicates, persulphates such as monopersulfate, perborates, peroxyacids such as
diperoxydodecandioic acid (DPDA), magnesium perphtalic acid, perlauric acid, perbenzoic
and alkylperbenzoic acids, hydroperoxides, aliphatic and aromatic diacyl peroxides,
and mixtures thereof. Preferred peroxygen bleaches herein are hydrogen peroxide, hydroperoxide
and/or diacyl peroxide. Hydrogen peroxide is the most preferred peroxygen bleach herein.
[0018] Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide,
2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, tert-amyl
hydroperoxide and 2,5-dimethyl-hexane-2,5-dihydroperoxide. Such hydroperoxides have
the advantage to be particularly safe to fabrics and color while delivering excellent
bleaching performance when used in any laundry application.
[0019] Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide, didecanoyl
peroxide, dimyristoyl peroxide, or mixtures thereof. Suitable aromatic diacyl peroxide
for use herein is for example benzoyl peroxide. Such diacyl peroxides have the advantage
to be particularly safe to fabrics and color while delivering excellent bleaching
performance when used in any laundry application.
[0020] The compositions herein comprise from 0.01% to 20% by weight of the total composition
of said peroxygen bleach or mixtures thereof, preferably from 1% to 15% and more preferably
from 2% to 10%.
[0021] As a second essential element the compositions according to the present invention
comprise an ethoxylated nonionic surfactant or a mixture thereof at a level of from
0.001% to 30% by weight of the total composition. Preferably, the compositions herein
comprise from 0.01% to 15% by weight of the total composition of said ethoxylated
nonionic surfactant or mixture thereof, more preferably from 0.5% to 10%, even more
preferably from 1% to 9% and most preferably from 1% to 6%.
[0022] Suitable ethoxylated nonionic surfactants herein are ethoxylated nonionic surfactants
according to the formula RO-(C
2H
4O)
nH, wherein R is a C
6 to C
22 alkyl chain or a C
6 to C
28 alkyl benzene chain, and wherein n is from 0 to 20, preferably from 1 to 15 and,
more preferably from 2 to 15 and most preferably from 2 to 12. The preferred R chains
for use herein are the C
8 to C
22 alkyl chains.
[0023] Preferred ethoxylated nonionic surfactants are according to the formula above and
have an HLB (hydrophilic-lipophilic balance) below 16, preferably below 15, and more
preferably below 14. Those ethoxylated nonionic surfactants have been found to provide
good grease cutting properties.
[0024] Accordingly suitable ethoxylated nonionic surfactants for use herein are Dobanol
R 91-2.5 (HLB= 8.1; R is a mixture of C9 and C
11 alkyl chains, n is 2.5), or Lutensol
R TO3 (HLB=8; R is a C
13 alkyl chains, n is 3), or Lutensol
R AO3 (HLB=8; R is a mixture of C
13 and C
15 alkyl chains, n is 3), or Tergitol
R 25L3 (HLB= 7.7; R is in the range of C
12 to C
15 alkyl chain length, n is 3), or Dobanol
R 23-3 (HLB=8.1; R is a mixture of C
12 and C
13 alkyl chains, n is 3), or Dobanol
R 23-2 (HLB=6.2; R is a mixture of C
12 and C
13 alkyl chains, n is 2), or Dobanol
R 45-7 (HLB=11.6; R is a mixture of C
14 and C
15 alkyl chains, n is 7) Dobanol
R 23-6.5 (HLB=11.9; R is a mixture of C
12 and C
13 alkyl chains, n is 6.5), or Dobanol
R 25-7 (HLB=12; R is a mixture of C
12 and C
15 alkyl chains, n is 7), or Dobanol
R 91-5 (HLB=11.6; R is a mixture of C
9 and C
11 alkyl chains, n is 5), or Dobanol
R 91-6 (HLB=12.5 ; R is a mixture of C
9 and C
11 alkyl chains, n is 6), or Dobanol
R 91-8 (HLB=13.7 ; R is a mixture of C
9 and C
11 alkyl chains, n is 8), Dobanol
R 91-10 (HLB=14.2 ; R is a mixture of C
9 to C
11 alkyl chains, n is 10), or mixtures thereof. Preferred herein are Dobanol
R 91-2.5 , or Lutensol
R TO3, or Lutensol
R AO3, or Tergitol
R 25L3, or Dobanol
R 23-3, or Dobanol
R 23-2, or mixtures thereof. These Dobanol
R surfactants are commercially available from SHELL. These Lutensol
R surfactants are commercially available from BASF and these Tergitol
R surfactants are commercially available from UNION CARBIDE.
[0025] Suitable chemical processes for preparing the ethoxylated nonionic surfactants for
use herein include condensation of corresponding alcohols with alkylene oxide, in
the desired proportions. Such processes are well-known to the man skilled in the art
and have been extensively described in the art.
[0026] The compositions herein may desirably comprise one of those ethoxylated nonionic
surfactants or a mixture of those ethoxylated nonionic surfactants having different
HLBs (hydrophilic-lipophilic balance). In a preferred embodiment the compositions
herein comprise an ethoxylated nonionic surfactant according to the above formula
and having an HLB up to 10 (i.e., a so called hydrophobic ethoxylated nonionic surfactant),
preferably below 10, more preferably below 9, and an ethoxylated nonionic surfactant
according to the above formula and having an HLB above 10 to 16 (i.e., a so called
hydrophilic ethoxylated nonionic surfactant), preferably from 11 to 14. Indeed, in
this preferred embodiment the compositions of the present invention typically comprise
from 0.01% to 15% by weight of the total composition of said hydrophobic ethoxylated
nonionic surfactant, preferably from 0.5% to 10% and from 0.01% to 15% by weight of
said hydrophilic ethoxylated nonionic surfactant, preferably from 0.5% to 10%. Such
mixtures of ethoxylated nonionic surfactants with different HLBs may be desired as
they allow optimum grease cleaning removal performance on a broader range of greasy
soils having different hydrophobic/hydrophilic characters.
