Note: Descriptions are shown in the official language in which they were submitted.
21 76224
Vo 9sll6023 r~ 92~
-- 1 --
TWO PART rr r~NTr~G CONPOSI~ION
COMPRISING ~ ~EAST ONE ~I~KO~lll~ C~ /U
FIELD OF THE INVENTION
The present invention relates to cleanin~ compositions
which comprise at least two components which are stored
separately and mixed shortly before use, at least one of
said components comprising a peroxide compound. By
peroxide compound is meant a compound comprising a peroxy
(HOO-) group, including hydrogen peroxide and both organic
and inorganic peroxides.
BACKGROUND TO THE INVENTION
The present invention provides compositions which are
particularly well adapted for use in cleaning and
st-or;l;~ing household surfaces and the removal of
discolouration caused by mould growth. Such
discolouration is a known problem, particularly under
humid conditions.
Compositions which remove, kill or bleach mould on
surfaces have previously comprised strong solutions of
alkali metal hypochlorite to be sprayed onto the surface.
One problem with said compositions is that the
30 hypochlorite has an unpleasant odour and, when sprayed,
hypochlorite solutions can produce droplets which cause
significant respiratory irritation.
Other bleaching agents are known, particularly peroxides.
However, peroxides are often either unstable in
_, ......... ... .. ..... .. .. .. . . . . .... . . . .
Wo 95JI6023 2 1 7 6 2 2 4 PCT/EP94/0392~ --
-- 2
formulations or exhibit poor bleaching performance at
their most stable pH.
Toothpastes and peroxide-based hair bleaching compositions
have been formulated as weakly acidic peroxide solutions
or ~els and separate weakly AlkA1;ne solutions or pastes
which are mixed just before use. The known advantage of
this form of product being that the peroxide is more
stable to decomposition under acidic conditions and yet is
more effective as a bleaching agent under ~lkAl ine
conditions .
Other two-part peroxide basea compositions are disclosed
in JP-A-60/038497 (LION BRANDS), which relates to a
foaming, two-part drain cleaning composition which
comprises:
a) 0.5-5096wt hydrogen peroxide,
b) alkali, having an alkalinity 0.1-50~ based on sodium
hydroxide,
c) surface active agent in (a) or (b), and,
d) terpene alcohol/cyclic terpene alcohol in ~a) or (b).
The compositions (a) and (b), including the surfactants
and terpene are setauentially or simultaneously dosed into
a toilet bowl and pass into the drains where the
composition produces a body of foam which acts to clean or
if necessary unblock the drain.
Other forms of simultaneous ~elivery of two components are
known .
21 76224
VO 95/16023 r~ Q~92
-- 3 --
US 3760986 (CASTNER et al: 1973), discloses a dispensing
bottle for dispensing two separate fluids to a common
point. Such a bottle is formed with an opening at the top
and a divider extending through the interior of the bottle
to define two compartments which provide dual reservoirs
for fluids. The apparatus disclosed further comprises
pump means to simultaneously withdraw fluid from each
compartment, via separate draw tubes, and discharge the
fluid to a common point. This device enables an alkaline
and an acid material to be stored separately and sprayed
from a single unit to a common point. The pumps used in
this apparatus are of a type wherein an inlet valve of a
working chamber comprises a ball held against a valve seat
by a spring such that as a piston compresses the working
fluid the ball is forced against the seat and the working
f luid cannot return down the draw tubes into the
reservoirs .
The device disclosed in CASTNER is an integral package and
dispenser. Although it can be envisaged that the device
could be disassembled and refilled, such an activity could
prove hazardous due to the nature of the liguids involved.
CASTNER proposes that the device be provided with closable
ports for ref; 11 in~, although such an activity is
envisaged to be dangerous where oxidising or corrosive
liguids are concerned.
Some attention has been given to the provision of
replaceable and/or refillable bottles in the general type
of dual reservoir packaging mentioned above: e.g. EP
427609 (S.T.E.P.: 1991) and in WO/90/01959 (CORUS MEDICAL
CORP: 1990) disclose spray means for attachment to a pair
of bottles . In the f irst of these separate pumps are
provided in each of the bottles. In the latter, the pumps
are provided within the spraying heads and the bottles are
... . . . . . . . . . . . . . . . ... .... . . .. .. . . ..
wo 95116023 2 1 7 6 2 2 4 PCTIEPg4/03924
-- 4 -- =
connected to the spraying head by being impaled on needles
which act as draw tubes.
