Technical field
[0001] The present invention relates to cleaning and bleaching compositions which are based
on hydrogen peroxide.
Background
[0002] Bleaching and cleaning compositions have been extensively described in the art. It
is also well known that it is desirable to use hydrogen peroxide rather than other
bleaches such as chlorine type bleaches. Indeed, hydrogen peroxide is much milder
and therefore safer, both for the item being bleached and for the user. However, hydrogen
peroxide based bleaches have the main inconvenient that they perform poorly at low
temperature. In response to this object, compositions have been designed which further
comprise a bleach activator. The bleach activator reacts with hydrogen peroxide to
yield a peracid which is the bleaching species.
[0003] Activated bleaching compositions however have the drawback that the activator and
the hydrogen peroxide tend to react in the composition. Thus, such activated bleaching
compositions tend to be chemically unstable upon storage. It is an object of the present
invention to provide activated bleaching compositions which are chemically stable.
[0004] Another problem is that bleach activators which are hydrophobic are problematic to
use in aqueous compositions as the product tends to separate into two different layer
phases which can be visualized by the consumer. Therefore, physical stability upon
storage is a further issue.
[0005] The present invention meets the above objects in proposing an aqueous cleaning and
bleaching composition comprising hydrogen peroxide and a liquid hydrophobic bleach
activator, wherein said bleach activator is emulsified in the composition by means
of a specific nonionic surfactant mixture.
[0006] EP 497 337 describes suspensions of solid water-insoluble peroxyacids in aqueous
compositions comprising a mixture of two nonionic surfactants. Compared to the compositions
in the '337 patent application, the compositions according to the present invention
allow for a faster dissolution of said liquid hydrophobic bleach activator in the
wash solution.
[0007] The present invention allows for great flexibility in formulating and provides compositions
which are chemically and physically stable. As an additional benefit, the nonionic
surfactant mixture used to emulsify the hydrophobic activator provides efficient cleaning.
[0008] As an additional advantage, it has been found that the nonionic surfactant system
used to emulsify said hydrophobic liquid ingredient improves the storage stability
of hydrogen peroxide.
[0009] Although the present invention finds a preferred application in formulating activated
bleaching compositions, the present invetion is also applicable to the formulation
of bleaching compositions which comprise any hydrophobic liquid ingredient which needs
to be kept separate from the hydrogen peroxide.
Summary of the invention
[0010] The present invention is an aqueous cleaning and bleaching composition having a pH
of from 0.5 to 6, comprising hydrogen peroxide or a source thereof and a hydrophobic
liquid ingredient, preferably a bleach activator, wherein said hydrophobic liquid
ingredient is emulsified in said composition by a mixture comprising at least one
nonionic surfactant with an HLB that is higher than or equal to the HLB of said hydrophobic
liquid ingredient and at least one nonionic surfactant with an HLB that is lower than
or equal to the HLB of said hydrophobic liquid ingredient, provided that the HLBs
of said nonionic surfactants , provided that the HLBs of said nonionic surfactants
are not identical.
[0011] The present invention also encompasses a process for the manufacture of said composition.
Detailed description of the invention
[0012] The compositions according to the present invention are aqueous. Accordingly, the
compositions according to the present invention comprise from 10% to 95% by weight
of the total composition of water, preferably from 30% to 90%, most preferably from
60% to 80%. Deionized water is preferably used.
[0013] The compositions according to the present invention are based on hydrogen peroxide.
Accordingly, the compositions according to the present invention comprise hydrogen
peroxide or a water-soluble source thereof. Suitable water-soluble sources of hydrogen
peroxide include perborate, percarbonate, persilicate and persulphate salts. In a
preferred embodiment, the compositions according to the present invention comprise
hydrogen peroxide. Typically, the compositions according to the present invention
comprise from 0.5% to 20% by weight of the total composition of hydrogen peroxide,
preferably from 2% to 15%, most preferably from 3% to 10%.
[0014] The compositions of the present invention have a pH as is of from 0.5 to 6. Formulating
the compositions according to the present invention in this acidic pH range contributes
to the stability of the composition. In a preferred embodiment, the compositions are
formulated in a pH range of from 1 to 5. The pH of the composition can be trimmed
by all means available to the man skilled in the art.
[0015] The compositions according to the present invention further comprise a hydrophobic
liquid ingredient. As used herein, the term "hydrophobic liquid ingredient" refers
both to liquid ingredients, and solid materials which are dissolved in a hydrophobic
liquid phase prior to incorporation into the compositions of the invention. By hydrophobic,
it is meant herein any material which is not substantially and stably miscible in
water. Hydrophobic materials herein typically have an HLB below 11. In a preferred
embodiment, said hydrophobic liquid ingredient is a bleach activator. By bleach activator,
it is meant herein any compound which reacts with hydrogen peroxide to form a peracid.
