Note: Descriptions are shown in the official language in which they were submitted.
CA 02549554 2001-06-19
Flushable Hard Surface Cleaning Wet Wipe
10
Technical Field
The present invention relates to a wet wipe suitable for cleaning hard
surfaces,
which has sufficient wet sfirength to remain intact during the cleaning
action, but
1s which is also sufficiently biodegradable as to be suitable for flushing.
The wipes
according to the present invention are especially suitable for cleaning
bathroom
and kitchen surfaces.
Background
Wet wipes are typically pre-moistened, disposable towelettes which may be
utilised in a variety of applications both domestic and industrial and perform
a
variety of functions. Wet wipes are typically used to wipe inanimate surfaces,
and may provide numerous benefits such as cleaning; cleansing, and
disinfecting.
One particular application for wet wipes is wiping andlor cleaning surfaces
and
the application of compositions to surfaces, for example kitchen and bathroom
surfaces, spectacles, shoes and surfaces which require cleaning in industry,
for
3o example surfaces of machinery or vehicles.
1
CA 02549554 2001-06-19
Wet wipes are commonly constructed from webs of combinations of synthetic,
man-made and natural fibres, such as polyolefin fibres, viscose fibres, cotton
fibres, which are generally moistened with an aqueous composition which may
contain amongsfi others ingredients surfactants, preservatives, oils and
scents
s depending on the end use envisaged.
A variety of webs and liquid compositions suitable for application to such
webs
are known and disclosed in the art fisted below. Typically the webs require a
binder in order to provide strength to the web, in particular when wet.
WO 89/05114 discloses disposable wipes for hard surface cleaning which are
impregnated with a liquid composition and EP 0 211 773 discloses a cloth for
polishing a car. EP 0 113 254 discloses an antimicrobial non-woven fabric.
The fabric may be provided from natural or synthetic fibres or blends thereof.
According to the disclosed invention an antimicrobial agent is selected which
forms a colloidal suspension with a given conventional binder.
EP 0 233 943 discloses a non-woven wet wipe which is said to be
antimicrobially active. In a preferred embodiment the web for the wet wipes is
2o provided from wood pulp and comprises a non-acrylate binder (ethylene vinyl
acetate). The wet wipes further comprise an antimicrobial agent, which is
mixed
into the binder and applied to the non-woven web therewith.
US 5 888 524 discloses an antimicrobial composition for use with conventional
25 wet wipes and lotions. The wet wipes can be provided from synthetic or
natural
fibres or a combination thereof. According to the disclosed invention the wet
wipes are saturated with a rather high amount of the antimicrobia!
composition,
indeed, it is taught that the weight of the lotion should be up to 6 times the
weight of the dry wipe.
Traditionally, hard surface cleaning wipes have been made using synthetic
fibres since only synthetic fibres provide sufficient strength in the wipe for
it to
2
CA 02549554 2001-06-19
withstand the stress and strain of the cleaning action. Wipes made using
natural
and/or synthetic fibres have generally been much weaker in terms of tensile
strength and have required the use of a binder or wet strength agent to
increase the tensile strength to a level suitable to withstand the cleaning
action.
EP 0 602 881 discloses a wet wipe comprising wood pulp and man-made fibres
made preferably for use in personal hygiene, for example as moist fioilet
paper.
The wipes also comprise a wet strength agent, for example polyacrylamide, to
improve the wet strength of the wipe.
1o Synthetic wipes and those wipes comprising a binder suffer the disadvantage
of
being less biodegradable than wipes made using natural fibres, to the point
where they are not suitable for flushing down a lavatory since they may cause
blockages in drains and/or septic tanks. It is therefore the object of the
present
invention to provide a wet wipe that is sufficiently strong to be suitable for
~5 cleaning hard surfaces, but which is also sufficiently biodegradable such
that°it
can be safely flushed down a lavatory.
A further object of the present invention has been to find a wet wipe
substrate
that is suitable for flushing down a lavatory but which can also sustain a
high
2o cleaning composition loading factor without adversely affecting either the
tensile
strength or absorbency of the wipe.
Summar)i of the Invention
25 According to the present invention there is provided a fiushable wet wipe
suitable for cleaning a hard surface comprising a substrate having tensile
strength of at least 5 N/inch and which is biodegradable.
According to a further aspect of the present invention there is provided a
3o flushable wet wipe suitable for cleaning a hard surface comprising a
cleaning
composition and a substrate, wherein the substrate has a loading factor of at
3
CA 02549554 2001-06-19
least 1.5 grams of cleaning composition per gram of substrate and is
biodegradable.
Detailed Description of the Invention
The wet wipe of the present invention comprises a substrate which has tensile
strength, even when wet of greater than 5 N/inch, but yet is also
biodegradable.
Tensile Strength can be measured according to known techniques. Tensile
strength herein is measured according to standard European Disposable
Absorbent Non-woven Association (EDANA) Industry Methodology, reference
method # 20.2-89.
The substrate of the present invention has tensile strength measured in either
the machine direction or the cross direction of at least SNrnch. Machine
direction is defined as the direction in which the substrate moves through the
manufacturing machine. The Cross direction is defined as the direction
perpendicular to the machine direction. In a preferred embodiment the tensile
strength of the substrate is at least 8 N/inch and most preferably at least 10
2o N/inch measured in either the machine or cross direction. Even more
preferably
the substrate is designed such that the tensile strength measured in the
machine direction is higher than in the cross direction. Such a design
therefore
takes into account the additional tension that is placed on the wipe during
dispensing of the individual wipe.
In an alternative embodiment of the present invention, the substrate of the
present invention is designed such that it can retain enough cleaning
composition for the wipe to be used as an efficient cleaning tool, yet still
be
biodegradable and preferably also have sufficient absorption and tensile
3o strength when wet to withstand the stress and strain of the cleaning
action.
Hence according to the present invention the wet wipe comprises a substrate
which has a loading factor of at least 1.5 grams of cleaning composition per
4
CA 02549554 2001-06-19
gram of substrate, but yet is also biodegradable. Preferably the substrate has
a
loading factor of at least 2 grams, more preferably at least 2.8 grams of
cleaning
composition per gram of substrate. Loading factor is expressed as the weight
ratio of cleaning composition loaded onto the substrate and the substrate. In
s this embodiment it is also preferred that the substrate has tensile strength
of at
least 5N/inch, more preferably at least 8 N/inch and most preferably at least
10
N/inch measured in either the machine or cross direction.
In a further aspect the substrate of the present invention has absorption
capacity of at least 6 grams of water per gram of substrate, more preferably
at
least 8, most preferably at least 8.5 grams of water per gram of substrate.
Absorption capacity is measured according the standard EDANA non-woven
industry methodology reference method number 10.3-99.
~5 The substrate of the present invention is capable of biodegrading 'tiy
disintegration in anaerobic conditions within a short period of time.
Anaerobic
disintegration is measured according to a test method which simulates the
anaerobic disintegration environment in a septic tank or a sewage treatment
facility. During the test the wipes are exposed to biologically active
anaerobic
zo sludge over a period of 4 weeks and the percent disintegration is measured
by
weight loss over time.
Test method
Anaerobic sludge is obtained from a sewage treatment facility that handles
z5 predominantly residential waste. The anaerobic sludge is screened through a
18 mesh screen to remove any particles larger than 1 mm. A reactor bottle is
partially filled with 1.5 L of sludge, at least 15g/L of which is solids and
the pre-
weighed sample of a wipe. The bottle is then sealed with a one-hole stopper
which allows venting of effluent gases. The bottle is placed in a 35 °C
incubator
3o for the duration of the test. The reactor bottle is mixed daily by
inverting several
times to keep the samples in the sludge. Samples are removed from duplicate
reactor bottles over time. The sample is poured onto an 18 mesh sieve and then
CA 02549554 2001-06-19
rinsed under running tap water. Any sample residue that remains on the screen
is gently rinsed off and placed in a beaker to dry in the oven at 40 °C
overnight.