US 4826048 (Pfeiffer: 1989) discloses a dispenser for
pharmaceutical or cosmetic li~[uids which comprises a pair
of bottles each provided with a separate pump. In this
case, the bottles may be removed for rPf;ll;ns or
replacement. US 5152461 (Proctor: 1992) discl~ses a
dispenser with a single pump and a pair of bottles which
can be detached ~or refilling or replacement.
~RIEF DESCRIPTION OF THE INVENTION
We have now determined that improved cleaning performance,
especially as regards the removal of moulds, can be
achieved by the use of two separate licluid compositions, a
first of which contains an acid or neutral composition
which comprises a peroxide and a second of which C~ntA;nc
an AlkAlin~ composition, said first and second
compositions being stored separately and sprayed from a
single unit to a common point.
sy ensuring that these compositions are sprayed, either
se~ nt;Ally or simultaneously onto a surface, whereby
they react together to produce an AlkAl;n~ peroxide
composition, it is possible to UVUL~ - the problems of
instability on storage and ensure that the mixed
compositions are delivered at a pH at which the peroxide
3 0 compound is active as a bleaching agent .
DETAILED DESCRIPTION OF THE INVENTION
As described above, the invention provides a kit of parts
comprising:
21 76224
;vo 95/16023 PCT/EPg4/03924
-- 5 --
a) a liquid, acidic or neutral composition comprising a
peroxide compound stable at the pH of the acidic or
neutral composition, and,
b) a liquid, illk;~l ;nf~ composition,
said compositions being contained in separate reservoirs
of a single unit adapted to produce a spray of at least
one of ~a) and (b).
sy 'spray' the present specification means a spray of
discrete droplets or a jet of foam, the operative
consideration being that one or preferably both of the
compositions are ejected from the unit with sufficient
force that can be deposited upon a surface which is
displaced horizontally from the unit.
It is preferred that the unit is adapted to produce a
spray comprising a mixture of compositions ~a) and (b).
In the alternative a unit can be adapted to produce
separate sprays of compositions (a) and (b) such as by
means of sequential spraying through a single spray means
or simultaneous spraying through separate spray means.
The production of a single spray which comprises a mixture
of (a) and (b) is preferred.
A second aspect of the present invention provides a method
of cleaning hard surfaces which comprises the steps of:
a) mixing a first, liquid, acidic or neutral composition
comprising a peroxide compound with a second, liquid,
alkaline composition so as to form an ~lk~l;ne
peroxide composition,
b) spraying the product of step (a) onto a surface to be
cleaned .
_ _ _ _ _ _ = _ _ _ _ _ _ ~ . . .. . ... . . .. ...
Wo 95116023 2 ~ 7 6 2 2 4 r~"~l . ,/"~924
-- 6 --
It is particularly preferred that the cleaning operation
comprises the step of contacting the product of step (a)
with the surface to be cleaned for a period in excess of 5
minutes.
Peroxides
The preferred peroxide compound is hydrogen peroxide
although it is envisaged that other peroxides could be
employed, provided that they are stable in the
compositions of the invention.
As mentioned above, hydrogen peroxide shows better
bleaching performance at an AlkAl ;n~ pH, particularly
above pH 10. However, hydrogen peroxide shows reduced
stability at this pH as compared with its stability at
acid or neutral pH.
In the alternative, it is envisaged that other peroxide
compounds can be employed. Among the preferred
alternatives are peracids, particularly peracetic acid and
persulphates particularly potassium mono-persulphate.
While suspensions of solid peroxides can be employed it is
preferred that solutions of a soluble peroxide are
employed .
Such solutions are preferably a~ueous although other
solvents can be employed when the pr~ctice is chemically
reactive with, or in the presence of water. Thus, in the
presence of peracetic acid the diacetyl ester of ethylene
glycol is a suitable solvent.
Preferred levels of peroxide compound range from 1-5096wt
of the composition containing the peroxide compound. For
hydrogen peroxide, levels below 496wt peroxide are less
C3~4 2 ~ 76224
i
-- 7
effective as bleaching agents, whereas solutions
containing more than 50%wt peroxide can be hazardous. For
peracetic and persulphates levels of 1-10%wt in the neat
compositions are preferred.