[0027] As a third essential element the compositions according to the present invention
comprise a zwitterionic betaine surfactant or a mixture thereof at a level of from
0.001% to 20% by weight of the total composition. Preferably, the compositions herein
comprise from 0.01% to 10% by weight of the total composition of said zwitterionic
betaine surfactant or mixture thereof, more preferably from 0.5% to 8% and most preferably
from 1% to 5%.
[0028] Suitable zwitterionic betaine surfactants to be used herein contain both a cationic
hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group
on the same molecule at a relatively wide range of pH's. The typical anionic hydrophilic
groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates,
and the like can be used. A generic formula for the zwitterionic betaine surfactants
to be used herein is:
R
1-N
+(R
2)(R
3)R
4X
-
wherein R
1 is a hydrophobic group; R
2 is hydrogen, C
1-C
6 alkyl, hydroxy alkyl or other substituted C
1-C
6 alkyl group; R
3 is C
1-C
6 alkyl, hydroxy alkyl or other substituted C
1-C
6 alkyl group which can also be joined to R
2 to form ring structures with the N, or a C
1-C
6 carboxylic acid group or a C
1-C
6 sulfonate group; R
4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically
an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon
atoms; and X is the hydrophilic group which is a carboxylate or sulfonate group.
[0029] Preferred hydrophobic groups R
1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
hydrocarbon chains that can contain linking groups such as amido groups, ester groups.
More preferred R
1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18,
and more preferably from 10 to 16. These simple alkyl groups are preferred for cost
and stability reasons. However, the hydrophobic group R
1 can also be an amido radical of the formula R
a-C(O)-NH-(C(R
b)
2)
m, wherein R
a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms,
preferably up to 18, more preferably up to 16, R
b is selected from the group consisting of hydrogen and hydroxy groups, and m is from
1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group
in any (C(R
b)
2) moiety.
[0030] Preferred R
2 is hydrogen, or a C
1-C
3 alkyl and more preferably methyl. Preferred R
3 is a C
1-C
4 carboxylic acid group or C1-C4 sulfonate group, or a C
1-C
3 alkyl and more preferably methyl. Preferred R
4 is (CH2)
n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is
from 1 to 3.
[0031] Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275,
2,702,279 and 2,255,082, incorporated herein by reference.
[0032] Examples of particularly suitable alkyldimethyl betaines include coconut-dimethyl
betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia)acetate,
2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl
betaine, cetyl dimethyl betaine, stearyl dimethyl betaine. For example Coconut dimethyl
betaine is commercially available from Seppic under the trade name of Amonyl 265®.
Lauryl betaine is commercially available from Albright & Wilson under the trade name
Empigen BB/L®.
[0033] Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine
or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine. For example C10-C14
fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from
Sherex Company under the trade name "Varion CAS® sulfobetaine".
[0034] A further example of betaine is Lauryl-immino-dipropionate commercially available
from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
[0035] Particularly preferred zwitterionic betaine surfactants for use herein are salt free,
i.e. that the zwitterionic betaine surfactant raw material contains less than 5% by
weight of salts, preferably less than 2%, more preferably less than 1% and most preferably
from 0.01% to 0.5%.
[0036] By

salts

is in meant herein any material having as base unit, a couple of positive ion (or
positive molecular ion) and negative ion (or negative molecular ion) containing one
or more halogen atoms. Such salts include sodium chloride, potassium chloride, sodium
bromide and the like.
[0037] Such salts free zwitterionic betaine surfactants are obtainable by conventional manufacturing
processes like inverse osmosis or fractionated precipitation. For example inverse
osmosis is based on the principle of contacting the zwitterionic betaine surfactant
raw material (commercially available ) with a polar solvent (it is to be understood
that such a solvent is free of salts) separated by a semi-permeable membrane for example
acetate-cellulose. An adequate pressure is applied on the system to allow the salts
to migrate from the surfactant raw material to the polar solvent phase. This way the
zwitterionic betaine surfactant raw material is purified, i.e. the salts is subtracted
from the raw material.
[0038] Advantageously, it has now been surprisingly found that the use of such salt free
zwitterionic betaine surfactants delivers improved fabric safety and/or color safety
when bleaching fabrics with a peroxygen bleach-containing composition comprising the
same, as compared to the use of the same zwitterionic betaine surfactant raw materials
with higher amount of salts. Thus, in its broadest aspect, the present invention also
encompasses the use of a composition comprising a salt free zwitterionic betaine surfactant
and a peroxygen bleach for bleaching fabrics whereby color safety is improved (i.e.
color damage/decoloration is reduced) and/or fabric safety is improved.
[0039] The betaine zwitterionic surfactants herein have the ability to further boost the
stain removal performance delivered by the ethoxylated nonionic surfactants herein
on greasy stains, while providing improved bleaching performance to the liquid peroxygen
bleach-containing compositions of the present invention comprising them.
[0040] Indeed, a significant cooperation has been observed between these ingredients to
get optimum stain removal performance on a variety of soils, from particulate to non-particulate
soils from hydrophobic to hydrophilic soils under any household application and especially
laundry application on both hydrophilic and hydrophobic fabrics.