Cooled, dried samples are weighed to calculate percent weight loss.
Samples are deemed to be biodegradable if at least 95°/a
disintegration in
anaerobic conditions is achieved after 4 weeks of anaerobic digestion. In a
preferred embodiment of the present invention at least 97%, more preferably
substantially 100% disintegration in anaerobic conditions is achieved after 4
weeks of anaerobic digestion.
~o
Furthermore, the substrate of the present invention is also biodegradable in
aerobic conditions. Aerobic biodegradation is measured according to the
American Society for Testing and Materials ASTM) method D5271-93 which is a
standard test method for determining the aerobic biQdegradation in an
~5 activated-sludge-wastewater-treatment system.
Substrate
The substrate is preferably provided by a web, typically as a sheet of
material
cut from the web. The web may be woven or non-woven, foam, sponge,
2o battings, balls, puffs or films. Most preferably the web is non-woven and
comprises man-made fibers, even more preferably the web comprises solely
man-made fibres.
According to the present invention the web may be produced by any method
25 known in the art. For example non-woven material substrates can be formed
by
dry forming techniques such as carding, air-laying or wet laying, such as on a
paper making machine. Other non-woven manufacturing techniques such as
melt blown, spun bonded, needle punched, spun laced may also be used.
Preferably the web used in the present invention is produced using the carding
3o method, during which entangled fibrous mats are transformed into parallel
fibrous webs.
6
CA 02549554 2001-06-19
While various embodiments of a web, to provide a substrate, are within the
scope of the present invention and are detailed below, in a preferred
embodiment the web is carded and non-woven comprising man-made fibres, In
a preferred embodiment the web comprises at least 95%, even more preferably
at least 97% and most preferably approximately 100% man-made fiibres.
Man-made fibres, as used herein, includes fibres manufactured from cellulose,
for example derivatives of or regenerated cellulose and thus are
distinguishable
from synthetic fibres, which are based on synthetic organic polymers. A
1o derivative fibre, as used herein, is a fibre formed when a chemical
derivative of
a natural polymer, e.g., cellulose, is prepared, dissolved, and extruded as a
continuous filament, and the chemical nature of the derivative is retained
after
the fibre formation process. A regenerated fibre, as used herein, is a fibre
formed when a natural polymer, or its chemical derivative, is dissolved and
~5 extruded as a continuous filament. Whilst the physical nature of the
natural
polymer is changed, the chemical nature of the natural polymer is
substantially
retained or regenerated after the fibre formation process. Preferred man-made
fibres have a denier of 0.5 dtex to 3.0 dtex, more preferably of 1.0 dtex to
2.0
dtex, most preferably of 1.5 dtex to 2.0 dtex.
Preferred man-made fibres used in the present invention include rayon
(viscose) that is produced by dissolving cellulose fibres in N-
methylmorpholine-
N-oxide, resulting in what is known as regenerated cellulosic fibres and which
are supplied by Tencel Fibres Europe, UK.
Man-made fibres are preferred fibres for use in webs of the present invention
due to their high consumer acceptance and their cheap and typically ecological
production. Man-made fibres and in particular cellulose derived man-made
fibres, are known to exhibit high biodegradability, however it had not
previously
so been realised that webs made entirely or substantially entirely of man-made
fibres could be suitable for use as a wet wipe substrate. Wet wipes composed
of man-made fiber web substrates provide further advantages in that the fibres
7
CA 02549554 2001-06-19
used can also be chemically or physically altered during the fiber formation
process so as to comprise further advantageous benefits such as softness,
roughness and absorbency.
s The web preferably has a weight of at least 20 gm-2 and preferably less than
150 gm-2, and most preferably the base weight is in the range of 20 gm-2 to
100 gm-2, more preferably from 40 gm-2 to 70 gm-2. The web may have any
caliper. Typically, when the web is made by an air laying process, the average
web caliper is less than 1.0 mm. More preferably the average caliper of the
web
is from 0.2 mm to 0.9 mm. The web caliper is measured according to standard
EDANA Non-woven Industry Methodology, reference method # 30.4-89.
In addition to the fibres used to make the web, the web can comprise other
components or materials added thereto as known in the art, to improve
~o appearance, surface texture, colour, and odour. An example is the use of
opacifying agents, for example titanium dioxide.
In order to achieve the strength requirement of one embodiment of the wet wipe
substrate, the fibres are hydroentangled. Hydroentanglement is a process
2o whereby fibers of the web are rearranged and entangled by means of fluid
forces. Hydroentanglement can in this way be used as a bonding means,
repositioning and entangling individual fibers into configurations that bring
about
frictional interlocking at the fiber level. In addition to the bonding
benefits,
hydroentanglement can also be used to provide surface texturing, whereby
2s hydroentanglement repositions fibers into open-patterned arrangements. Webs
that have undergone a hydroentanglement treatment, contain no chemical
binders, and have not been thermally bonded. Hydroentangled non-woven
webs are mechanically strong, can .withstand stretching, pulling and abrasion,
but can are be made to be tactil and soft. Furthermore the absorbency and
so wetting cpability of the web is not adversely affected by the
hydroentanglement
process.
a
CA 02549554 2001-06-19
Hence according to the present invention the substrate of the most preferred
embodiment is. composed of substantially 100% hydroentangled man-made
regenerated cellulosic fibres.
According to a preferred embodiment of the present invention the substrate
incorporates a cleaning composition as described herein. By "incorporates" it
is
meant herein that said substrate or wet wipe is coated or impregnated with a
preferably liquid cleaning composition as described herein.
In preparing wet wipes according to the present invention, the composition is
applied to at least one surface of the substrate material. The composition can
be applied at any time during the manufacture of the wet wipe. Preferably the
composition can be applied to the substrate after the substrate has been
dried.
Any variety of application methods that evenly distribute lubricious materials
having a molten or liquid consistency can be used. Suitable methods include
spraying, printing, (e.g. flexographic printing), coating (e.g. gravure
coating or
flood coating) extrusion whereby the composition is forced through tubes in
contact with the substrate whilst the substrate passes across the tube or
combinations of these application techniques. For example spraying the
2o composition on a rotating surface such as calender roll that then transfers
the
composition to the surface of the substrate. The composition can be applied
either to one surface of the substrate or both surfaces, preferably both
surfaces.
The preferred application method is extrusion coating.
The composition can also be applied uniformly or non uniformly to the surfaces
of the substrate. By non uniform it is meant that for example the amount,
pattern
of distribution of the composition can vary over the surface of the substrate.
For
example some of the surface of the substrate can have greater or lesser
amounts of composition, including portions of the surface that do not have any
so composition on it. Preferably however the composition is uniformly applied
to
the surfaces of the wipes.
9
CA 02549554 2001-06-19
Preferably, the composition can be applied to the substrate at any point after
it
has been dried. For example the composition can be applied to the substrate
preferably after calendering and prior to being wound up onto a parent roll.
Typically, the application will be carried out on a substrate unwound from a
roll
s having a width equal to a substantial number of wipes it is intended to
produce.
The substrate with the composition applied thereto is then subsequently
perforated utilising standard techniques in order to produce the desired
perforation line, Alternatively the substrate may be unwound from a roll,
pertorated to form wipes of the correct size, folded and then the composition
is
1o applied to the substrate.
Comloosition
The composition of the present invention is preferably suitable for use as a
cleaning and/or disinfecting composition. The compositions may be formulated
~s in any suitable form for example as a solid, paste or liquid. In the case
where
the compositions according to the present invention are formulated as solids,
they can be applied to the substrate as a solid or alternatively can be mixed
with
an appropriate solvent, typically water, before application to the substrate.