S - _
~ixin~ Ratio
As will be understood from the above an important aspect
of the present invention is that two components are mixed
either before or during the spraying operation. It is
preferred that the mixing ratio falls into the range 2 :1-
1:2, with ratios around 50:50 being particularly
preferred. It will be appreciated that the optimal mixing
ratio will be to scme degree dependent on the nature and
quantities of the components present, the o~erative
consideration being that the mixed composition should have
an alkaline pH overall.
~H ~r~x1; fvin~ a~ents
In order to attain the correct pH in the compositions
which embocy the present invention it can be necessary to
add pH modifying agents.
In the case of acid solutions containing peroxides,
further acidification may not be necessary. .2,s is
illustratêd by the examples given hereafter, aq.ueous
solutions according to the present invention can attain a
natural acid pH. It is particularly preferred that the pH
of the acid or neutral peroxide composition falls into the
range of above 2 to less than 8, with preferred pH~ s being
around 5. ~'hile solutions of pH below 2 can be used it is
preferable to avoid such acid compositions due to hazards
of spillage or contact with the skin of a user.
~EII~ED SHE~
Wo 95/16023 2 1 7 6 2 2 4 . ~ 1)3924
-- 8
In the case of alkaline compositions a pH above 10 is
preferred. The most preferred pH range is 11-13. The
alkaline reserve of the ~lki91 ;nf~ composition should be
such that the pH remains high, preferably at pH 8 or above
and more preferably above pH 10, after the addition of the
acidic or neutral peroxide compound ~ n~l;n;ng
composition. However, the alkaline composition should
preferably not have a pH so high as to be hazardous to
use .
Where further acidification is re~uired mineral or organic
acids, with optional buffer salts, can be employed
provided that these acids and salts are not peroxide
sensitive. We have determined that di-sodium hydrogen
citrate and/or trisodium citrate can be used to achieve
the required acid pH. The presence of the trisodium
citrate or other buffer salt being advantageous in that it
prevent a downward drift in the pH of the acidic peroxide
compound containing composition over prolonged storage.
Alk;~l ;ne pH can be attained by the use of alkali earth or
metal or ammonium hydroxides, particularly potassium and
sodium hydroxides. Carbonates and/or bicarbonates can be
present in the alkaline composition, as can borates,
silicates, phosphates, and/or other buffers. Preferably
the alkaline composition comprises 0 . 5-1. 5 molar
commercial caustic soda in aqueous solution.
In the method aspects of the present invention the
alkaline and the acidic or neutral compositions can be
mixed in any ratio between 1:10 and 10:1. The required
ratio being somewhat dependent on the pH of the two
compositions and the particular pH modifying agents
present. As mentioned above, compositions should
generally be formulated such that when mixed in a ratio of
~rom 2:1-1:2, preferably, 1:1 the resulting solution has
21 76224
~o 95/16023 PcrlEps~lo3924
_ g _
the desired pH, i . e . a pH at which the peroxide compound
present is effective as a bleaching agent. For hydrogen
peroxide the preferred pH after mixing with alkali is pH
10-12, more preferably ph 11-11.5. For monopersulphate
and peracetic acid the preferred pH after mixing is around
pH 8.
Thickeners
Thickener is an optional component of the present
invention, being essential only in certain aspects of the
invention. It is believed that thickeners can function in
two ways.
We have determined that the presence of small amounts of
thickener in at least one of said first and second
compositions modif=ies the spraying behaviour of the
composition to prevent the formation of an irritant mist.
An irritant mist comprises relatively large population of
fine droplets, whereas in the presence of a thickening
agent a relatively small population of fine droplets is
produced .
We have determined that certain ~ 7Ae derivatives,
particularly hydroxy alkyl cellulose derivatives incl~ding
hydroxy propyl methyl cellulose are particuIarly ef f ective
at thickening the acid peroxide composition to the extent
re~auired to achieve good spraying characteristics.
-30
Second, thickeners can be selected such that the
compositions thicken significantly when the ~ ts are
mixed. This has the significant advantage that the
composition does not run off sloping or vertical surfaces
~such as the walls of shower stalls) when applied.
WO 95/16023 2 1 7 6 2 2 4 r~l" . I' ~92-~ 0
-- 10 --
Either or both of these characteristics of thickeners may
be exploited in embodiments of the invention.
~ypical levels of thickener range from 0 . 05-5%wt .
Typically, the thickener component is a polymer.
Where it is required that the compositions thicken on
mixing, the most preferred thickeners are those which
exhibit a marked increase in composition viscosity at
above the pH of the acidic peroxide-c~nt~in;
composition .