[0041] Optimum stain removal performance and bleaching performance are obtained when the
ethoxylated nonionic surfactant and the zwitterionic betaine surfactant are present
in the compositions of the present invention comprising a peroxygen bleach (pH up
to 7), at weight ratio of the ethoxylated nonionic surfactant to the zwitterionic
betaine surfactant of from 0.01 to 20, preferably from 0.1 to 15, more preferably
from 0.5 to 5 and most preferably from 0.8 to 3.
[0042] Advantageously excellent stain removal performance and bleaching performance can
be obtained with the compositions herein at low total level of surfactants. Typically,
the compositions herein comprise from 0.01% to 35% by weight of the total composition
of ethoxylated nonionic surfactant and zwitterionic betaine surfactant, preferably
from 0.1% to 15%, more preferably from 0.5% to 10%, even more preferably below 10%
and most preferably from 1% to 8%.
[0043] Indeed, the present invention is based on the finding that the use of zwitterionic
betaine surfactant on top of the ethoxylated nonionic surfactant at the appropriate
ratios, in a liquid aqueous composition comprising a peroxygen bleach (pH up to 7),
boosts the bleaching performance and the removal of various types of stains including
greasy stains (e.g., lipstick, olive oil, mayonnaise, vegetal oil, sebum, make-up),
as compared to the bleaching and stain removal performance delivered by the same composition
based only on one of these surfactants (i.e., ethoxylated nonionic surfactant or zwitterionic
betaine surfactant) at equal total level of surfactants. For example, it is only at
very high levels of nonionic surfactants as compared the total level of ethoxylated
nonionic surfactants and zwitterionic betaine surfactants present in the compositions
of the present invention that similar grease cleaning benefit is observed. Importantly,
the improved stain removal benefit and bleaching benefit are delivered with a liquid
aqueous composition which is a water-like, clear and transparent composition.
[0044] The appearance of a composition can be evaluated via turbidimetric analysis. For
example, the transparency of a composition can be evaluated by measuring its absorbency
via a spectrophotometer at 800 nm wave length.
[0045] The stain removal performance may be evaluated by the following test methods on various
type of stains.
[0046] A suitable test method for evaluating the stain removal performance on a soiled fabric
for example under pretreatment condition is the following: A composition according
to the present invention is applied neat to a fabric preferably to the soiled portion
of the fabric, left to act from 1 to 10 minutes, and said pretreated fabric is then
washed according to common washing conditions, at a temperature of from 30° to 70°C
for from 10 to 100 minutes. The stain removal is then evaluated by comparing side
by side the soiled fabric pretreated with the composition of the present invention
with those pretreated with the reference, e.g., the same composition but comprising
only an alkoxylated nonionic surfactant or only a zwitterionic betaine surfactant
as the sole surfactant. A visual grading may be used to assign difference in panel
units (psu) in a range from 0 to 4.
[0047] A suitable test method for evaluating cleaning performance on a hard-surface is the
following: synthetic soil representative of typical hard surface household kitchen
dirt soil can be used. The test-soil is applied on an enamel-coated metal plate (cleaned
with a detergent and then with alcohol) with a paint roller, and the plates are baked
at 130° C for 30 minutes. After 24 hours they can be used for the test. This test
is evaluated in a Gardner straight-line scrub machine. The results are given in number
of strokes a given composition needs to clean a standard soiled plate. The lower the
number of strokes needed the more efficient in terms of satin removal is the composition
used to clean the dirt from the test plates.
[0048] The bleaching performance may be evaluated as for the stain removal performance but
the stains used are bleachable stains like coffee, tea and the like.
[0049] An advantage of the liquid aqueous compositions of the present invention is that
they are physically and chemically stable upon prolonged periods of storage.
[0050] Chemical stability of the compositions herein may be evaluated by measuring the concentration
of available oxygen (often abbreviated to AvO2) at given storage time after having
manufactured the compositions. The concentration of available oxygen can be measured
by chemical titration methods known in the art, such as the iodometric method, thiosulphatimetric
method, the permanganometric method and the cerimetric method. Said methods and the
criteria for the choice of the appropriate method are described for example in "Hydrogen
Peroxide", W. C. Schumb, C. N. Satterfield and R. L. Wentworth, Reinhold Publishing
Corporation, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int.
Science, 1970.
[0051] By "physically stable" it is meant herein that no phase separation occurs in the
compositions for a period of 7 days at 50°C.
Optional ingredients
[0052] The compositions herein may further comprise a variety of other optional ingredients
such as chelating agents, builders, other surfactants, stabilisers, bleach activators,
soil suspenders, soil suspending polyamine polymers, polymeric soil release agents,
radical scavengers, catalysts, dye transfer agents, solvents, brighteners, perfumes,
pigments and dyes.
[0053] In a preferred embodiment of the present invention the ionic strength of the compositions
is higher than 1.10
-4 M, preferably higher than 5.10
-3 M, and more preferably higher than 1.10
-3 M. Indeed, it has been observed that formulating the compositions of the present
invention with such high ionic strength further contributes to their benefits, i.e.,
improved stain removal performance and improved bleaching performance. The higher
the ionic strength the better the stain removal and bleaching performance. Indeed,
it is speculated that under the pH conditions of the present compositions (acidic
to neutral), especially when the pH of the composition is higher than the pka of the
zwitterionic betaine surfactant present therein, said surfactant is in a dipolar form
and its packing is strongly influenced by the ionic strength.