Where the composition is in liquid form, the compositions are preferably but
not
2o necessarily formulated as aqueous compositions. Liquid compositions are
preferred herein for convenience of use.
In a preferred embodiment the liquid compositions according to the present
invention are aqueous compositions typically comprising from 50% to 99.9% by
2s weight of the total composition of water, preferably from 70% to 99% and
more
preferably from 80% to 99%. These aqueous compositions preferably have a
pH as is of not more than 13.0, more preferably from 1 to 11, and most
preferably from 2 to 10. The pH of the compositions can be adjusted by using
organic or inorganic acids, or alkalinising agents, such as sodium hydroxide.
Compositions suitable for use as a cleaning composition preferably have pH in
the range of from 5 to 13, more preferably from 7 to 13 and most preferably
CA 02549554 2001-06-19
from 8 to 10. Compositions for use as disinfecting compositions preferably
have a pH in the range of from 0 to 7, more preferably from 1 to 5 and most
preferably from 2 to 4.
s The compositions herein may comprise a variety of ingredients including, but
not limited to peroxygen bleach, disinfecting components, organic acids,
surfactants, chelants, solvents, builders, stabilisers, bleach activators,
soil
suspenders, dye transfer agents, brighteners, perfumes, anti dusting agents,
enzymes, dispersant, dye transfer inhibitors, pigments, perfumes, radical
scavengers, pH buffers, dyes or mixtures thereof.
Surfactant System
According to the present invention the substrate preferably incorporates a
composition comprising a surfactant system. The surfactant system consists of
a
15 synergistic system comprising at least three surfactants, namely an
anionic, a
nonionic and an amphoteric and/or zwitterionic surfactant.
The compositions preferably comprises the surfactant system at a level by
weight
of the total composition of from 0.05-20%, more preferably from 0.1-5% and
2o most preferably from 0.2-3%.
Anionic Surfactant:
Suitable anionic surfactants for use herein include alkyl sulphates. Suitable
alkyl
sulphates for use herein include water-soluble salts or acids of the formula
25 ROS03M wherein R is a Cg-C24 linear or branched, saturated or unsaturated
alkyl group, preferably a Cg-C20 alkyl group, more preferably a Cg-C16 alkyl
group and most preferably a C10-C14 alkyl group, 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
3o cations and quaternary ammonium cations, such as tetramethyl-ammonium and
dimethyl piperdinium cations and quaternary ammonium cations derived from
11
CA 02549554 2001-06-19
alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures
thereof, and the like).
Suitable anionic surfactants for use herein further include alkyl aryl
sulphates.
s Suitable alkyl aryl sulphates for use herein include water-soluble salts or
acids
of the formula ROSOgM wherein R is an aryl, preferably a benzyl, substituted
by a C6-C24 linear or branched saturated or unsaturated alkyl group,
preferably
a Cg-C20 alkyl group and more preferably a C1p-C1g alkyl group and M is H or
a ration, e.g., an alkali metal ration (e.g., sodium, potassium, lithium,
calcium,
1o magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-,
dimethyl-, and trimethyl ammonium rations and quaternary ammonium rations,
such as tetramethyl-ammonium and dimethyl piperdinium rations and
quaternary ammonium rations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like).
Suitable anionic surfactants for use herein further include alkoxylated
sulphate
surfactants. Suitable alkoxylated sulphate surfactants for use herein are
according to the formula RO(A)mSOgM wherein R is an unsubstituted Cg-C24
alkyl, hydroxyalkyl or alkyl aryl group, having a linear or branched Cg-C24
alkyl
2o component, preferably a C12-C~0 alkyl or hydroxyalkyl, more preferably C12-
C1g alkyl or hydroxyalkyl, A is an ethoxy or propoxy or butoxy unit or a
mixture
thereof, m is greater than zero, typically between 0.5 and 6, more preferably
between 0.5 and 3, and M is H or a ration which can be, for example, a metal
ration (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium
or substituted-ammonium ration. Alkyl ethoxylated sulphates, alkyl butoxylated
sulphates as well as alkyl propoxylated sulphates are contemplated herein.
Specific examples of substituted ammonium rations include methyl-, dimethyl-,
trimethyl-ammonium and quaternary ammonium rations, such as tetramethyl-
ammonium, dimethyl piperdinium and rations derived from alkanolamines such
3o as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
Exemplary surfactants are C12-C1g alkyl polyethoxylate (1.0) sulphate (C12-
12
CA 02549554 2001-06-19
CIgE(1.0)SM), C12-C1g alkyl polyethoxylate (2.25) sulphate (C12-
C1 gE(2.25)SM), C12-C1 g alkyl polyethoxylate (3.0) sulphate (C12-
CIgE(3.0)SM), and C12-Cog alkyl polyethoxylate (4.0) sulphate (C12-
CIgE(4.0)SM), wherein M is conveniently selected from sodium and potassium.
Suitable anionic surfactants for use herein further include alkyl sulphonates.
Suitable alkyl sulphonates for use herein include water-soluble salts or acids
of
the formula RS03M wherein R is a Cg-C20 linear or branched, saturated or
unsaturated alkyl group, preferably a Cg-C1g alkyl group and more preferably a
1o Cg-C12 linear or branched alkyl group, 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 rations and
quaternary ammonium rations, such as tetramethyl-ammonium and dimethyl
piperdinium rations and quaternary ammonium rations derived ~ from
alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures
thereof, and the like).
Suitable anionic surfactants for use herein further include alkyl aryl
sulphonates.
Suitable alkyl aryl sulphonates for use herein include water-soluble salts or
2o acids of the formula RS03M wherein R is an aryl, preferably a benzyl,
substituted by a Cg-C20 linear or branched saturated or unsaturated alkyl
group, preferably a Cg-C1g alkyl group and more preferably a Cg-Coq, alkyl
group, and M is H or a ration, e.g., an alkali metal ration (e.g., sodium,
potassium, lithium, calcium, magnesium and the like) or ammonium or
substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium
rations and quaternary ammonium rations, such as tetramethyl-ammonium and
dimethyl piperdinium rations and quaternary ammonium rations derived from
alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures
thereof, and the like).
13
CA 02549554 2001-06-19
Particularly suitable alkyl sulphonates include Clq.-C17 paraffin sulphonate
like
Hostapur ~ SAS commercially available from Hoechst. An example of
commercially available alkyl aryl suiphonate is Lauryl aryl sulphonate from
Su.Ma.. Particularly preferred alkyl aryl sulphonates are alkyl benzene
sulphonates commercially available under trade name Nansa~ available from
Albright&Wilson.
Suitable anionic surfactants for use herein further include alkoxylated
sulphonate surfactants. Suitable alkoxylated sulphonate surfactants for use
1o herein are according to the formula R(A)mSOgM wherein R is an unsubstituted
Cg-C20 alkyl, hydroxyalkyl or alkyl aryl group, having a linear or branched Cg-
C2p alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
preferably C12-C1g alkyl or hydroxyalkyl, A is an ethoxy or propoxy or butoxy
unit, m is greater than zero, typically between 0.5 and 6, more preferably
between 0.5 and 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 sulphonates, alkyl
butoxylated sulphonates as well as alkyl propoxylated sulphonates are
contemplated herein. Specific examples of substituted ammonium cations
2o 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 C12-C1 g alkyl
polyethoxylate (1.0) sulphonate (C12-CIgE(1.0)SM), C12-C1g alkyl
polyethoxylate (2.25) sulphonate (C12-C1 gE(2.25)SM), C12-C1 g alkyl
polyethoxylate (3.0) sulphonate (C12-CIgE(3.0)SM), and C12-C1g alkyl
polyethoxyiate (4.0) sulphonate (C12-C1 gE(4.0)SM), wherein M is conveniently
selected from sodium and potassium. Particularly suitable alkoxylated
sulphonates include alkyl aryl polyether sulphonates like Triton X-200~
3o commercially available from Union Carbide.