Thus, in certain embodiments of the invention, the
thickener is originally present in an acidic, peroxide
compound .~nt~;n;n~ composition at a pH where a low
viscosity is exhibited, and, in use the solution is mixed
with a more ~lk~l in~ composition in a quantity such that
the pH of the resulting mixture is one at which the
thickener exhibits an increased viscosity.
Suitable polymers include those which only thicken
compositions subst~nt'~lly at ~lkA1;n~ pH. Such polymers
include polyacrylic acids (such as those^available in the
market as the 'Carbopol' (TM) series and acrylate
copolymers .
We have found that a 2%wt solution of Acusol 820 (RTM ex.
Rohm and Haas) an acrylate copolymer, forms a viscous gel
3 0 at pH 6, whereas very little thickening is exhibited at pH
3 . 0 . ~ower Levels of this polymer are employed when
slight thickening so as to modify spraying behaviour are
re~uired. We have determined that acceptable sprayiny
behaviour can be obtained when levels of this thickener of
35 0.05-0.5%wt are employed in the ~lk~l;n~ component.
~W0951160t3 2 1 7 6224 r~llrl~ 4
Alternative thickeners are those which exhibit poor
thickening at very high pH. In embodiments of the
invention where thickening on mixing is required, the
thickener can be present in the AlkAl;nl composition,
provided that the pH of this composition is sufficiently
high, and that when an acidic or neutral peroxide-
containing composition is added in sufficient quantity the
pH falls into a region where an increased viscosity is
exhibited .
Thickener components include clays, silicas, and mixed
surfactant systems. Where significant thickening on
mixing is required, the common factor between the
thickeners is that when the acidic or neutral peroxide
compound containing composition and the alkaline
composition are mixed in the presence of the thickener
components, the resulting mixture has a higher viscosity
than either of the compositions taken alone.
From the above it can be seen that it is not essential for
all embodiments of the invention that the thickener
components are all peroxide stable, but only required
that, where used, the or each thickener c~ t is
chemically stable in either the acidic or neutral peroxide
compound containing composition or the AlkAl ;no
composition .
Cationic Surfactant
It is preferred that at least one of said peroxide
containing or alkaline compositions further comprises a
cationic surf actant .
WO 95/16023 2 1 7 6 2 2 4 F~~ 924 0
-- 12 --
Preferred cationic surfactants include the quaternary
ammonium compounds of the formula:
Rl . R2 . R3 . R4 . NX
Wherein Rl-R4 are alkyl and X is an anion.
Preferably Rl and R2 are C8-C18 alkyl and R2 and R3 are
Cl-C4 alkyl. Preferably X is a halide.
Particularly pref erred cationics include dialkyl dimethyl
ammonium halides. We have determined that didecyl
dimethyl ammonium chloride i9 particularly suitable.
We have determined that the abc,v~ t; ~ne~l cationics are
stable both in the ~lkiql inl~ solution and the acid peroxide
solution and that no significant loss of peroxide occurs
when the cationic is present in the peroxide compound
containing composition, when the peroxide compound is
2 0 hydrogen peroxide . ~ :
Other Surfactants
Other surfactants, in addition to the cationic surfactant,
are generally present in the compositions of the present
invention so as to assist in the cleaning process in which
the compositions are used. The presence of further
surfactant is however optional.
Whether the surf~-t~nt~ are re~uired to be peroxide-stable
or not will be determine whether the surfactant is
incorporated in the acid/neutral or ~lk;llinF~ composition.
Preferred, peroxide-stable surfactants include anionic
surfactants such as primary or secondary alkane
~o 95/16023 2 1 7 6 2 2 4 r~.,t~ ~~0392~
-- 13 --
sulphonates, primary alkyl sulphates and/or alkyl aryl
sulphonates. Most preferable are nonionic surfactants,
particularly those which comprise alkoxylated alcohols.
Mixtures of two or more of these surfactants can be used.
Alkyl sulphate surfactants and/or ethoxylated alcohols are
particularly pref erred .
Where the surfactants are unstable in acidic, peroxide
containing compositions the surfactant can be provided as
a component of the alkaline component. We have determined
that ethoxylated alcohols are stable in either
acid/neutral hydrogen peroxide solutions or AlkAline
solutions .