[0054] The ionic strength of a composition may be increased by the addition of various ingredients
like chelating agents or mixtures thereof.
[0055] Accordingly, the compositions of the present invention may comprise a chelating agent
as a preferred optional ingredient. Suitable cheating agents may be any of those known
to those skilled in the art such as the ones selected from the group comprising phosphonate
cheating agents, amino carboxylate chelating agents, other carboxylate cheating agents,
polyfunctionally-substituted aromatic cheating agents, ethylenediamine N,N'- disuccinic
acids, or mixtures thereof.
[0056] A cheating agent may be desired in the compositions of the present invention as it
allows to increase the ionic strength of the compositions herein and thus their stain
removal and bleaching performance on various surfaces. The presence of chelating agents
may also contribute to reduce tensile strength loss of fabrics and/or color damage,
especially in a laundry pretreatment application. Indeed, the chelating agents inactivate
the metal ions present on the surface of the fabrics and/or in the cleaning compositions
(neat or diluted) that otherwise would contribute to the radical decomposition of
the peroxygen bleach.
[0057] Suitable phosphonate chelating agents to be used herein may include alkali metal
ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well
as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid)
(ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene
phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP). 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 phosphonate chelating agents
to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and
ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially
available from Monsanto under the trade name DEQUEST®.
[0058] Polyfunctionally-substituted aromatic chelating agents may also be useful in the
compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et
al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such
as 1,2-dihydroxy -3,5-disulfobenzene.
[0059] A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-
disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium
salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially
the (S,S) isomer have been extensively described in US patent 4, 704, 233, November
3, 1987, to Hartman and Perkins. Ethylenediamine N,N'- disuccinic acids is, for instance,
commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
[0060] Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates,
diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine
triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates,
ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic
acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted
ammonium salt forms. Particularly suitable amino carboxylates to be used herein are
diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which
is, for instance, commercially available from BASF under the trade name Trilon FS®
and methyl glycine di-acetic acid (MGDA).
[0061] Further carboxylate chelating agents to be used herein include salicylic acid, aspartic
acid, glutamic acid, glycine, malonic acid or mixtures thereof.
[0062] Another chelating agent for use herein is of the formula:

wherein R
1, R
2, R
3, and R
4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl,
aryloxy, -Cl, -Br, -NO
2, -C(O)R', and -SO
2R''; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl,
and aryloxy; R'' is selected from the group consisting of alkyl, alkoxy, aryl, and
aryloxy; and R
5, R
6, R
7, and R
8 are independently selected from the group consisting of -H and alkyl.
[0063] Particularly preferred cheating agents to be used herein are amino aminotri(methylene
phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta
methylene phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic
acid, and mixtures thereof.
[0064] Typically, the compositions according to the present invention comprise up to 5%
by weight of the total composition of a chelating agent, or mixtures thereof, preferably
from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5%.
[0065] The compositions of the present invention may further comprise other surfactants
than the ones mentioned hereinbefore including other nonionic surfactants, anionic
surfactants, cationic surfactants and/or amphoteric surfactants.
[0066] Typically, the compositions according to the present invention may comprise from
0.01% to 30% by weight of the total composition of another surfactant on top of the
zwitterionic betaine surfactant and ethoxylated nonionic surfactant, preferably from
0.1% to 25 % and more preferably from 0.5% to 20%.
[0067] Suitable nonionic surfactants to be used herein include polyhydroxy fatty acid amide
surfactants, or mixtures thereof, according to the formula
R
2 - C(O) - N(R
1) - Z,
wherein R
1 is H, or C
1-C
4 alkyl, C
1-C
4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R
2 is C
5-C
31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof.
[0068] Preferably, R
1 is C
1-C
4 alkyl, more preferably C
1 or C
2 alkyl and most preferably methyl, R
2 is a straight chain C
7-C
19 alkyl or alkenyl, preferably a straight chain C
9-C
18 alkyl or alkenyl, more preferably a straight chain C
11-C
18 alkyl or alkenyl, and most preferably a straight chain C
11-C
14 alkyl or alkenyl, or mixtures thereof. Z preferably will be derived from a reducing
sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable
reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and
xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and
high maltose corn syrup can be utilised as well as the individual sugars listed above.
These corn syrups may yield a mix of sugar components for Z. It should be understood
that it is by no means intended to exclude other suitable raw materials. Z preferably
will be selected from the group consisting of -CH
2-(CHOH)
n-CH
2OH, -CH(CH
2OH)-(CHOH)
n-1-CH
2OH, -CH
2-(CHOH)
2-(CHOR')(CHOH)-CH
2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic
monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls
wherein n is 4, particularly CH
2-(CHOH)
4-CH
2OH.
[0069] In formula R
2 - C(O) - N(R
1) - Z, R
1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy
ethyl, or N-2-hydroxy propyl. R
2 - C(O) - N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide,
capricamide, palmitamide, tallowamide and the like. Z can be 1-deoxyglucityl, 2-deoxyfructityl,
1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl
and the like.
[0070] Suitable polyhydroxy fatty acid amide surfactants to be used herein may be commercially
available under the trade name HOE® from Hoechst.
[0071] Methods for making polyhydroxy fatty acid amide surfactants are known in the art.
In general, they can be made by reacting an alkyl amine with a reducing sugar in a
reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and
then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride
in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide
product. Processes for making compositions containing polyhydroxy fatty acid amides
are disclosed for example in GB patent specification 809,060, published February 18,
1959, by Thomas Hedley & Co., Ltd., US patent 2,965,576, issued December 20, 1960
to E.R. Wilson, US patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, US
patent 1,985,424, issued December 25, 1934 to Piggott and WO92/06070, each of which
is incorporated herein by reference.