14
CA 02549554 2001-06-19
Suitable anionic surtactants for use herein further include Cg-C20 alkyl
alkoxylated linear or branched diphenyl oxide disulphonate surfactants.
Suitable
Cg-C20 alkyl alkoxylated linear or branched diphenyl oxide disulphonate
surfactants for use herein are according to the following formula:
0
So3-X+ Sp3-X+
wherein R is a Cg-C20 linear or branched, saturated or unsaturated alkyl
group;
preferably a C6-C1 g.alkyl group and more preferably a Cg-C14 alkyl group, and
1o X+ is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium,
lithium,
calcium, magnesium and the like). Particularly suitable Cg-C20 alkyl
alkoxylated
linear or branched diphenyl oxide disulphonate surfactants to be used herein
are the C12 branched di phenyl oxide disulphonic acid and C1 g linear di
phenyl
oxide disulphonate sodium salt respectively commercially available by DOW
~ 5 under the trade name Dowfax 2A1 ~ and Dowfax 8390~.
Other suitable anionic surfactants for use herein include alkyl-carboxyiates
Other anionic surtactants can include salts (including, for example, sodium,
potassium, ammonium, and substituted ammonium salts such as mono-, di- and
20 triethanolamine salts) of soap, Cg-C2q. 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; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl
phenol
ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl
25 isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6-C14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as
CA 02549554 2001-06-19
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(CH2CH20)kCH2C00-M+ wherein R is a C8-
C22 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. 1 and il by Schwartz, Perry and Berch). A variety of such
surfactants are also generally disclosed in U.S. Patent 3,929,678, issued
1o December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column
29,
line 23.
In one preferred embodiment, preferred anionic surfactants for use herein are
the C8-C16 alkyl sulfonates, C8-C16 alkyl sulfates, including branched alkyl
1s sulphates, C8-C16 alkyl alkoxylated sulfates (e.g., C8-C16 alkyl
ethoxylated
sulfates), C8-C16 alkyl alkoxylated sulphonates and mixtures thereof. Such
anionic surfactants are preferred herein as it has been found that they
contribute to the disinfecting properties of a disinfecting composition
herein. For
example, C8-C16 alkyl sulfate acts by disorganizing the bacteria cell
2o membrane, inhibiting enzymatic activities, interrupting the cellular
transport
and/or denaturing cellular proteins. Indeed, it is speculated that the
improved
disinfecting performance further associated with the addition of an anionic
surfactant, especially a C8-C16 alkyl sulfonate, a C8-C16 alkyl sulfate and/or
a
C8-C16 alkyl alkoxylated sulfate, in a composition according to the present
2s invention, is likely due to multiple mode of attack of said surfactant
against the
bacteria.
In a second preferred embodiment, the anionic surfactant is selected from the
group consisting of : C6-24 alkyl sulphates; Cg_24 alkyl aryl sulphates; Cg_24
3o alkyl alkoxylated sulphates; C6_24 alkyl sulphonates, including paraffin
sulphonates; Cg_24 alkyl aryl sulphonates; C6_24 alkyl alkoxylated
sulphonates;
16
CA 02549554 2001-06-19
Cg-C24 alkyl alkoxylated linear or branched diphenyl oxide disulphonates;
naphthalene sulphonates; and mixtures thereof. More preferably the anionic
surtactant is selected from the group consisting of : Cg_24 alkyl sulphonates;
C6-24 alkyl sulphates; Cg_24 alkyl alkoxylated sulphates; C6_24 alkyl aryl
sulphonates; and mixtures thereof. Even more preferably the anionic surfactant
for use herein is a paraffin sulphonate. Most preferably the anionic
surfactant for
use herein is a C14-C17 paraffin sulphonate.
In a third preferred embodiment the anionic surfactant is a branched alkyl
1o sulphate surfactant. Branched alkyl sulphate is herein defined to mean a an
alkyl
sulfate comprising a sulfate group and a carbon chain of preferably from 2 to
20,
more preferably from 2 to 16, most preferably from 2 to 8 carbon atoms. The
carbon chain of the branched alkyl sulfate comprises at least one branching
group attached to the carbon chain. The branching group is selected from the
group consisting of an alkyl group having from 1 to 20 , more preferably from
/~1 to
10 and most preferably from 1 to 4 carbon atoms. The branching group may be
located at any position along the alkyl chain of the branched alkyl sulfate.
More
preferably the branching group is located at position from 1 to 4 along the
alkyl
chain. The sulfate group can be at any point along the length of the alkyl
chain,
2o most preferable at a terminus.
Suitable preferred branched alkyl sulfates include those available from
Albright &
Wilson under the tradename Empicol 0585/A.
Nonionic Surfactant:
Suitable nonionic surfactants for use herein are fatty alcohol ethoxylates
and/or
propoxylates which are commercially available with a variety of fatty alcohol
chain lengths and a variety of ethoxylation degrees. Indeed, the HLB values of
such alkoxylated nonionic surfactants depend essentially on the chain length
of
so the fatty alcohol, the nature of the alkoxylation and the degree of
alkoxylation.
Surfactant catalogues are available which list a number of surfactants,
including
nonionics, together with their respective HLB values. Preferred nonionic
17
CA 02549554 2001-06-19
surfactants for one embodiment are those having an average HLB from 8 to 20,
more preferably from 10 to 18, most preferably from 11 to 16. These
hydrophobic nonionic surfactants have been found to provide good grease
cutting properties.
Preferred hydrophobic nonionic surfactants for use in the compositions
according
to the present invention are surfactants having an HLB below 16 and, being
according to the formula RO-(C2H40)n(C3H60)mH, wherein R is a Cg to C22
alkyl chain or a C6 to C2g alkyl benzene chain, and wherein n+m is from 0 to
20
1o and n is from 0 to 15 and m is from 0 to 20, preferably n+m is from 1 to 15
and, n
and m are from 0.5 to 15, more preferably n+m is from 1 to 10 and, n and m are
from 0 to 10. The preferred R chains for use herein are the Cg to C22 alkyl
chains. Accordingly, suitable hydrophobic nonionic surfactants for use herein
are
Dobanol R 91-2.5 (HLB= 8.1; R is a mixture of C9 and C1~ alkyl chains, n is
2.5
1s and m is 0), or Lutensol R T03~(HLB=8; R is a C13 alkyl chains, n is 3 and
m is
0), or Lutensol R A03 (HLB=8; R is a mixture of C13 and C15 alkyl chains, n is
3
and m is 0), or Tergitol R 25L3 (HLB= 7.7; R is in the range of C12 to C15
alkyl
chain length, n is 3 and m is 0), or Dobanol R 23-3 (HLB=8.1; R is a mixture
of
C12 and C13 alkyl chains, n is 3 and m is 0), or Dobanol R 23-2 (HLB=6.2; R is
2o a mixture of C12 and C13 alkyl chains, n is 2 and m is 0), or Dobanol R 45-
7
(HLB=11.6; R is a mixture of C14 and C15 alkyl chains, n is 7 and m is 0)
Dobanol R 23-6.5 (HLB=11.9; R is a mixture of C12 and C13 alkyl chains, n is
6.5 and m is 0), or Dobanol R 25-7 (HLB=12; R is a mixture of C12 and C15
alkyl
chains, n is 7 and m is 0), or Dobanol R 91-5 (HLB=11.6; R is a mixture of Cg
2s and C11 alkyl chains, n is 5 and m is 0), or Dobanol R 91-6 (HLB=12.5 ; R
is a
mixture of Cg and C11 alkyl chains, n is 6 and m is 0), or Dobanol R 91-8
(HLB=13.7 ; R is a mixture of Cg and C11 alkyl chains, n is 8 and m is 0),
Dobanol R 91-10 (HLB=14.2 ; R is a mixture of Cg to C11 alkyl chains, n is 10
18
CA 02549554 2001-06-19
and m is 0), or mixtures thereof. Preferred herein are Dobanol R 91-2.5 , or
Lutensol R T03, or Lutensol R A03, or Tergitol R 25L3, or Dobanol R 23-3; or
Dobanol R 23-2, or mixtures thereof. These DobanolR surfactants are
commercially available from SHELL. These LutensolR surfactants are
commercially available from BASF and these Tergitol R surfactants are
commercially available from UNION CARBIDE.