~pical levels of surfactants range from 0.1-20%wt of the
component c~ntA;n;rg them. Levels of surfactant around 2-
1096wt on total liquid component are particularly
pref erred . -
Funqicides and Minors
Fungicides and/or other biocides, antimicrobials etc.
other than the peroxides can be present,^provided that
they are stable in either the acidic/neutral component or
the alkaline component.
Other minor components which are optional are perfumes,
solvents, which may be required to solvate certain
fungicides, and bleach stabilizers.
Bleach stabilisers will be required in the peroxide
compound is decomposed by transition metals present in the
composition. Accordingly it is preferable that the
composition further comprises a transition metal
complexing bleach stabiliser selected from phosphates,
_ _ _ _ _ _ _ _ = _ . . , .. . .. . .. . . ... . . _ . .
WO 9S/16023 21 7 6 2 2 4 r~ 924 0
-- 14 --
phosphonic acids or phosphonates, stannates, and
carboxylates .
Preferred metal ion complexing agents are selected from
dipicolinic acid, ethylene diamine tetra acetic acid
(EDTA) and its salts, hydroxy-ethylidene di~h~s~hnn; c acid
(De~uest 2010, RTM), ethylene diamine tetra (methylene
phosphonic acid) (Dequest 2040, RTM), diethylene triamine
penta(methylene phosphonic acid) (Dequest 2060, RTM). The
phosphonic acid derivatives are particularly preferred.
It is pref erred that the level of metal ion complexing
agent should fall into the range 0 . 01-5%wt, with levels
around 0.1%wt being particularly preferred.
While the reactions of peroxides with the transition
metals have previously been though detrimental, the
reaction can be used to advantage in the compositions of
the present invention. In an: ~ _a;m~nt of the invention
the ~lkAl ;ni~ component further comprises a transition
metal or halide bleach ~lecnmrnsing agent which reacts with
the acidic or neutral peroxide rr~ntA;n;ng composition.
According to an ~mho~l;rn~ant of the invention in which the
acidic or neutral component comprises monopersulphate as
the peroxy compound, the Al kAl; n~ component comprises a
halide, preferably a bromide. We have determined that
when acidic monopersulphate solution and alkaline bromide
solution are sprayed together onto a surface, so as to
give a final pH of around 8, a reaction occurs which
produces hypobromite, an effective bleaching agent at pH 6
and above.
As mentioned above, solvents can be included in the
compositions of the invention so as to solvate components
of the compositions. In addition, solvents can function
~voss/l6023 21 7 6224 r~ !A~924
-- 15 --
to improve the cleaning and or wetting properties of the
product as sprayed onto a surface to be cleaned.
Suitable solvents include the glycol ethers. A preferred
solvent is BUTYL DIGOL (TM), which we have determined to
be stable in the alkaline composition. Preferred solvent
levels range from 2-12%wt with 3-8%wt being particularly
pref erred .
A~1~aratus
The apparatus aspect of the present invention provides for
a two-part container which enables simultaneous or
se~uential spraying of compositions which comprise:
a~ a liquid, acidic or neutral, composition comprising a
peroxide compound stable at the pH of the
composition, and,
b) a liquid, alkaline composition.
Such containers are known from the art and are described
in US 3760986 (CASTNER et al: 1973), which discloses a
dispensing bottle for dispensing two separate fluids to a
common point.
It is particularly advantageous that the ~ ,,ntAl n~rs which
define the reservoirs for the compositions comprise a draw
tube, valve means to prevent li~[uid returning along said
draw tube and meaning to releasably engage said cr)ntA;n~r
with a pumping and spraying head.
The container described above is ~f particular utility
when used in combination with a dual-reservoir pumping and
spraying head of the type described with reference to the
Wo9~/16023 21 76224 ~"~ 1~92~J ~
-- 16 --
background of the invention. Whereas the prior art
envisages that the containers alone can be disassembled
f rom the spraying apparatus, or that the containers be
disassembled from the spraying apparatus together with an
associated pump, there is no disclosure of a container
with an inte~ral draw tube and non-return valve which can
be removed from the pumping and spraying apparatus.
In such an embodiment as is described above it is
essential that the valve means allows li~uid to be drawn
from the container when the container is engaged with the
pumping and spraying head. Suitable valve means include a
valve seat and a check element urged against the seat by
spring means. It is preferred to use a ball valve urged
against an annular seat by a helical spring.