In the case of bleach activators, such hydrophobic bleach activators typically belong
to the class of esters, amides, imides, or anhydrides. A particular family of bleach
activators of interest in the present invention were disclosed in applicant's co-pending
European patent application No 91870207.7. Particularly preferred in that family is
acetyl triethyl citrate which was also disclosed in the context of bar soaps in FR
2 362 210. Acetyl triethyl citrate has the advantages that it is environmentally friendly
as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl
citrate has a good hydrolytical stability in the product upon storage and it is an
efficient bleach activator. Finally, it provides good building capacity to the composition.
As used herein and unless otherwise specified, the term bleach activator includes
mixtures of bleach activators. Apart from bleach activators, hydrophobic liquid ingredients
of interest herein include hydrophobic peroxyacids, enzymes, brighteners, perfumes
and the like.
[0016] As used herein, the term hydrophobic liquid ingredient refers to single ingredients
or mixtures thereof.
[0017] In the compositions according to the present invention, said hydrophobic liquid ingredient
is emulsified in the composition by means of a mixture of nonionic surfactants. Said
mixture of nonionic surfactants comprises at least two nonionic surfactants.
[0018] The first of said nonionic surfactant must have an HLB which is lower than or equal
to the HLB of said hydrophobic liquid ingredient, whereas the second nonionic surfactant
must have an HLB which is higher than or equal to the HLB of said hydrophobic liquid
ingredient, provided the HLBs of said nonionic surfactants are not identical. In a
preferred embodiment of the present invention the difference between the HLB values
of the two nonionic surfactants herein must be of at least 3. Upon using this nonionic
surfactant system, the hydrophobic liquid ingredient is stably emulsified in the composition.
The emulsion is physically stable and the hydrophobic liquid ingredient is kept separate
from the hydrogen peroxide, thus the composition is also chemically stable. Suitable
nonionic surfactants for use herein include alkoxylated fatty alcohols. Indeed, a
great variety of such alkoxylated fatty alcohols are commercially available which
have very different HLB values. The HLB values of such alkoxylated nonionic surfactants
depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation
and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high
degree of ethoxylation and a short chain fatty alcohol, while hydrophobic surfactants
tend to have a low degree of ethoxylation and a long chain fatty alcohol. Surfactants
catalogs are available which list a number of surfactants including nonionics, together
with their respective HLB values.
[0019] The exact nonionic surfactant system to be chosen depends on the hydrophobic liquid
ingredient to be emulsified. Accordingly, a suitable way to proceed is to determine
the HLB value of the hydrophobic liquid ingredient, then select two nonionic surfactants
which have HLB values below and above said HLB value of said hydrophobic liquid ingredient,
wherein the difference in the HLB values of said nonionic surfactants is preferably
at least 3.
[0020] In a preferred embodiment, the amount by weight of said nonionic surfactant with
an HLB lower than or equal to the HLB of said hydrophobic liquid ingredient should
be at least equal to or higher than the weight amount of said liquid hydrophobic ingredient.
[0021] Also, the amount of said nonionic surfactant with an HLB higher than or equal to
the HLB of said liquid hydrophobic ingrdient should be chosen so that the weighted
average of the HLB values of said nonionic surfactants is equal to the HLB of said
hydrophobic liquid ingredient.
[0022] In other words, the emulsifying system meets the equation:

and

where X refers to the hydrophobic liquid ingredient to emulsify, A refers to one of
said nonionic surfactants, and B refers to the other said nonionic surfactant.
[0023] In a particularly preferred embodiment of the invention, the hydrophobic liquid ingredient
is a bleach activator and said bleach activator is acetyl triethyl citrate. Acetyl
triethyl citrate has an HLB of about 10. An adequate nonionic surfactant system would
therefore comprise a first nonionic surfactant with an HLB from 1 to 10, and a second
nonionic surfactant with an HLB of above 11. A particularly suitable system comprises
a first nonionic surfactant with an HLB of about 6, for instance a Dobanol ® 23-2
and a second nonionic surfactant with an HLB of about 15, for instance a Dobanol ®
91-10. Another suitable nonionic surfactant system comprises a Dobanol ® 23-6.5 (HLB
about 12) and a Dobanol ® 23 (HLB below 6). All these Dobanol ® surfactants are commercially
available from Shell.
[0024] The compositions according to the present invention may further comprise other nonionic
surfactants which should however not significantly alter the weighted average HLB
value of the overall composition.
[0025] Preferably, the compositions according to the present invention are free of other
surfactant types, especially anionic surfactants.