In a preferred embodiment the nonionic surfactant herein is an alkoxylated
nonionic surfactant according to the formula RO-(A)nH, wherein : R is a Cg to
C22, preferably a Cg to C22, more preferably a Cg to C14 alkyl chain, or a Cg
to C2g alkyl benzene chain; A is an ethoxy or propoxy or butoxy unit; and
wherein n is from 0 to 20, preferably from 1 to 15 and, more preferably from 2
to
15 even more preferably from 2 to 12 and most preferably from 4 to 10.
Preferred R chains for use herein are the Cg to C22 alkyl chains. Even more
15 preferred R chains for use herein are the Cg to C12 alkyl chains.
Ethoxy/butoxylated, ethoxylpropoxylated, butoxylpropoxylated and
ethoxy/butoxylpropoxylated nonionic surfactants may also be used herein.
Preferred alkoxylated nonionic surfactants are ethoxylated nonionic
surfactants.
2o Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No.
4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from about 10 to
about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic
group. For acidic or alkaline cleaning compositions/solutions suitable for use
in
25 no-rinse methods, the preferred alkyl polysaccharide preferably comprises a
broad distribution of chain lengths, as these provide the best combination of
wetting, cleaning, and low residue upon drying. This "broad distribution" is
defined by at least about 50% of the chainlength mixture comprising from about
carbon atoms to about 16 carbon atoms. Preferably, the alkyl group of the
so alkyl polysaccharide consists of a mixtures of chainlength, preferably from
about
6 to about 18 carbon atoms, more preferably from about 8 to about 16 carbon
19
CA 02549554 2001-06-19
atoms, and hydrophilic group containing from about one to about 1.5
saccharide, preferably glucoside, groups per molecule. This "broad chainlength
distribution" is defined by at least about 50% of the chainlength mixture
comprising from about 10 carbon atoms to about 16 carbon atoms. A broad
s mixture of chain lengths, particularly Cs-C~6, is highly desirable relative
to
narrower range chain length mixtures, and particularly versus lower (i.e., Ce-
C,o
or Ce C~2) chainlength alkyl polyglucoside mixtures. It is also found that the
preferred C8_,6 alkyl polyglucoside provides much improved perfume solubility
versus lower and narrower chainlength alkyl polyglucosides, as well as other
preferred surfactants, including the C$-C,4 alkyl ethoxylates. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose,
galactose and galactosyl moieties can be substituted for the glucosyl
moieties.
(optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.
positions thus
giving a glucose or galactose as opposed to a glucoside or galactoside.) The
is intersaccharide bonds can be, e.g., between the one position of the
additional
saccharide units and the 2-, 3-, 4-, andlor 6- positions on the preceding
saccharide units. The glycosyl is preferably derived from glucose,
Optionally, and less desirably, there can be a polyalkyleneoxide chain joining
2o the hydrophobic moiety and the polysaccharide moiety. The preferred
alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl
groups, either saturated or unsaturated, branched or unbranched containing
from 8 to 18, preferably from 10 to 16, carbon atoms. Preferably, the alkyl
group
is a straight-chain saturated alkyl group. The alkyl group can contain up to
25 about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up
to
about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl
polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-,
and
hexaglucosides and/ or gaiatoses. Suitable mixtures include coconut alkyl, di-
,
so tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, yenta- and
hexaglucosides.
CA 02549554 2001-06-19
To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed
first and then reacted with glucose, or a source of glucose, to form the
glucoside
(attachment at the 1-position). The additional glycosyl units can then be
attached between their 1-position and the preceding glycosyl units 2-,3-, 4-
and/or 6-position, preferably predominantly the 2-position.
In the alkyl polyglycosides, the alkyl moieties can be derived from the usual
sources like fats, oils or chemically produced alcohols while their sugar
moieties
are created from hydrolyzed polysaccharides. Alkyl polyglycosides are the
1o condensation product of fatty alcohol and sugars like glucose with the
number
of glucose units defining the relative hydrophilicity. As discussed above, the
sugar units can additionally be alkoxylated either before or after reaction
with
the fatty alcohols. Such alkyl polyglycosides are described in detail in WO
86/05199 for example. Technical alkyl polyglycosides are generally not
~5 molecularly uniform products, but represent mixtures of alkyl groups ar~~!
mixtures of monosaccharides and different oligosaccharides. Alkyl
polyglycosides (also sometimes referred to as "APG's") are preferred for the
purposes of the invention since they provide additional improvement in surface
appearance relative to other surtactants. The glycoside moieties are
preferably
2o glucose moieties. The alkyl substituent is preferably a saturated or
unsaturated
alkyl moiety containing from about 8 to about 18 carbon atoms, preferably from
about 8 to about 10 carbon atoms or a mixture of such alkyl moieties. Ce-C,B
alkyl polyglucosides are commercially available (e.g., Simusol~ surfactants
from Seppic Corporation, 75 Quai d'Orsay, 75321 Paris, Cedex 7, France, and
25 Glucopon~425 available from Henkel. However, it has been found that purity
of
the alkyl polyglucoside can also impact performance, particularly end result
for
certain applications, including daily shower product technology. In the
present
invention, the preferred alkyl polyglucosides are those which have been
purified
enough for use in personal cleansing. Most preferred are "cosmetic grade"
alkyl
3o polyglucosides, particularly Ce to C,6 alkyl polyglucosides, such as
Plantaren '
2000~, Plantaren 2000 N~, and Plantaren 2000 N UP~, available from Henkel
Corporation (Postfach 101100, D 40191 Dusseldorf, Germany).
21
CA 02549554 2001-06-19
Amphoteric/Zwitterionic Surfactant:
Suitable amphoteric surfactants for use herein include amine oxides having the
following formula R1 R2R3N0 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 follqwing
formula R1 R2R3N0 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 and Clariant.
2o Suitable zwitterionic surfactants for use herein contain both cationic and
anionic
hydrophilic groups on the same molecule at a relatively wide range of pH's.
The
typical cationic group is a quaternary ammonium group, although other
positively charged groups like phosphonium, imidazolium and sulfonium groups
can be used. 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 some zwitterionic surfactants to be used herein
is
R1-N~~R2)~R3)R4X_
wherein R1 is a hydrophobic group; R2 and R3 are each C1-C4 alkyl, hydroxy
alkyl or other substituted alkyl group which can also be joined to form ring
22
CA 02549554 2001-06-19
structures with the N; 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 the hydrophilic group
which is preferably a carboxylate or sulfonate group. Preferred hydrophobic
s groups R1 are alkyl groups containing from 1 to 24, preferably less than 18,
more preferably less than 16 carbon atoms. The hydrophobic group can contain
unsaturation and/or substituents and/or linking groups such as aryl groups,
amido groups, ester groups and the like. In general, the simple alkyl groups
are
preferred for cost and stability reasons.
Highly preferred zwitterionic surfactants include betaine and sulphobetaine
surfactants, functionalized betaines such as acyl betaines, alkyl imidazoline
alanine betaines, glycine betaines, derivatives thereof and mixtures thereof.
Said betaine or sulphobetaine surfactants are preferred herein as they help
disinfection by increasing the permeability of the bacterial cell wall, thus
allowing
other active ingredients to enter the cell.