[0072] Suitable anionic surfactants to be used in the compositions herein include water-soluble
salts or acids of the formula ROSO
3M wherein R preferably is a C
10-C
24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C
10-C
20 alkyl component, more preferably a C
12-C
18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.,
sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium
and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C
12-
16 are preferred for lower wash temperatures (e.g., below about 50°C) and C
16-
18 alkyl chains are preferred for higher wash temperatures (e.g., above about 50°C).
[0073] Other suitable anionic surfactants for use herein are water-soluble salts or acids
of the formula RO(A)
mSO
3M wherein R is an unsubstituted C
10-C
24 alkyl or hydroxyalkyl group having a C
10-C
24 alkyl component, preferably a C
12-C
20 alkyl or hydroxyalkyl, more preferably C
12-C
18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically
between about 0.5 and about 6, more preferably between about 0.5 and about 3, and
M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium,
lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium
and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium
and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine,
mixtures thereof, and the like. Exemplary surfactants are C
12-C
18 alkyl polyethoxylate (1.0) sulfate, C
12-C
18E(1.0)M), C
12-C
18 alkyl polyethoxylate (2.25) sulfate, C
12-C
18E(2.25)M), C
12-C
18 alkyl polyethoxylate (3.0) sulfate C
12-C
18E(3.0), and C
12-C
18 alkyl polyethoxylate (4.0) sulfate C
12-C
18E(4.0)M), wherein M is conveniently selected from sodium and potassium.
[0074] Other anionic surfactants useful for detersive purposes can also be used herein.
These can include salts (including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap,
C
9-C
20 linear alkylbenzenesulfonates, C
8-C
22 primary or secondary alkanesulfonates, C
8-C
24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the
pyrolyzed product of alkaline earth metal citrates, e.g., as described in British
patent specification No. 1,082,179, C
8-C
24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl
ester sulfonates such as C
14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates,
isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated
C
12-C
18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C
6-C
14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described below), branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH
2CH
2O)
kCH
2COO-M
+ wherein R is a C
8-C
22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin
acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated
rosin, and resin acids and hydrogenated resin acids present in or derived from tall
oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al.
at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
[0075] Other suitable anionic surfactants to be used herein also include acyl sarcosinate
or mixtures thereof, in its acid and/or salt form, preferably long chain acyl sarcosinates
having the following formula:

wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of from
11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms. Preferred M are hydrogen
and alkali metal salts, especially sodium and potassium. Said acyl sarcosinate surfactants
are derived from natural fatty acids and the amino-acid sarcosine (N-methyl glycine).
They are suitable to be used as aqueous solution of their salt or in their acidic
form as powder. Being derivatives of natural fatty acids, said acyl sarcosinates are
rapidly and completely biodegradable and have good skin compatibility.
[0076] Accordingly, suitable long chain acyl sarcosinates to be used herein include C
12 acyl sarcosinate (i.e., an acyl sarcosinate according to the above formula wherein
M is hydrogen and R is an alkyl group of 11 carbon atoms) and C
14 acyl sarcosinate (i.e., an acyl sarcosinate according to the above formula wherein
M is hydrogen and R is an alkyl group of 13 carbon atoms). C
12 acyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied
by Hampshire. C
14 acyl sarcosinate is commercially available, for example, as Hamposyl M-30® supplied
by Hampshire.
[0077] Suitable amphoteric surfactants to be used herein include amine oxides having the
following formula R
1R
2R
3NO wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted,
linear or branched hydrocarbon chains of from 1 to 30 carbon atoms. Preferred amine
oxide surfactants to be used according to the present invention are amine oxides having
the following formula R
1R
2R
3NO wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably
from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein
R2 and R3 are independently substituted or unsubstituted, linear or branched hydrocarbon
chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and
more preferably are methyl groups. R1 may be a saturated substituted or unsubstituted
linear or branched hydrocarbon chain. Suitable amine oxides for use herein are for
instance natural blend C8-C10 amine oxides as well as C12-C16 amine oxides commercially
available from Hoechst.
[0078] The compositions of the present invention may comprise a radical scavenger or a mixture
thereof. Suitable radical scavengers for use herein include the well-known substituted
mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures
thereof. Preferred such radical scavengers for use herein include di-tert-butyl hydroxy
toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone,
tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butyl catechol,
benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate
or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene. Such radical
scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories
under the trade name Nipanox S1 ®. Radical scavengers when used, are typically present
herein in amounts ranging from up to 10% by weight of the total composition and preferably
from 0.001% to 0.5% by weight.
[0079] The presence of radical scavengers may contribute to reduce tensile strength loss
of fabrics and/or color damage when the compositions of the present invention are
used in any laundry application, especially in a laundry pretreatment application.
[0080] The compositions according to the present invention may further comprise an antioxidant
or mixtures thereof. Typically, the compositions herein comprise up to 10% by weight
of the total composition of an antioxidant or mixtures thereof, preferably from 0.002%
to 5%, more preferably from 0.005% to 2%, and most preferably from 0.01% to 1%.
[0081] Suitable antioxidants to be used herein include organic acids like citric acid, ascorbic
acid, tartaric acid, adipic acid and sorbic acid, or amines like lecithin, or aminoacids
like glutamine, methionine and cysteine, or esters like ascorbil palmitate, ascorbil
stearate and triethylcitrate, or mixtures thereof. Preferred antioxidants for use
herein are citric acid, ascorbic acid, ascorbil palmitate, lecithin or mixtures thereof.