[0026] The compositions according to the present invention may further comprise the usual
optional ingredients such as perfumes, dyes, optical brighteners, builders and chelants,
pigments, enzymes, soil release agents, dye transfer inhibitors, solvents, buffering
agents and the like.
[0027] The present invention further encompasses a process for the manufacture of the composition
described herein. The process according to the present invention comprises at least
three steps:
In the first step, a hydrophobic mixture is prepared which comprises at least said
hydrophobic liquid ingredient and said nonionic surfactant with a low HLB. This hydrophobic
mixture preferably further comprises other hydrophobic ingredients which are to be
formulated in the composition, such as perfumes, solvents, enzymes and polymers.
[0028] In the second step, a hydrophilic mixture is prepared which comprises at least said
water, said hydrogen peroxide and said nonionic surfactant with a high HLB. Said hydrophilic
mixture preferably further comprises other hydrophilic ingredients which are to be
formulated in the composition such as dyes, optical brighteners, builders, chelants
and buffering agents. In this second step hydrogen peroxide is preferably added last,
after said buffering agent has been added.
[0029] Naturally, said first and said second steps can be performed in any order, i.e second
step first is also suitable.
[0030] In the third step of the process according to the present invention, said hydrophobic
mixture and said hydrophilic mixture are mixed together.
[0031] The present invention is further illustrated by the following examples.
Examples
[0032] Compositions are made which comprise the listed ingredients in the listed proportions
(weight %).
| |
I |
II |
III |
IV |
V |
| Dobanol ® 45-7 |
- |
- |
- |
- |
6.0 |
| Dobanol ® 91-10 |
6.6 |
6.6 |
- |
- |
- |
| Dobanol ® 23-2 |
8.4 |
8.4 |
8.0 |
5.2 |
4.0 |
| Dobanol ® 23-6.5 |
- |
- |
4.0 |
9.8 |
5.0 |
| Acetyl triethyl citrate |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
| Hydrogen peroxide |
7.5 |
7.5 |
7.5 |
7.5 |
7.5 |
| Citric acid |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
| S,S-ethylene diamino disuccinic acid |
0.1 |
- |
- |
- |
- |
| Brightener 49 ® |
0.1 |
0.1 |
- |
- |
- |
| Deionized water |
---------------balance------------ |
[0033] Compositions I to IV are each made by preparing two mixtures. A hydrophilic mixture
is prepared which comprises the water, citric acid, brightener, S,S-EDDS and the Dobanol
® 91-10 or Dobanol ® 23-6.5. Hydrogen peroxide is added in said hydrophilic mixture
as last step, after the buffering agent is added. A second, hydrophobic, mixture is
prepared which comprises the acetyl triethyl citrate and the Dobanol ® 23-2.
[0034] Then said hydrophobic mixture is poured into said hydrophilic mixture, while mixing.
[0035] Compositions I to IV were obtained which were stable emulsions, both from a chemical
and a physical standpoint.
1. An aqueous cleaning and bleaching composition having a pH of from 0.5 to 6, comprising
hydrogen peroxide or a source thereof and a hydrophobic liquid ingredient, characterized in that said liquid ingredient is emulsified in said composition by a mixture comprising
at least one nonionic surfactant with an HLB that is higher than or equal to the HLB
of said hydrophobic liquid ingredient and at least one nonionic surfactant with an
HLB that is lower than or equal to the HLB of said bleach activator, provided that
the HLBs of said nonionic surfactants are not identical.
2. A composition according to claim 1 wherein said hydrophobic liquid ingredient is a
bleach activator.
3. A composition according to claim 2 wherein said bleach activator is acetyl triethyl
citrate.
4. A composition according to claim 1 which has a pH of from 1 to 5.
5. A composition according to any of the preceding claims which comprises from 0.5% to
20% by weight of the total composition of hydrogen peroxide.
6. A composition according to claim 3 wherein said nonionic surfactant with a high HLB
has an HLB above 11.
7. A composition according to claim 3 wherein said nonionic surfactant with a low HLB
has an HLB of from 1 to 10.
8. A composition according to any of the preceding claims wherein said emulsifying system
meets the equation:

and

where X refers to the hydrophobic liquid ingredient to emulsify, A refers to one of
said nonionic surfactants, and B refers to the other said nonionic surfactant.
9. A process for the manufacture of a composition according to any of the preceding claims
wherein:
- a hydrophobic mixture is prepared which comprises at least said hydrophobic liquid
ingredient and said nonionic surfactant with a low HLB;
- a hydrophilic mixture is prepared which comprises at least said water, said hydrogen
peroxide or source thereof and said nonionic surfactant with a high HLB;
- said hydrophobic mixture and said hydrophilic mixture are mixed together.
10. A process according to claim 9 wherein said hydrogen peroxide or source thereof is
added last in the preparation of said hydrophilic mixture