Furthermore, due to the mild action profile of said betaine or sulphobetaine
surfactants, they are particularly suitable for the cleaning of delicate
surfaces,
2o e.g., delicate laundry or surfaces in contact with food and/or babies.
Betaine
and sulphobetaine surfactants are also extremely mild to the skin and/or
surfaces to be treated.
Suitable betaine and sulphobetaine surfactants for use herein are the
2s betaine/sulphobetaine 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, incorporated herein by
so reference. Preferred betaine and sulphobetaine surfactants herein are
according to the formula
23
CA 02549554 2001-06-19
R2
R1 - N+ - (CH2)n - Y-
n
R3
wherein R1 is a hydrocarbon chain containing from 1 to 24 carbon atoms,
preferably from 8 to 18, more preferably from 12 to 14, wherein R2 and R3 are
hydrocarbon chains containing from 1 to 3 carbon atoms, preferably 1 carbon
atom, wherein n is an integer from 1 to 10, preferably, from 1 to 6, more
preferably is 1, Y is selected from the group consisting of carboxyl and
sulfonyl
radicals and wherein the sum of R1, R2 and R3 hydrocarbon chains is from 14
to 24 carbon atoms, or mixtures thereof.
Examples of particularly suitable betaine surfactants include C12-C18 alkyl
2o dimethyl betaine such as coconut-betaine and C10-C16 alkyl dimethyl betaine
such as laurylbetaine. Coconutbetaine is commercially available from Seppic
under the trade name of Amonyl 265~. Laurylbetaine is commercially available
from Albright & Wilson under the trade name Empigen BB/L~.
25 Other specific zwitterionic surfactants have the generic formulas:
R1-C(O)-N(R2)-(C(R3)2)n-N(R2)2(+)-(C(R3)2)n-S03(-)
or R1-C(O)-N(R2)-(C(R3)2)n-N(R2)2(+)-(C(R3)2)n-COO(-)
so wherein each R1 is a hydrocarbon, e.g. an alkyl group containing from 8 up
to
20, preferably up to 18, more preferably up to 16 carbon atoms, each R2 is
24
CA 02549554 2001-06-19
either a hydrogen (when attached to the amido nitrogen), short chain alkyl or
substituted alkyl containing from one to 4 carbon atoms, preferably groups
selected from the group consisting of methyl, ethyl, propyl, hydroxy
substituted
ethyl or propyl and mixtures thereof, preferably methyl, each R3 is selected
from the group consisting of hydrogen and hydroxy groups and each n is a
number from 1 to 4, preferably from 2 to 3, more preferably 3, with no more
than one hydroxy group in any (C(R3)2) moiety. The R1 groups can be
branched and/or unsaturated. The R2 groups can also be connected to form
ring structures. A surfactant of this type is a C1p-C14 fatty
acylamidopropylene(hydroxypropylene)sulfobetaine that is available from the
Sherex Company under the trade name "Varion CAS sulfobetaine"~.
Peroxvaen Bleach
The compositions according to the present invention may comprise a peroxyg~~n
bleach as an optional feature.
A preferred peroxygen bleach is hydrogen peroxide, or a water soluble source
thereof, or mixtures thereof. As used herein a hydrogen peroxide source refers
to any compound which produces hydrogen peroxide when said compound is in
contact with water. Suitable water-soluble sources of hydrogen peroxide for
use
2o herein include percarbonates, persilicates, persulphates such as
monopersulfate, perborates and peroxyacids such as diperoxydodecandioic
acid (DPDA), magnesium perphthalic acid and mixtures thereof.
In addition, other classes of peroxides can be used as an alternative to
hydrogen peroxide and sources thereof or in combination with hydrogen
peroxide and sources thereof. Suitable classes include dialkylperoxides,
diacylperoxides, preformed percarboxylic acids, organic and inorganic
peroxides and/or hydroperoxides. The most preferred peroxygen bleach is
hydrogen peroxide.
CA 02549554 2001-06-19
The presence of said peroxygen bleach especially hydrogen peroxide,
persulfate and the like, in the compositions according to the present
invention
can contribute to disinfection properties of said compositions. Indeed, said
peroxygen bleach may attack the vital function of the micro-organism cells,
for
s example, it may inhibit the assembling of ribosomes units within the
cytoplasm
of the microorganisms cells. Also said peroxygen bleach like hydrogen
peroxide, is an oxidiser that generates hydroxyl free radicals which attack
proteins and nucleic acids. Furthermore, the presence of said peroxygen
bleach, especially hydrogen peroxide, provides strong stain removal benefits
which are particularly noticeable for example in laundry and hard surfaces
applications.
Typically, peroxygen bleach or a mixture thereof is present in the
compositions
according to the present invention at a level of at least 0.01 % by weight of
the
~s total composition, preferably from 0.1 % to 15%, and more preferably from 1
% to
10%.
Disinfecting agent
2o Another preferred component of the compositions of the present invention is
a
disinfecting agent. Any suitable known disinfecting agent may be used herein
including organic acids, quaternary ammonium compounds, antimicrobial
essential oils or actives thereof, or a mixtures thereof.
2s Preferred therein include organic acids, antimicrobial essential oils or
actives
thereof, or a mixtures thereof. Preferred organic acids include citric acid,
tartaric acid, salicylic acid, lactic acid and mixtures thereof.
Suitable antimicrobial essential oils to be used herein are those essential
oils
so which exhibit antimicrobial activity. By "actives of essential oils", it is
meant
herein any ingredient of essential oils or natural extracts that exhibit
antimicrobial
activity. It is speculated that said antimicrobial essential oils and actives
thereof
26
CA 02549554 2001-06-19
act as proteins denaturing agents. Also said antimicrobial oils and actives
thereof
are compounds.which contribute to the safety profile of a composition
comprising
them when it is used to disinfect any surface. A further advantage of said
antimicrobial oils .and actives thereof is that they impart pleasant odor to a
composition comprising them without the need of adding a perfume.
Such antimicrobial essential oils include, but are not limited to, those
obtained
from thyme, lemongrass, citrus, lemons, oranges, anise, clove, aniseed, pine,
cinnamon; geranium, roses, mint, lavender, citronella, eucalyptus, peppermint,
camphor, ajowan, sandalwood, rosmarin, vervain, fleagrass, lemongrass,
ratanhiae, cedar, origanum, cypressus, propolis extracts and mixtures thereof.
Preferred antimicrobial essential oils to be used herein are thyme oil; clove
oil,
cinnamon oil, geranium oil, eucalyptus oil, peppermint oil, citronella oil,
ajowan
oil, mint oil, origanum oil, propolis, cypressus oil cedar , garlic extract or
mixtures
thereof.
Actives of essential oils to be used herein include, but are not limited to,
thymol
(present for example in thyme, ajowan), eugenol (present for example in
cinnamon and clove), menthol (present for eXample in mint), geraniol (present
for
2o example in geranium and rose, citronella), verbenone (present for example
in
vervain), eucalyptol and pinocarvone (present in eucalyptus), cedrol (present
for
example in cedar), anethol (present for example in anise), carvacrol,
hinokitiol,
berberine, ferulic acid, cinnamic acid, methyl salicylic acid, methyl
salycilate,
terpineol, limonene and mixtures thereof. Preferred actives of essential oils
to be
used herein are thymol, eugenol, verbenone, eucalyptol, terpineol, cinnamic
acid,
methyl salicylic acid, limonene, geraniol, ajolene or mixtures thereof.
Thymol may be commercially available for example from Aidrich, eugenoi may be
commercially available for example from Sigma, Systems - Bioindustries (SBI) -
so Manheimer Inc.