[0082] As an optional ingredient, the compositions of the present invention may comprise
a bleach activator or mixtures thereof. By "bleach activator", it is meant herein
a compound which reacts with hydrogen peroxide to form a peracid. The peracid thus
formed constitutes the activated bleach. Suitable bleach activators to be used herein
include those belonging to the class of esters, amides, imides, or anhydrides. Examples
of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and
GB 2 143 231 and a method for their formation into a prilled form is described in
European Published Patent Application EP-A-62 523. Suitable examples of such compounds
to be used herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl hexanoyloxybenzene
sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and
nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate
(NOBS). Also suitable are N-acyl caprolactams selected from the group consisting of
substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam,
hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam,
acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam
or mixtures thereof. A particular family of bleach activators of interest was disclosed
in EP 624 154, and particularly preferred in that family is acetyl triethyl citrate
(ATC). Acetyl triethyl citrate has the advantage that it is environmental-friendly
as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl
citrate has a good hydrolytical stability in the product upon storage and it is an
efficient bleach activator. Finally, it provides good building capacity to the composition.
The compositions according to the present invention may comprise from 0.01% to 20%
by weight of the total composition of said bleach activator, or mixtures thereof,
preferably from 1% to 10%, and more preferably from 3% to 7%
Cleaning processes
[0083] In the present invention, the liquid aqueous cleaning composition of the present
invention needs to be contacted with the surface to clean.
[0084] By "surfaces" it is meant herein any inanimate surface. These inanimate surfaces
include, but are not limited to, hard-surfaces typically found in houses like kitchens,
bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth
vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary
fittings such as sinks, showers, shower curtains, wash basins, WCs and the like, as
well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table
cloths, sleeping bags, tents, upholstered furniture and the like, and carpets. Inanimate
surfaces also include household appliances including, but not limited to, refrigerators,
freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers
and so on.
[0085] Thus, the present invention also encompasses a process of cleaning a fabric, as the
inanimate surface. In such a process a composition, as defined herein, is contacted
with the fabrics to be cleaned. This can be done either in a so-called "pretreatment
mode", where a composition, as defined herein, is applied neat onto said fabrics before
the fabrics are rinsed, or washed then rinsed, or in a "soaking mode" where a composition,
as defined herein, is first diluted in an aqueous bath and the fabrics are immersed
and soaked in the bath, before they are rinsed, or in a "through the wash mode", where
a composition, as defined herein, is added on top of a wash liquor formed by dissolution
or dispersion of a typical laundry detergent. It is also essential in both cases,
that the fabrics be rinsed after they have been contacted with said composition, before
said composition has completely dried off.
[0086] Indeed, it has been found that water evaporation contributes to increase the concentration
of free radicals onto the surface of the fabrics and, consequently, the rate of chain
reaction. It is also speculated that an auto-oxidation reaction occurs upon evaporation
of water when the liquid compositions are left to dry onto the fabrics. Said reaction
of auto-oxidation generates peroxy-radicals which may contribute to the degradation
of cellulose. Thus, not leaving the liquid compositions, as described herein, to dry
onto the fabric, in a process of pretreating soiled fabrics, contributes to reduce
the tensile strength loss and/or color damage when pretreating fabrics with liquid
peroxygen bleach-containing compositions.
[0087] In the pretreatment mode, the process comprises the steps of applying said liquid
composition in its neat form onto said fabrics, or at least soiled portions thereof,
and subsequently rinsing, or washing then rinsing said fabrics. In this mode, the
neat compositions can optionally be left to act onto said fabrics for a period of
time ranging from 1 min. to 1 hour, before the fabrics are rinsed, or washed then
rinsed, provided that the composition is not left to dry onto said fabrics. For particularly
though stains, it may be appropriate to further rub or brush said fabrics by means
of a sponge or a brush, or by rubbing two pieces of fabrics against each other.
[0088] In another mode, generally referred to as "soaking", the process comprises the steps
of diluting said liquid composition in its neat form in an aqueous bath so as to form
a diluted composition. The dilution level of the liquid composition in an aqueous
bath is typically up to 1:85, preferably up to 1:50 and more preferably about 1:25
(composition:water). The fabrics are then contacted with the aqueous bath comprising
the liquid composition, and the fabrics are finally rinsed, or washed then rinsed.
Preferably in that embodiment, the fabrics are immersed in the aqueous bath comprising
the liquid composition, and also preferably, the fabrics are left to soak therein
for a period of time ranging from 1 minute to 48 hours, preferably from 1 hour to
24 hours.
[0089] In yet another mode which can be considered as a sub-embodiment of "soaking", generally
referred to as "bleaching through the wash", the liquid composition is used as a so-called
laundry additive. And in that embodiment the aqueous bath is formed by dissolving
or dispersing a conventional laundry detergent in water. The liquid composition in
its neat form is contacted with the aqueous bath, and the fabrics are then contacted
with the aqueous bath containing the liquid composition. Finally, the fabrics are
rinsed.
[0090] In another embodiment the present invention also encompasses a process of cleaning
a hard-surface, as the inanimate surface. In such a process a composition, as defined
herein, is contacted with the hard-surfaces to be cleaned. Thus, the present invention
also encompasses a process of cleaning a hard-surface with a composition, as defined
herein, wherein said process comprises the step of applying said composition to said
hard-surface, preferably only soiled portions thereof, and optionally rinsing said
hard-surface.