In pref erred embodiments of the invention said valve means
further comprise means to prevent discharge of the
contents of the cnntAin~r prior to attA:' t of the spray
2 0 head . This f eature is particularly useful if the contents
of the container are chemically aggressive, i.e. if
corrosive or oxidising contents are employed.
Said means to prevent discharge can comprise a membrane
closing the egress from the container. The arrangement
being such that the membrane is pierced before or as the
container is engaged with the pumping and spraying head.
Particularly preferred containers have a second valve
means which acts to prevent discharge of the container
contents when the container is not engaged with the
pumping means. Such a construction has the advantage that
a partially empty contained can be disengaged from the
pumping and spraying head without risk that the contents
will be discharged. In one such embodiment a second check
element is held against a second valve seat by spring
~lo 9SI16023 2 1 7 6 2 2 ~ PCTIEP94/03924
means, unless displaced by a member projecting from the
pumping and spraying head.
The invention extends to the c~nt~in~rS described above
filled with an a~aueous solution of a peroxide compound
and/or alkali. All of these species are either corrosive
or otherwise harmful and gas-evolving reactions can occur
when they are mixed.
A f urther advantage of containers according to the
preferred embodiment of the present invention is that the
valve means prevents the container being ref illed by an
unskilled or ill-informed user. If the cr~nt~in~rs could
be refilled with ease, a user might be led to operate a
dual reservoir pumping and spraying device of the type
described above with solutions such as hypochlorite and
strong acid, which produce a potentially deadly cloud of
chlorine gas when these solutions are allowed to react.
In order that the present invention can be further
understood it will be described hereinafter by reference
to non-limiting examples and with reference to the
accompanying f igures wherein:
FIG 1 and la: show a container according to the present
invention, in isolation as in figure la or assembled
together with a similar container and a spraying and
pumping head.
FIG 2 and 2a show alternative embodiments of the invention
with particular detail of the valve means.
FIG 3 shows a detail of a preferred valve means in an
embodiment of the present invention.
wo 9~/16023 2 1 7 6 2 2 4 ~ 92~ --
-- 18 --
EXAMPLES
EXAMPLE 1: comPositions
Unglazed ceramic tiles (simulating glazed tile grout) were
treated with a fungal li~uid medium (Saboraud Liquid
Medium~ and inoculated with spores of Penicillium
chrysogenum ( a green mould common in bathrooms and
kitchens) by exposure of the tiles to spores released from
a culture of the fungus maintained on an agar plate
(Czapek Dox agar + 2% malt extract) . The tiles were
stored in damp conditions (relative humidity around 90%)
to encourage growth and the backs of the tiles were
sprayed with water to maintain conditions which favoured
growth of the mould. The tiles were used as such to
evaluate the effect of the composition of the invention on
fresh mould, whereas the effect of the composition on aged
mould was determined after autoclaving of the tiles.
Two separate solutions, 'Composition A' and 'Composition
B' were made up as follows, the components being added to
distilled water to reach the given final concentration.
Additions were in the order listed, with a f ive minute
stirring period between each addition.
Composition A:
0.15% Methocell J12MS (hydroxy propyl methyl
cellulose),
0 . 2 % DEQUE ST 2 0 6 0 ( TM ex . Monsant o ),
6 . 0% ~Iydrogen Peroxide,
1. 0% Disodium hydrogen citrate,
4 . 0% NE-208T (TM ex. Nippon Oil) primary alcohol
ethoxylate, nonionic surfactant,
0 . 2 % Perf ume
. 35
2 1 76224
~0 9~/16023 PCr/Eps~o392~
- 19 -
composition 'A' was adjusted to pH 5 . 0 with 20% sodium
hydroxide solution.
296 Methocell solution was ~L~ d by gradually adding the
polymer to distilled water and stirrin~ to disperse. The
dispersion was heated to approximately 60 Celcius and the
pH adjusted to 9 . 0 with NaOH. The solution was stirred
for around one hour while cooling to ambient to give a
clear viscous stock solution.
Composition B:
0.1% ACUSOL 810 ~TM ex. Rohm and Haas): acrylic
crosslinked copolymer,
1. 9% NaOH
4 . 0% NE-208T (TM ex. Nippon Oil) primary alcohol
ethoxylate, nonionic surfactant,
1. 0% Didecyl dimethyl ammonium chloride,
4 . 0% BUTYL DIGOL (TM),
These compositions were separately loaded into identical
trigger spray bottles and sprayed simultaneously from a
single unit onto the same region of a tile prepared as
described above while the tile was maintained with a near
vertical slope. A small amount of foam formed on the
surface of the tile and remained. It was determined that
aged (autoclaved~ mould was partially bleached over a
period of 20 min whereas substantial bleaching of fresh
mould occurred in the same period. After overnight
treatment ( around 14 hours ) nearly complete bleaching of
3 0 both f resh and aged mould was observed .