27
CA 02549554 2001-06-19
Typically, the antimicrobial essential oil or active thereof or mixture
thereof is
present in the composition at a level of at least 0.001 % by weight of the
total
composition, preferably from 0.006% to 10%, more preferably from 0.01 % to 8%
and most preferably of from 0.03% to 3%.
s
It has now been found that combining said antimicrobial essential oil or an
active thereof or a mixture thereof with a peroxygen bleach, in a composition,
delivers not only excellent immediate disinfecting properties to the surfaces
treated with said composition, but also Long lasting disinfecting properties.
~o Indeed, it is speculated that peroxygen bleach and said essential
oils/actives
adsorb on a surface having been treated with said composition and thus reduce
or even prevent the contamination of microorganisms over time, typically up to
48 hours after the surface has been treated with said composition, thereby
delivering long lasting disinfection. In other words, it is speculated that a
~5 microfilm of said active ingredients is deposited on the surface treated
with said
compositions allowing protection against microorganisms recontamination
overtime. Advantageously, this long lasting disinfection benefits is obtained
with
the compositions of the present invention comprising peroxygen bleach and
antimicrobial essential oils/actives even when used under highly diluted
2o conditions, i.e., up to dilution levels of from 1:100 (composition:water).
Excellent long lasting disinfection is obtained by treating a surface with a
composition comprising a peroxygen bleach and an antimicrobial essential oil
or
active thereof as described herein, on a variety of microorganisms, e.g., the
2s growth of Gram positive bacteria like Staphylococcus aureus, and Gram
negative
bacteria like Pseudomonas aeroginosa as well as of fungi like Candida albicans
is reduced or even prevented on a surface having been treated with said
composition.
3o Long lasting disinfection properties of the compositions herein may be
measured by the bactericidal activity of said compositions. A test method
suitable to evaluate the long lasting bactericidal activity of a composition
may be
28
CA 02549554 2001-06-19
as follow: First, the surfaces (e.g. glass) to be tested are respectively
treated
with either a composition according to the present invention or a reference
composition, e.g., a negative control composed of pure water (for example by
spraying the composition directly on the surface or first spraying the
composition on a sponge used to clean the surface or when the composition
herein is executed in the form of wipe by wiping the surtace therewith). After
a
variable time frame (e.g. 24 hours) each surface is respectively inoculated
with
bacteria (106-7cfu/slide) cultured in for example TSB (Tryptone Soya Broth)
and
left typically from a few seconds to 2 hours before evaluating the remaining
living bacteria. Then living bacteria (if any) are recovered from the surface
(by
touching TSA + neutraliser plates and by re-suspending the bacteria into the
neutralisation broth and plating them on agar) and incubated at appropriate
temperature, e:g. 37°C to let them grow typically over night. Finally,
a visual
grading of the living bacteria is made by comparing side by side the cultures
~ s and/or dilutions thereof (e.g. 10'2 or 10-1 ) resulting from the surfaces
treated
with the compositions according to the present invention and the reference
composition.
In a particular embodiment of the present invention, depending on the end use
2o desired with said compositions they may further comprise, as optional
ingredients, other antimicrobial compounds that further contribute to the
antimicrobial/antibacterial activity of the compositions according to the
present
invention. Such antimicrobial ingredients include parabens like ethyl paraben,
propyl paraben, methyl paraben, glutaraldehyde or mixtures thereof.
Chelatina Agent
The compositions herein may further comprise a chelating agent as a preferred
optional ingredient. Suitable chelating agents may be any of those known to
those skilled in the art such as the ones selected from the group comprising
3o phosphonate chelating agents, aminophosphonate chelating agents,
substituted
heteroaromatic chelating agents, amino carboxylate chelating agents, other
carboxylate chelating agents, polyfunctionally-substituted aromatic chelating
29
CA 02549554 2001-06-19
agents, biodegradable chelating agents like ethylene diamine N,N'- disuccinic
acid, or mixtures thereof.
Suitable phosphonate chelating agents to be used herein include etidronic acid
(1-hydroxyethylene-diphosphonic acid (HEDP)), and/or alkali metal ethane 1-
hydroxydiphosphonates.
Suitable amino phosphonate chelating agents to be used herein include amino
alkylene poly (alkylene phosphonates), nitrilotris(methylene)triphosphonates,
ethylene diamine tetra methylene phosphonates, and/or diethylene triamine
penta methylene phosphonates. Preferred aminophosphonate chelating agents
to be used herein are diethylene triamine penta methylene phosphonates.
These phosphonate/amino phosphonate chelating agents may be present either
in their acid form or as salts of different cations on some or al( of their
acid
functionalities. Such phosphonate/amino phosphonate chelating agents are
commercially available from Monsanto under the trade name DEQUEST~.
Substituted heteroaromatic chelating agents to be used herein include
2o hydroxypiridine-N-oxide or a derivative thereof.
Suitable hydroxy pyridine N-oxides and derivatives thereof to be used
according
to the present invention are according to the following formula:
i~
~OH
Y
wherein X is nitrogen, Y is one of the following groups oxygen, -CHO, -OH, -
(CH2)n-GOOH, wherein n is an integer of from 0 to 20, preferably of from 0 to
10 and more preferably is 0, and wherein Y is preferably oxygen. Accordingly
particularly preferred hydroxy pyridine N-oxides and derivatives thereof to be
CA 02549554 2001-06-19
used herein is 2-hydroxy pyridine N-oxide. Hydroxy pyridine N-oxides and
derivatives thereof may be commercially available from Sigma.
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.
A preferred biodegradable chelating agent for use herein is ethylene diamine
1o 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 acid is, for instance, commercially available under the tradename
ssEDDS~ from Palmer Research Laboratories. Ethylene diamine N,N'- disuccihic
acid is particularly suitable to be used in the compositions of the present
invention.
Suitable amino carboxylate chelating agents useful herein include ethylene
diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine
2o pentoacetate (DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotri-
acetates, ethylenediamine tetraproprionates, 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
to be used herein are diethylene triamine penta acetic acid (DTPA), 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).
3o Further carboxylate chelating agents to be used herein includes malonic
acid,
salicylic acid, glycine, aspartic acid, glutamic acid, or mixtures thereof.
31
CA 02549554 2001-06-19
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 3% by weight and more preferably from 0.01 % to
1.5%.
Radical Scavenger
The compositions herein may comprise a radical scavenger as another optional
ingredient. Suitable radical scavengers for use herein include the well-known
substituted mono and di hydroxy benzenes and derivatives thereof, alkyl- and
aryl carboxylates and mixtures thereof. Preferred radical scavengers for use
herein include di-tart-bufiyl hydroxy toluene (BHT), p-hydroxy-toluene,
hydroquinone (HQ), di-tart-butyl hydroquinone (DTBHQ), mono-tart-butyl
hydroquinone (MTBHQ), tart-butyl-hydroxy anysole (BHA), p-hydroxy-anysol,
benzoic acid, 2,5-dihydroxy benzoic acid, 2,5-dihydroxyterephtalic acid,
toluic
i5 acid, catechol, t-butyl catechol, 4-allyl-catechol, 4-acetyl catechol, 2-
methoxy-
phenol, 2-ethoxy-phenol, 2-methoxy-4-(2-propenyl)phenol, 3,4-dihydroxy
benzaldehyde, 2,3-dihydroxy benzaldehyde, benzylamine, 1,1,3-tris(2-methyl-4-
hydroxy-5-t-butylphenyl) butane, tart-butyl-hydroxy-anyline, p-hydroxy anyline
as
well as n-propyl-gallate. Highly preferred for use herein are di-tart-butyl
hydroxy
2o toluene, which is for example commercially available from SHELL under the
trade
name IONOL CP~ and/or tent-butyl-hydroxy anysole. These radical scavengers
further contribute to the stability of the peroxygen bleach-containing
compositions
herein.