[0091] In the process of cleaning hard-surfaces according to the present invention the composition,
as defined herein, may be applied to the surface to be cleaned in its neat form or
in its diluted form typically up to 200 times their weight of water, preferably into
80 to 2 times their weight of water, and more preferably 60 to 2 times.
[0092] When used as hard surfaces cleaners the compositions of the present invention are
easy to rinse and provide good shine characteristics on the cleaned surfaces.
[0093] Depending on the end-use envisioned, the compositions herein can be packaged in a
variety of containers including conventional bottles, bottles equipped with roll-on,
sponge, brusher or sprayers.
[0094] The invention is further illustrated by the following examples.
Examples
[0095] Following compositions were made by mixing the listed ingredients in the listed proportions
(weight % unless otherwise specified).
| Compositions |
I |
II |
III |
IV |
V |
VI |
VII |
VIII |
| Dobanol® 91-10 |
- |
- |
- |
1.6 |
0.8 |
- |
1.6 |
- |
| Dobanol® 45-7 |
1.6 |
2.0 |
1.6 |
- |
0.8 |
1.6 |
- |
2.0 |
| Dobanol® 23-3 |
2.0 |
- |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
- |
| Lauryl Betaine |
- |
- |
2.4 |
2.4 |
2.4 |
5.0 |
5.0 |
5.0 |
| Mirataine H2C-HA® |
5.0 |
2.4 |
- |
- |
- |
- |
- |
- |
| H2O2 |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
| HEDP |
0.16 |
- |
0.16 |
0.16 |
- |
0.16 |
0.16 |
0.16 |
| DTPMP |
- |
0.18 |
- |
- |
0.18 |
- |
- |
- |
| Propyl gallate |
0.1 |
0.1 |
0.1 |
0.1 |
0.3 |
0.1 |
0.1 |
0.1 |
| Citric acid |
0.05 |
0.05 |
0.05 |
0.05 |
0.05 |
0.05 |
0.05 |
0.05 |
| Water and minors |
up to 100% |
| H2SO4 up to pH 4 |
|
|
|
|
|
|
|
|
HEDP is 1-hydroxy-ethane diphosphonate.
DTPMP is diethylene triamine penta methylene phosphonate.
Mirataine H2C-HA® is Lauryl-immino-dipropionate |
| Compositions |
IX |
X |
XI |
XII |
XIII |
XIV |
XV |
XVI |
| Dobanol® 91-10 |
- |
- |
- |
1.6 |
- |
- |
1.6 |
- |
| Dobanol® 45-7 |
- |
2.0 |
1.6 |
- |
2.6 |
1.6 |
- |
2.0 |
| Dobanol® 23-3 |
- |
- |
2.0 |
2.0 |
1.0 |
2.0 |
2.0 |
- |
| Salt-free Betaine* |
5.0 |
2.4 |
2.4 |
2.4 |
2.4 |
5.0 |
5.0 |
5.0 |
| H2O2 |
7.0 |
7.0 |
6.0 |
7.0 |
5.8 |
7.0 |
7.0 |
7.0 |
| HEDP |
0.16 |
- |
0.16 |
- |
0.16 |
0.16 |
0.16 |
0.16 |
| DTPMP |
- |
0.18 |
- |
0.18 |
- |
- |
- |
- |
| Propyl gallate |
0.1 |
0.1 |
- |
- |
- |
0.1 |
0.1 |
0.1 |
| BHT |
- |
- |
0.1 |
0.1 |
0.1 |
- |
- |
- |
| Citric acid |
0.05 |
0.05 |
0.50 |
0.05 |
0.50 |
0.05 |
0.05 |
0.05 |
| Water and minors |
up to 100% |
| H2SO4 up to pH 4 or 5 |
|
|
|
|
|
|
|
|
[0096] Salt-free Betaine* is Lauryl di-methyl betaine containing 0.3% by weight of sodium
chloride. This betaine is obtained by purification from commercially available Lauryl
di-methyl betaine GENAGEN LAB® (Hoechst) (which contains 7.5% by weight of sodium
chloride).
[0097] Compositions I to XVI when used to clean soiled colored fabrics exhibit excellent
overall stain removal performance especially on greasy stains like lipstick, make-up,
olive oil, mayonnaise, sebum and the like, and improved bleaching performance.
[0098] When used in a pretreatment mode, any of the compositions I to XVI is applied neat
on the stained portion of a fabric and left to act thereon for 5 minutes. Then the
fabric is washed with a conventional detergent and rinsed.
[0099] When used in a bleaching-through-the-wash mode, any of the compositions I to XVI
is contacted with an aqueous bath formed by dissolution of a conventional detergent
in water. Fabrics are then contacted with the aqueous bath comprising the liquid detergent,
and the fabrics are rinsed. They can also be used in a soaking mode, where 100 ml
of the liquid compositions are diluted in 10 litres of water. The fabrics are then
contacted with this aqueous bath containing the composition, and left to soak therein
for a period of time of 24 hours. The fabrics are eventually rinsed.
[0100] Compositions I to XVI when used to clean soiled hard-surfaces exhibit excellent overall
stain removal performance especially on kitchen dirt greasy stains.
[0101] Compositions IX to XVI when used to clean soiled colour fabrics in any laundry application
and especially in pretreatment conditions are safe to both the fabrics and colours.