It was determined that optimum bleaching was achieved with
a 1:1 mixing ratio.
Wo 95/16023 2 1 7 6 2 2 4 PCT/EP9~/0392~ --
-- 20 -
Storage tests for up to 32 days showed that the was
comparatively little loss of peroxide and/or cationic in
the separately stored solutions.
EXAMPI,E II: aPlsaratus
Figures 1 and la shows container [1] with draw tube [2]
and valve means [3] in the upper surface [4].
In figure 1 the container [1] is assembled together with a
second container [11] and a spraying and pumping head
[10]. When the spraying and pumping head is operated,
liquid is drawn by pump means within the head from each of
the containers [1] and [11], mixed, and ejected in the
form of a spray via nozzle [12].
Figures 2 and 2a show detail of the valve means [3] in the
upper surface [4] with the pumping and spraying head [10]
removed. The valve means [3] comprise a cylindrical body
with openings at opposed ends. The body houses a spring
means such as helical spring [7 ] and a check element such
as ball [6]. Unless disturbed, the spring means [7]
urges the check element [6] against a valve seat [7a] to
prevent flow of liquid from within the cylindrical body
into the draw tube [2 ] . When assembled as in figure 1 the
pumping means within the pumping and spraying head [10]
are connected to the valve means [3]. ~atching means,
such as fittings [5] are provided to assist and maintain
engagement of the valve means [3] with the spraying and
pumping head [10].
In the embodiments shown in f igures 2 and 2a means are
provided to prevent egress of li~luid from within container
[1] before the container[1] is attached to the spraying
and pumping head.
21 76224
vo 9S/16023 PCT/EP9~/0392
-- 21 --
In figure 2a said means comprise a mem.brane [9] which
closes the upper opening of the cylindrical body until
pierced by an element within the spraying and pumping
head: in this ~m~o~ nt the seat of the spring [7] is
provided by stop [9a] upon which defines an aperture
closed by the membrane. A particular advantage of this
embodiment is that it is tamper-evident.
In figure 2 said means comprise a second ball valve which
comprises a valve seat [8a] against which ball [8] is
urged by spring 7 . In the em. bodiment shown in f igure 2 an
element within the spraying and pumping head pushes the
ball [8] off the seat [8a] when the valve means [3] are
engaged with the spraying and pumping head. A particular
advantage of this em.bodiment is that the second ball valve
closes when the ~nnt~in~r [1] is detached from the
spraying and pumping head [10].
Figure 3 shows further detail of the valve means [3] in
the upper surface [4] with the pumping and spraying head
[10] removed. As in figures 2 and 2a the valve means [3]
comprise a cylindrical body with openings at opposed ends.
The body again houses a spring means such as helical
spring [7] and a check element such as ball [6]. Latching
means, such as fittings [5] are provided to assist and
maintain engagement of the container with the spraying and
pumping head [10]. Figure 3 also shows a venting aperture
[13] and a porous plug [14] located between the body and
the outer shroud [15]. The venting aperture [13] allows
gas generated within the container [1] to escape. The
aperture [13] also allows air to flow into the container
so as to equalise the pressure within the container with
the ambient when the liquid contents of the c~nti~in~r are
removed by the spraying and pumping head via the draw tube
, 35 [2]-
Wo 95/16023 21 7 6 2 2 4 PCTIEP94~0392~ --
-- 22 --
n use, pumping means within the spraying and pumping head
[lO] generates a partial vacuum in the cylindrical body:
excess pressure within the c~ntAin~r [l] forces liquid up
the draw tube [2] and urges ball [6] off the seat [6a]
against the resistance of the spring [7]. Li~uid can then
flow from the c~nt~;n.or [l] to into the spraying and
pumping head. Within the spraying and pumping head [lO]
liquids f rom containers [ l ] and [ ll ] are mixed prior to
ejection through the nozzle [12]. When operation of the
spraying and pumping head ceases, flow of the mixed
li~uids back into container [l] is prevented by ball [6].