25 Typically, the compositions according to the present invention comprise up
to 5%
by weight of the total composition of a radical scavenger, or mixtures
thereof,
preferably from 0.002% to 1.5% by weight and more preferably from 0.002% to
1 %.
30 Solvent
The compositions herein may comprise as a preferred optional ingredient a
solvent or mixtures thereof. When used, solvents will, advantageously, give an
32
CA 02549554 2001-06-19
enhanced cleaning to the compositions herein. Suitable solvents for
incorporation in, the compositions according to the present invention include
propylene glycol derivatives such as n-butoxypropanol or n-
butoxypropoxypropanol, water-soluble CARBITOL~ solvents or water-soluble
CELLOSOLVE~ solvents. Water-soluble CARBITOL~ solvents are compounds
of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived
from
ethyl, propyl or butyl. A preferred water-soluble carbitol is 2-(2-
butoxyethoxy)ethanol also known as butyl carbitol. Water-soluble
CELLOS4LVE~ solvents are compounds of the 2-alkoxyethoxyethanol class,
1o with 2-butoxyethoxyethanol being preferred. Other suitable solvents are
benzyl
alcohol, methanol, ethanol, isopropyl alcohol and diols such as 2-ethyl-1,3-
hexanediol and 2,2,4-trimethyl-1,3-pentanediol, volatile silicones and mixture
thereof. Preferred solvents for use herein are n-butoxypropoxypropanol, butyl
carbitol~, benzyl alcohol, isopropanol, 1-propanol and mixtures thereof. Most
95 preferred solvents for use herein are butyl carbitol~, benzyl alcohol, 1-
propariol
and/or isopropanol.
The solvents may typically be present within the compositions according to the
invention at a level up to 15% by weight, preferably from 0.5% to 7% by weight
of the composition.
pH buffer
In the embodiment of the present invention wherein the compositions are
formulated in the alkaline pH range, typically from 7.5 to 12, the
compositions
according to the present invention may further comprise a pH buffer or a
mixture thereof, i.e. a system composed of a compound or a combination of
compounds, whose pH changes only slightly when a strong acid or base is
added.
3o Suitable pH buffers for use herein include borate pH buffer, phosphonate,
silicate and mixtures thereof. Suitable borate pH buffers for use herein
include
33
CA 02549554 2001-06-19
alkali metal salts of borates and alkyl borates and mixtures thereof. Suitable
borate pH buffers to be used herein are alkali metal salts of borate,
metaborate,
tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride and/or
alkyl
borate containing from 1 to 12 carbon atoms, and preferably from 1 to 4.
Suitable alkyl borate includes methyl borate, ethyl borate and propyl borate.
Particularly preferred herein are the alkali metal salts of metaborate (e.g.
sodium metaborate), tetraborate (e.g., sodium tetraborate decahydrate) or
mixtures thereof.
Boron salts like sodium metaborate and sodium tetraborate are commercially
available from Borax and Societa Chimica Larderello under the trade name
sodium metaborate~ and Borax~.
The pH of the composition can also be adjusted to an acidic pH and/or buffered
i5 at that pH using any suitable acidifying agent, for example organic acids
for
example citric acid, tartaric acid, lactic acid and mixtures thereof.
Typically, the compositions according to the present invention may comprise up
to 15% by weight of the total composition of a pH buffer, or mixtures thereof,
2o preferably from 0.01 % to 10%, more preferably from 0.01 % to 5% and most
preferably from 0.1 % to 3%.
Packaging form of the wet wipes
In a preferred embodiment according to the presenfi invention, the wet wipes
2s are packaged in the container in any convenient configuration which allows
_ easy removal of a single or multiple wet wipe from the container. Preferably
the
wipes are packaged in rolls, stacks or piles. More preferably the wipes are
provided in a stacked configuration which may comprise any number of wipes.
Typically, the stack comprises from 2 to 150, more preferably from 5 to 100,
3o most preferably from 10 to 60 wipes. Moreover the wipes may be provided
folded or unfolded. Most preferably, the wipes are stacked in a folded
configuration.
34
CA 02549554 2001-06-19
Process of treating a surface
In a preferred embodiment, the present invention encompasses a process of
cleaning and/or disinfecting a surface, preferably a hard surface, comprising
the
step of contacting, preferably wiping, said surface with a substrate which
incorporates a composition as described herein.
In a preferred embodiment of the present application, said process comprises
the steps of contacting parts of said surface, more preferably soiled parts of
said surface, with said substrate which incorporates a composition as
described
~ o herein.
In another preferred embodiment said process, after contacting said surface
with said substrate which incorporates a composition as described herein,
further comprises the step of imparting mechanics! action to said surface
using
~s said substrate which incorporates a composition as described herein. By
"mechanical action" it is meant herein, agitation of the wet wipe on the
surface,
as for example rubbing the surface using the wet wipe.
By "surface", it is meant herein any surface including animate surface like
2o human skin, mouth, teeth, and inanimate surfaces. 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
25 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 surtaces also include household appliances including, but
not limited to, refrigerators, freezers, washing machines, automatic dryers,
ovens, microwave ovens, dishwashers and so on.
35
CA 02549554 2001-06-19
Experimental Data
The tensile strength and biodegradability of the substrate of the present
invention was compared against substrates found in the prior art using the
test
s methods described above.
Substrate Loading Wet Anaerobic
tensile disintegration
(dry
factor strength substrate)
(N/inch) % weight
loss
MD CD Week Week 2 Week 4
1
100% 3.0 32 10 100 100 100
hydroentangled
viscose'
Walkisoft 2 4.0 7.0 6.3 60.3 85.1 87.1
~
Dover 3 3.25 10 5 43.2 61 68.3
Tesco 4 approx. 12.5 6.5 na na approx.
80%
3.5
Kao 5 approx 1 5 100% 100% 100%
1.5
1 Substrate according to the present invention
2 Air-laid latex bond substrate from Walkisoft (UPM-Kymmene Group). This
substrate comprises 85% celluiosic frbres and 15% Styrene-butadiene resin as
a binder
3 Air-laid latex bond substrate made by Procter & Gamble. This substrate
comprises 70% cellulose natural fibres, 15% synthetic fibres and 15% Styrene-
butadiene resin as a binder
36
CA 02549554 2001-06-19
4 Wet Wipe sold under the Tesco Toilet Wipes by Tesco ltd. The Tesco
substrate is resin bonded and comprises 40% hydroentangled viscose, 33%
woodpulp and 22% polyethylene tetraphthalate (PET)
5 Wet Wipe sold under the Quickie bathroom wipes by Kao. The Kao
substrate comprises 100% wood pulp, obtained by a wet-laid consolidation
process.
~ Examples
Provided below are, non-limiting, examples A to D of cleaning compositions
which may be incorporated into the wipes of the present invention.
In redient A B C ~~a D
w/w % w/w % w/w % w/w
Ethanol 9.4 9.4 9.5 9.5
C12-14 Amine Oxide 0.4 0.4 - -
Pro lene GI col But I Ether 0.55 0.55 - -
Dieth lena GI col But I Ether 0.55 0.55 - -
Pol ro lene I col mono but I ether0.25 0.25 - -
Silicone ~ 0.003 0.003 0.003 0.003
Citric acid 0.75 0.75 - -
Sodium h droxide 0.1 - - -
H dro en Peroxide - 1.00 - -
Salic lic acid - 0.03 - -
BHT - 0.01 - -
Geraniol - 0.0375 0.1 0.1
Th mol ~ - 0.025 -
C12-14 Betaine - - 0.2 -
Dobanol91-8 - - 0.8 0.8
C8 alk I sul hate branched - - 0.6 0.6
C10 Amine Oxide - - - 0.2
Lactic acid - - 1.5 1.5
Perfume 0.18 0.0375 0.15 0.15
Water 87.82 86.95 87.15 87.15
37