1. A liquid aqueous composition having a pH up to 7 and comprising from 0.01% to 20%
by weight of the total composition of a peroxygen bleach, from 0.001% to 30% by weight
of the total composition of an ethoxylated nonionic surfactant, from 0.001% to 20%
by weight of a zwitterionic betaine surfactant at a weight ratio of the ethoxylated
nonionic surfactant to the zwitterionic betaine surfactant of from 0.01 to 20, with
the proviso that said composition is free of an antimicrobial essential oil or an
active thereof or a mixture thereof.
2. A composition according to claim 1 wherein said composition comprises from 0.01% to
15% by weight of the total composition of said ethoxylated nonionic surfactant or
mixture thereof, more preferably from 0.5% to 10% and most preferably from 1% to 6%.
3. A composition according to any of the preceding claims wherein said composition comprises
from 0.01% to 10% by weight of the total composition of said zwitterionic betaine
surfactant or mixture thereof, more preferably from 0.5% to 8% and most preferably
from 1% to 5%.
4. A composition according to any of the preceding claims wherein said peroxygen bleach
is hydrogen peroxide or a water soluble source thereof typically selected from the
group consisting of percarbonates, persilicates, persulphates, perborates, peroxyacids,
hydroperoxides, aromatic and aliphatic diacyl peroxides and mixtures thereof, preferably
is hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide,di-isopropylbenzenemonohydroperoxide,
tert-amyl hydroperoxide, 2,5-dimethyl-hexane-2,5-dihydroperoxide, dilauroyl peroxide,
didecanoyl peroxide, dimyristoyl peroxide, benzoyl peroxide or a mixture thereof,
and more preferably is hydrogen peroxide.
5. A composition according to any of the preceding claims which comprises from 1% to
15% by weight of the total composition of said peroxygen bleach or mixtures thereof,
preferably from 2% to 10%.
6. A composition according to any of the preceding claims wherein said zwitterionic betaine
surfactant is according to the formula:
R
1-N
+(R
2)(R
3)R
4X
-
wherein R1 is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
hydrocarbon chain that can contain linking groups such as amido groups, ester groups,
preferably an alkyl group containing from 1 to 24 carbon atoms, preferably from 8
to 18, and more preferably from 10 to 16, or an amido radical of the formula Ra-C(O)-NH-(C(Rb)2)m, wherein Ra is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms,
preferably up to 18, more preferably up to 16, Rb is selected from the group consisting of hydrogen and hydroxy groups, and m is from
1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group
in any (C(Rb)2) moiety;
R2 is hydrogen, C1-C6 alkyl, hydroxy alkyl or other substituted C1-C6 alkyl group;
R3 is C1-C6 alkyl, hydroxy alkyl or other substituted C1-C6 alkyl group which can also be joined to R2 to form ring structures with the N, or a C1-C6 carboxylic acid group or a C1-C6 sulfonate group;
R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically
an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon
atoms;
and X is a carboxylate or sulfonate group.
7. A composition according to any of the preceding claims wherein said zwitterionic betaine
surfactant contains less than 5% by weight of salts, preferably less than 2%, more
preferably less than 1% and most preferably from 0.01% to 0.5%.
8. A composition according to any of the preceding claims wherein said ethoxylated nonionic
surfactant is according to the formula RO-(C2H4O)nH, wherein R is a C6 to C22 alkyl chain or a C6 to C28 alkyl benzene chain, and wherein n is an integer from 0 to 20, preferably from 1
to 15, more preferably from 2 to 15 and most preferably from 2 to 12.
9. A composition according to any of the preceding claims wherein said composition further
comprises a chelating agent or a mixture thereof typically up to 5% by weight of the
total composition, preferably from 0.01% to 1.5%.
10. A composition according to claim 9 wherein said chelating agent is a phosphonate cheating
agent, an amino carboxylate chelating agent, another carboxylate chelating agent,
a polyfunctionally-substituted aromatic chelating agent, ethylenediamine N, N'-disuccinic
acid or mixtures thereof, and more preferably amino aminotri(methylene phosphonic
acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta methylene
phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic acid
or mixtures thereof.
11. A composition according to any of the preceding claims wherein said composition further
comprises at least an optional ingredient selected from the group consisting of builders,
other surfactants apart the ethoxylated nonionic surfactant and zwitterionic betaine
surfactants, stabilisers, bleach activators, soil suspenders, soil suspending polyamine
polymers, polymeric soil release agents, radical scavengers, catalysts, dye transfer
agents, solvents, brighteners, perfumes, dyes, pigments and mixtures thereof.
12. A process of cleaning fabrics which includes the steps of diluting in an aqueous bath
a liquid composition according to any of the preceding claims, in its neat form, contacting
said fabrics with said aqueous bath comprising said liquid composition, and subsequently
rinsing, or washing then rinsing said fabrics.
13. A process according to claim 12, wherein the fabrics are left to soak in said aqueous
bath comprising said liquid composition for a period of time ranging from 1 minute
to 48 hours, preferably from 1 hour to 24 hours.
14. A process according to claim 12, wherein said aqueous bath is formed by dissolving
or dispersing a conventional laundry detergent in water.
15. A process of pretreating fabrics which comprises the steps of applying a liquid composition
according to any of the claims 1 to 11, in its neat form, onto said fabrics, preferably
only soiled portions thereof, before rinsing said fabrics, or washing then rinsing
said fabrics.
16. A process of cleaning a hard-surface with a composition according to any of the claims
1 to 11, wherein said process comprises the step of applying said composition to said
hard-surface and optionally rinsing said hard-surface.
17. The use of a composition comprising a salt free zwitterionic betaine surfactant and
a peroxygen bleach for cleaning/bleaching fabrics whereby color safety is improved
and/or fabric safety is improved.